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030-535-907-794-531
|
US
|
[
"WO"
] |
H04L29/06
| 2007-05-15T00:00:00 |
2007
|
[
"H04"
] |
technique for delivering caller-originated alert signals in ip-based communication sessions
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a technique for delivering caller-originated alert signals in ip-based communication sessions is disclosed. according to one embodiment, the technique may be realized as a method comprising the steps of: receiving, from a first user equipment (ue a), a request to initiate a communication session with a second user equipment (ue b), the request further including information associated with a caller-originated alert to be provided to the second user equipment (ue b); notifying the second user equipment (ue b) of the communication session and the incoming caller-originated alert, the notification being transmitted via a first communication channel; and causing a phonepage server (d) to transmit, via a second communication channel, the caller-originated alert to the second user equipment (ue b) for rendering thereon to alert a user associated with the second user equipment (ue b).
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claims what is claimed is: 1. a method for delivering caller-originated alert signals in an ip-based communication session, characterized in that the method comprises: receiving, from a first user equipment (ue a), a request to initiate a communication session with a second user equipment (ue b), the request further including information associated with a caller-originated alert to be provided to the second user equipment (ue b); notifying the second user equipment (ue b) of the communication session and the incoming caller-originated alert, the notification being transmitted via a first communication channel; and causing a phonepage server (d) to transmit (2510), via a second communication channel, the caller-originated alert to the second user equipment (ue b) for rendering (2512) thereon to alert a user associated with the second user equipment (ue b). 2. the method according to claim 1 , characterized in that at least a portion of the communication session is carried on a packet-switched network. 3. the method according to claim 1 , characterized in that the at least one portion of the information associated with the caller-originated alert includes an identity of the caller-originated alert. 4. the method according to claim 1 , characterized in that the method further comprises forwarding an identity of the second user equipment (ue b) and at least one portion of the information associated with the personalized alert signal to the phonepage server (d). 5. the method according to claim 4, characterized in that the at least one portion of the information associated with the caller-originated alert includes an identity of the first user equipment (ue a), and in that the phonepage server (d) selects the caller-originated alert based on a pre-stored preference associated with the first user equipment (ue a). 6. the method according to claim 1 , characterized in that the caller-originated alert is downloaded from the phonepage server (d) to the second user equipment (ue b) before being rendered (2512) thereon. 7. the method according to claim 1 , characterized in that the caller-originated alert is streamed from the phonepage server (d) to the second user equipment (ue b) and the rendering (2512) of the caller-originated alert starts before it is fully downloaded. 8. the method according to claim 1 , characterized in that the method further comprises receiving, from the phonepage server (d), a status to indicate whether the transmission of the caller-originated alert to the second user equipment (ue b) is successful. 9. the method according to claim 8, characterized in that the method further comprises instructing the second user equipment (ue b) to render a default ring-tone if the transmission of the caller-originated alert from the phonepage server (d) to the second user equipment (ue b) fails. 10. the method according to claim 1 , characterized in that the alert signal is customized based on one or more factors selected from a group consisting of: an identity of the second user, a type of the communication session, and predetermined triggering events associated with the communication session. 11. the method according to claim 1 , characterized in that the second user rejects the caller-originated alert. 12. the method according to claim 11 , characterized in that the phonepage server (d) overrides the rejection of the second user. 13. a system for delivering caller-originated alert signals in an ip-based communication session, the system comprising a communication server (c), a phonepage server (d), a first user equipment (ue a), and a second user equipment (ue b), characterized in that: the first user equipment (ue a) is configured to transmit (2504), to the communication server (c), a request to initiate a communication session with the second user equipment, the request further including information associated with a caller- originated alert to be provided to the second user equipment (ue b); the communication server (c) is configured to notify (2506) the second user equipment (ue b) of the communication session and the incoming caller-originated alert, the notification being transmitted via a first communication channel; the communication server (c) is further configured to contact (2508) the phonepage server (d) for the caller-originated alert; the phonepage server (d) is configured to transmit (2510), via a second communication channel, the caller-originated alert to the second user equipment (ue b); and the second user equipment (ue b) is configured to render (2512) the caller-originated alert to alert a user associated with the second user equipment (ue b). 14. a user equipment (2600) for delivering caller-originated alert signals in an ip-based communication session, the user equipment (2600) comprising a processor (2650) operatively coupled to at least one memory unit (2651 ), a user interface (2620, 2630, 2640, 2652), and a communication unit (2610), characterized in that the processor (2650) is configured to: transmit (2504), to a communication server (c), a request to initiate a communication session with a second user equipment; cause the communication server (c) to notify (2506) the second user equipment (ue b) of the communication session and an incoming caller-originated alert; and cause the caller-originated alert to be transmitted (2510), from a phonepage server (d), to the second user equipment (ue b) for rendering thereon to alert a user associated with the second user equipment (ue b). 15. a downloadable application or module for delivering caller-originated alert signals in an ip-based communication session, the downloadable application or module being stored on a computer-readable media, characterized in that the downloadable application or module is executable to perform: receiving, from a first user equipment (ue a), a request to initiate a communication session with a second user equipment, the request further including information associated with a caller-originated alert to be provided to the second user equipment (ue b); notifying (2506) the second user equipment (ue b) of the communication session and the incoming caller-originated alert, the notification being transmitted via a first communication channel; and causing a phonepage server (d) to transmit (2510), via a second communication channel, the caller-originated alert to the second user equipment (ue b) for rendering thereon to alert a user associated with the second user equipment (ue b).
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technique for delivering caller-originated alert signals in ip-based communication sessions related applications this patent application claims priority to u.s. provisional patent application no. 60/917,992, filed may 15, 2007, and u.s. patent application no. 1 1/761 ,591 , filed june 12, 2007, each of which is hereby incorporated by reference herein in its entirety. technical field the present invention relates generally to a method and apparatus for exchanging information in a communication system. more specifically, the invention relates to a technique for delivering caller-originated alert signals in ip-based communication sessions. background of the invention with the convergence of voice and data communication networks, portable communication devices are increasingly likely to support several communication modes, as well as a number of communication-related applications. single-purpose cellular phones and alphanumeric pagers have given way to complex mobile devices supporting voice communications, e-mail, and instant messaging. a typical device often includes a camera, a music player, and sound recorder, and may include a global positioning system (gps) receiver. many of these devices and their supporting wireless networks now enable simultaneous use of multiple communication modes. thus, a device user today might engage in a voice call and simultaneously send or receive text messages, digital images, video clips, or the like. a few applications have been developed to take advantage of this simultaneous availability of multiple communications modes. in particular, several patents and patent application publications describe a so-called phone pages system, in which the generation and transfer of multimedia data objects is triggered by various communication-related events. these data objects, or phone pages, thus supplement a primary communication session, such as a voice call, an e-mail exchange, or an instant message conversation. the phone pages concept is described in the following patents and patent application publications, the contents of which are each incorporated by reference herein: u.s. patent no. 6,922,721 , titled "exchange of information in a communication system" and issued on july 26, 2005 to minborg et al.; u.s. patent application publication 2005/0271041 a1 , titled "exchange of information in a communication system" and filed on june 1 , 2005 by minborg et al.; u.s. patent no. 6,996,072, titled "method and apparatus for exchange of information in a communication network" and issued on february 7, 2006 to minborg; u.s. patent no. 6,977,909, titled "system and method for exchange of information in a communication network" and issued on december 20, 2005 to minborg; and u.s. patent application publication 2006/0114845, also titled "system and method for exchange of information in a communication network" and filed on november 14, 2005 by minborg. the communication techniques and systems described in the preceding references provide a variety of enhancements to conventional modes of communication, facilitating the convenient exchange of various data objects between users of communications devices. these enhancements may be quite valuable both for promoting personal relationships and for supporting business and enterprise communications. however, if unrestrained, the increased flow of data objects may be overwhelming, both for system users and for the system itself. summary of the invention the present invention overcomes the above identified deficiencies of identifying and finding a data object and navigating between a set of data objects by applying a novel connection between a data-communications network and a telecommunications network. in one aspect of the present invention a technique for connecting a dialed b-party number to a data object is described. a data object can for example be graphical, text, sound, voice, animations, static or dynamic pictures, or any combination. the connecting of a b-party number to a specific data object, hereafter referred to as phonepage, will allow an a-party direct access to information that a b-party wishes to display to a calling party. the phonepage resides in a memory in a telecommunications network, or in a memory in a data-communications network connected thereto. the phonepage may have a similar appearance to an internet web page, but may also take other appearances. the displaying of the phonepage may be made dependent upon the capabilities of the a-party user equipment. dependent on the type of equipment used by the a-party, the node storing the phonepages may, upon detection of type of equipment, select the most advantageous way of displaying a selected data object. also, dependent on the a-party user equipment, the phonepage may provide different levels of interaction possibilities, i.e., only display information, or be a fully interactive data object with a duplex communication between the a-party and the node housing the memory in which the phonepage is stored. the phonepages may be configured to be displayed automatically or by indication from the a-party. in a variant of the invention also a b-party has the same capabilities of obtaining phonepages upon reception of an a-number in conjunction with an incoming call. in another aspect of the present invention, a node in a data-communication or telecommunication system is described. the node consists of at least a database memory including at least indications of the phonepages and upon access from a remote request, respond with said indication. the transfer of the indication to a calling a-party may be dependent on type of connection and access technology used in the connection. for example in a connection where both circuit switched and packet switched communication is simultaneously possible, the indication may be transferred on a packet switched communication resource and, e.g., voice communication may be initiated on the circuit switched communication resource. in other types of connections, two data flows may be set-up on one or several simultaneous packet switched communication resources, e.g., speech and data transfer. another example is when voice communication is initiated over a circuit switched communication resource and the phonepage indications are transferred over a packet switched channel with limited performance such as an sms channel. brief description of the drawings the invention will now be more thoroughly described and features and advantages will become readily apparent by reading the following detailed description, where references will be made to the accompanying figures, where: figure 1 illustrates an overview of a communication network according to one embodiment of the invention; figure 2 shows a block diagram illustrating an exemplary system for delivering caller- originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention; figure 3 shows a flow chart illustrating an exemplary method for delivering caller- originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention; and figure 4 shows a block diagram illustrating an exemplary user equipment for requesting and/or receiving caller-originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention. detailed description the present invention is described below in reference to a wireless telecommunications system providing voice and data services to a mobile device. various systems providing voice and data services have been deployed, such as gsm networks (providing circuit-switched communications) and gprs (providing packet-switched communications); still others are currently under development. these systems may employ any or several of a number of wireless access technologies, such as time division multiple access (tdma), code division multiple access (cdma), frequency division multiple access (fda), orthogonal frequency division multiple access (ofdma), time division duplex (tdd), and frequency division duplex (fdd). the present invention is not limited to any specific type of wireless communications network or access technology. indeed, those skilled in the art will appreciate that the network configurations discussed herein are only illustrative. the inventive techniques disclosed herein may be applied to "wired" devices accessing conventional voice or data networks, as well as wireless devices. the invention may be practiced with devices accessing voice and/or data networks via wireless local area networks (wlans) or via one or more of the emerging wide-area wireless data networks, such as those under development by the 3 rd - generation partnership project (3gpp). figure 1 illustrates an exemplary communications system in which the present invention may be employed. communications device 100 communicates with other devices through base station 1 10, which is connected to wireless network 120. wireless network 120 is in turn connected to the public switched telephone network (pstn) 125 and the internet 130. wireless device 100 can thus communicate with various other devices, such as wireless device 135, conventional land-line telephone 140, or personal computer 145. in figure 1 , wireless device 100 also has access to data server 150 via the internet 130; data server 150 may be configured to provide access through internet 130 to data or applications stored in storage device 160. storage device 160 may comprise one or more of a variety of data storage devices, such as disk drives connected to data server 150 or one or more other servers, a redundant array of inexpensive drives (raid) system, or the like. communications device 100 may be a cordless telephone, cellular telephone, personal digital assistant (pda), communicator, computer device, or the like, and may be compatible with any of a variety of communications standards, such as the global system for mobile communications (gsm) or one or more of the standards promulgated by 3gpp. communications device 100 may include a digital camera, for still and video images, as well as a digital sound recorder and digital music player application. communications device 100 may also support various applications in addition to voice communications, such as e-mail, text messaging, picture messaging, instant messaging, video conferencing, web browsing, and the like. communications device 100 also includes a wireless local-area network (wlan) transceiver configured for communication with wlan access point 170. wlan access point 170 is also connected to internet 130, providing communications device 100 with alternative connectivity to internet-based resources such as data server 150. also connected to wireless network 120 is location server 180. location server 180 is typically maintained by the operator of wireless network 120, but may be separately administered. the main function of location server 180 is to determine the geographic location of mobile terminals (such as mobile terminal 100) using the wireless network 120. location information obtained by location server 180 may range from information identifying the cell currently serving mobile terminal 100 to more precise location information obtained using global positioning system (gps) technology. other technologies, including triangulation methods exploiting signals transmitted from or received at several base stations, may also be used to obtain location information. triangulation techniques may include time difference of arrival (tdoa) technology, which utilizes measurements of a mobile's uplink signal at several base stations, or enhanced- observed time difference (e-otd) technology, which utilizes measurements taken at the mobile terminal 100 of signals sent from several base stations. gps-based technologies may include assisted-gps, which utilizes information about the current status of the gps satellites derived independently of the mobile terminal 100 to aid in the determination of the terminal's location. in some embodiments, the various systems and methods described herein facilitate the selective delivery of data objects to a communication device, such as mobile terminal 125, in communication with another device, such as mobile terminal 100. the data object may be transferred from one device to the other, e.g., from mobile terminal 100 to mobile terminal 125, or from a data object server, such as server 150 or server 180, in response to a request from either of the communication devices. typically, the users of the communication devices are engaged in a communication session, which may comprise a voice call (whether circuit-switched or packet-switched), an instant message (im) session, or any other modes of communication such as those described herein or combinations thereof. in some embodiments, one or both of the communication devices may include a module or application that is able to determine the occurrence of a communications-related trigger event in the communication device and to thereafter transmit and/or receive data, such as data specifically related to the trigger event. the trigger event may comprise, for example, any of the following events or combinations thereof: • the establishment of a session or call between the devices; • the arrival or departure of a device in a multi-party communication session; • activation by the user of one or both of the communication devices (e.g., an explicit request by one user for transfer of a data object to the other); • timer-based periodic or random trigger event in communication device; • crossing a geographic boundary, such as a boundary established by the user of one of the communication devices; or • other events related to the communication, such as those described in u.s. patent no. 6,996,072. other trigger events might include, but are not limited to: • an outgoing call is or is about to be initiated. • a called party answers a call. • a called party is busy. • a called party does not answer after a pre-determined time or number of rings. • a called party rejects a call. • a called party is unavailable (e.g., an addressed mobile phone is out of coverage). • an incoming call is imminent or has just started. • a conference call is or is about to be initiated. • a call is disconnected. • a call is conducted (under which several triggering events can be generated). • a party is placed on hold. • the location of a party has changed. • a communication device is switched on or off. • a special-function button is pressed on a communication device. • a button or other user interface device is activated in response to a query. • a voice mail, text message, e-mail, instant message, or the like is received. • a voice mail, text message, e-mail, instant message, or the like is received. while many of the preceding trigger events are related to traditional voice communications, those skilled in the art will appreciate that many analogous trigger events will apply to other communication modes, such as instant messaging, e-mail, video conferencing, "chat" sessions, and so on. according to one aspect of the present invention, while a first user equipment (ue) such as a mobile device or stationary device is attempting to establish a communication session (e.g., a voice call session or an instant messaging session) with a second ue, the first ue may cause a customized alert signal to be sent to the second ue, prior to the establishment of the communication session, to alert the user of the second ue of the upcoming communication session. specifically, upon selection of the second ue for communication, the first ue may transmit a call setup request to a communication server and also indicate to the communication server the intent to send a customized alert signal. this customized alert signal may be referred to generally as "a caller-originated alert" or "a caller-originated alert signal," wherein the word "caller" refers to a party who initiates a communication session but is not limited to voice calls. the communication server may initiate the call setup with the second ue and instruct it to wait for the caller-originated alert signal. the communication server may also contact a phonepage server to cause it to deliver the caller-originated alert signal to the second ue. the second ue may then render the caller-originated alert signal to alert its user of the communication session. referring to figure 2, there is shown a block diagram illustrating an exemplary system 2400 for delivering caller-originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention. the system 2400 may comprise a first user equipment (ue a), a second user equipment (ue b), a communication server c, and a phonepage server d. the ue a may be a mobile telephone or a mobile telephone connected to any kind of data equipment, e.g., personal digital assistant (pda) devices or laptop computer. the ue a may also be a fixed non-mobile device such as a desktop computer, a gaming device, an ip telephone, or other devices which can initiate and receive communications.. the ue a is capable of communicating with other user equipment such as ue b in a variety of ways. for example, ue a may establish a voice call, such as a voice-over-ip (voip) call, with ue b. ue a may also establish a wireless "walkie-talkie" session based on the push-to-talk (ptt) technology. ue a may alternatively establish a data or multimedia communication session (e.g., email, instant messaging, online meeting, document sharing, and file transfers) with ue b. ue b may typically have comparable or at least compatible functionalities in order to communicate with ue a. both ue a and ue b may be configured to communicate with the phonepage server d. the phonepage server d may comprise a phonepages number server (pns) and/or phonepage web server (pws). the phonepage server d may communicate with ue a and ue b via one or more logical channels, typically to receive requests (directly or indirectly) from ue a and to fulfill those requests according to an established messaging or signaling protocol. the communication server c may be any type of communication equipment that hosts or facilitates communication sessions among two or more user equipment. for example, the communication server c may be a proxy server or a similar network element. the communication session between ue a and ue b may be carried on a packet-switched network. for example, the communication session may be a voip call or an instant messaging (im) session that traverses an ip-based network (e.g., the internet). or, the communication session may be a voice call or data session that is partially carried on an ip-based network and partially carried on a telephone (land-line and/or wireless) network. according to one embodiment of the present invention, a first user who is associated with ue a, i.e., user a, may attempt to initiate a communication session with a second user who is associated with ue b, i.e., user b. prior to establishment of the communication session, user a may select user b either from a locally-stored or online phonebook or buddy list or by directly entering an identifier of user b or ue b. in conjunction with the selection, user a may create or select a caller-originated alert signal that will be used to alert user b of the upcoming communication session. for example, user a may record a personalized voice message or ring-tone or alert signal or, more typically, select a pre-recorded alert signal that is stored locally or online. then, ue a may transmit session initiation information to the communication server c to be relayed to ue b. the session initiation information may include the identity of user b or ue b. the session initiation information may also include or be accompanied by a request for a caller-originated alert to be provided to ue b. the request for the caller-originated alert may include an indication of user a's intent to alert user b of the communication session with a caller-originated alert. in addition, the request may also include the identity of or selection criteria for the caller-originated alert to be sent to ue b. alternatively, the request may include an address or identifier of the phonepage server d (or another data source) from which the call- originated alert is available. upon receiving the session initiation information and the request for the caller-originated alert, the communication server c may initiate the communication session with ue b. the communication server c may forward at least a portion of the session initiation information to ue b. the communication server c may further notify ue b of the incoming caller-originated alert and instruct ue b to wait for its arrival. prior to or while communicating with ue b, the communication server c may contact the phonepage server d to forward the identity of ue b and at least a portion of ue a's request for the caller-originated alert. for example, the communication server may forward the identity of the caller-originated alert to the phonepage server d such that it can locate the pre-stored alert signal. alternatively, the communication server may only forward the identities of user a and user b to the phonepage server d and instruct the phonepage server d to select a suitable, personalized alert signal based on user a's preference(s) and/or other factors. selection of a pre-recorded alert signal may be done automatically based on one or more factors such as the identity of user b, the proximity of user b to user a, the type/context of the attempted communication session, time of day, and other specific triggering events that may trigger a phonepage request as described above. in some instances, the phonepage server d may need to retrieve the requested alert signal from another source of data objects. once the caller-originated alert has been selected and/or retrieved, the phonepage server d may contact ue b to initiate transferring the caller-originated alert to ue b without waiting for any request from ue b. according to one embodiment of the present invention, the phonepage server d may transmit the caller-originated alert to ue b in one data package. once the data package has been fully downloaded to ue b, ue b may render the caller- originated alert to notify the user b that a communication session with user a is pending. alternatively, according to another embodiment of the present invention, the caller-originated alert may be streamed to ue b. that is, without waiting for the caller-originated alert to be fully downloaded, ue b may start rendering it to alert user b of the communication session. if user b has muted alert functions on ue b, for example, during a meeting or in a theater, ue b may reject the incoming caller-originated alert from the phonepage server d. alternatively, ue b may still proceed to receive the caller-originated alert signal and then apply user b's settings to determine how ue b renders the alert signal. both options may be accommodated by a protocol between ue b and the phonepage server d. the protocol may allow ue b to reject the caller-originated alert or allow the phonepage server d to override ue b's rejection in case user b does not have the right to reject a certain alert, either for commercial (e.g., condition of service) or regulatory reasons. upon a successful delivery of the caller-originated alert to ue b, the communication session between ue a and ue b may be fully set up after ue b renders the alert and user b accepts the session initiated by user a. if the phonepage server d fails to provide the caller- originated alert to ue b as requested, the phonepage server d may notify the communication server c of the failure status. the communication server c may then instruct ue b either to render a default alert signal to alert user b or to simply forego the step of rendering any alert signal. the communication between ue a and ue b, via the communication server c, may be carried on a first logical channel at least a portion of which traverses a packet-switched network (e.g., internet or a private intranet). the communication between the phonepage server d and ue b may be carried on a second logical channel. the communication between the communication server c and the phonepage server d may be carried over yet another network channel. figure 3 shows a flow chart illustrating an exemplary method for delivering caller- originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention. in step 2502, user a (ue a) may select user b (ue b) for communication. the attempted communication session may be any type of ip-based sessions such as voice, data, multimedia sessions, or a combination thereof. for illustration purposes, ue a and ue b will be described hereinafter as mobile telephone devices although they may be any type of user equipment as described above. to select user b for communication, user a may simply choose user b from a list of contacts or enter a mobile phone number associated with user b. in step 2504, ue a may send a call setup request to a communication server. the communication server may be typically a network element in an ip network that helps call signaling and routing between any two or more user equipment. depending on the type of communication as well as the specific network or application used, ue a may follow the relevant protocol to send, for example, session initiation messages to the communication server. the communication session is not limited to a one-to-one type of communication, but may be part of a multiple-party communication (e.g., a conference call or an online meeting). that is, either or both of ue a and ue b may simultaneously communicate with other parties. the call setup request sent to the communication server may also indicate user a's intent to delivery a caller-originated alert, such as a personalized alert signal, to ue b. for example, when dialing the call, user a may indicate whether the attempted communication session will be in a conventional alert mode (i.e., without any caller-originated alert) or a caller- originated alert mode (i.e., with a caller-originated alert). user a may depress one or more assigned keys to indicate a caller-originated alert mode. user a may also include in the call setup request one of the following items: the alert signal itself, an identity of the alert signal, an address or identifier of a phonepage server from which to download the alert signal, or an instruction to select an alert signal for user b optionally coupled with one or more selection criteria for picking a suitable alert signal. in step 2506, the communication server may initiate the call setup with ue b. if user b is not available (e.g., offline), the communication server may notify user a of this status. if user b is available, the communication server may notify ue b of the incoming call, for example, by forwarding at least a portion of the session initiation messages from ue a, either as received or with modification. in addition, the communication server may notify ue b of the incoming personalized alert signal and instruct ue b to wait for its arrival. at substantially the same time, in step 2508, the communication server may contact a phonepage server to cause the personalized alert signal to be provided to ue b. if the identity of the personalized alert signal has been received from ue a, the communication server may simply forward that identity to the phonepage server. otherwise, the communication server may send the identities of users a and b to the phonepage server and instruct the phonepage server to select a pre-stored alert signal according to user a's preferences and/or other factors. in step 2510, the phonepage server may transmit the personalized alert signal to ue b over a logical channel such as an internet connection. as mentioned above, the entire personalized alert signal may be delivered to ue b before ue b begins rendering it. alternatively, the personalized alert signal may be streamed to ue b in a series of data packets which ue b can start rendering without waiting for the entire alert signal to be downloaded. the delivery of the personalized alert signal may follow any ip-based, multimedia streaming or download protocol such as stream control transmission protocol (sctp). in step 2512, the personalized alert signal may be rendered on ue b. prior to establishment of the communication session with ue a, ue b may play back the personalized alert signal to alert user b of the pending communication session with user a. how ue b handles the session notification and the related alert signal(s) may have already been configured, and the pre-configured rules or preferences may be automatically executed without prompting user b for a selection. for example, ue b may establish default rules for handling incoming calls accompanied by personalized alert signals, and the default rules may either be globally applicable to all callers or vary according to specific callers. typically, a caller- originated alert may be treated by ue b like any other alert signal or alert signal. for example, the caller-originated alert may be muted when user b is in an environment where quietness is necessary. in step 2514, the communication server may proceed to establish the communication session between users a and b. the phonepage server may report back to the communication server whether the personalized alert signal has been successfully delivered to ue b as requested. if the alert signal delivery is successful, the communication server may cause the call to be set up between ue a and ue b as usual. if the alert signal delivery fails, the communication server might contact another phonepage server to forward a suitable alert signal to ue b. alternatively, the communication server may instruct ue b to either use a locally stored alert signal or proceed with the call setup without any alert signal. figure 4 shows a block diagram illustrating an exemplary user equipment 2600 for requesting and/or receiving caller-originated alert signals in an ip-based communication session in accordance with an embodiment of the present invention. the ue 2600 may comprise a central processing unit (cpu) 2650, at least one memory unit 2651 , at least one display 2620, at least one user input device 2652 which may be a keypad, keyboard, touchscreen, or the like, a radio unit 2610, an antenna 261 1 , at least one speaker 2630 for audio outputo, at least one microphone 2640 for audio input. the ue 2600 may further comprise a plurality of programs 2670, including, for example, a browser 2671 that can render at least one type of data object (e.g., voice-based alerts) and an encode/decode unit 2672 that encodes (or encrypts) requests for data objects and decodes (or decrypts) data objects. in addition, in order to implement the provision of customized voice- based alert signals, the ue 2600 may also comprise a caller-originated alert management application 2673 (alert_manage), an application for requesting caller-originated alerts 2674 (alert_req), and a caller-originated alert preference module 2675 (alert_pref). both the alert_manage application 2673 and the alert_req application 2674 may be embedded software programs that run automatically or in response to activation. the alert_req application 2674 may respond to an express or implied selection of a caller-originated alert signal and automatically generate a request to be sent to a communication server with a call setup request. selection methods may include the user press of an appropriate dedicated or non-dedicated ("soft") selection key, completion of the recording of an alert signal, or default instructions and options stored in the ue memory. the alert_req application 2674 may include in the request either the caller-originated alert itself or relevant information, such as an identity of the caller- originated alert signal and/or the identity of the called party, to enable a phonepage server to identify a pre-recorded caller-originated alert signal. the radio unit 2610 may then transmit the request to the communication server. the alert_manage application 2673 may be responsible for handling caller-originated alerts that are associated with incoming calls or communication sessions. generation of the requests for caller-originated alerts and/or the management of any received caller-originated alerts may be conditioned on or related to preference settings that are stored in and/or managed by the alert_pref module 2675. at this point it should be noted that the technique for delivering caller-originated alert signals in ip-based communication sessions in accordance with the present disclosure as described above typically involves the processing of input data and the generation of output data to some extent. this input data processing and output data generation may be implemented in hardware or software. for example, specific electronic components may be employed in a ue, a communications server, or similar or related circuitry for implementing the functions associated with delivering caller-originated alert signals in ip-based communication sessions in accordance with the present disclosure as described above. alternatively, one or more processors operating in accordance with stored instructions may implement the functions associated with delivering caller-originated alert signals in ip-based communication sessions in accordance with the present disclosure as described above. if such is the case, it is within the scope of the present disclosure that such instructions may be stored on one or more processor- readable program storages (e.g., a magnetic or optical disk or solid-state memory), or transmitted to one or more processors via one or more signals. the present disclosure is not to be limited in scope by the specific embodiments described herein. indeed, other various embodiments of and modifications to the present disclosure, in addition to those described herein, will be apparent to those of ordinary skill in the art from the foregoing description and accompanying drawings. thus, such other embodiments and modifications are intended to fall within the scope of the present disclosure. further, although the present disclosure has been described herein in the context of a particular implementation in a particular environment for a particular purpose, those of ordinary skill in the art will recognize that its usefulness is not limited thereto and that the present disclosure may be beneficially implemented in any number of environments for any number of purposes. accordingly, the claims set forth below should be construed in view of the full breadth and spirit of the present disclosure as described herein.
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032-457-933-943-299
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US
|
[
"US"
] |
H01F27/42,H02J17/00
| 2008-09-27T00:00:00 |
2008
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[
"H01",
"H02"
] |
wireless energy transfer using magnetic materials to shape field and reduce loss
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in embodiments of the present invention improved capabilities are described for a method and system comprising a source resonator optionally coupled to an energy source and a second resonator located a distance from the source resonator, where the source resonator and the second resonator are coupled to provide near-field wireless energy transfer among the source resonator and the second resonator and where the field of at least one of the source resonator and the second resonator is shaped using a magnetic material to avoid a loss-inducing object.
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1. a system, comprising: a source resonator optionally coupled to an energy source; and a second resonator located a distance from the source resonator, wherein the source resonator and the second resonator are coupled to provide near-field wireless energy transfer among the source resonator and the second resonator and wherein the field of at least one of the source resonator and the second resonator is shaped using a magnetic material. 2. the system of claim 1 , wherein at least one of the source resonator and the second resonator have a quality factor, q>100. 3. the system of claim 1 , wherein the source resonator q is greater than 100 and the second resonator q is greater than 100. 4. the system of claim 1 , wherein the square root of the resonator q times the second resonator q is greater than 100. 5. the system of claim 1 , comprising more than one resonator. 6. the system of claim 1 , comprising more than one second resonator. 7. the system of claim 1 , comprising more than three resonators. 8. the system of claim 1 , wherein the field is shaped to avoid a loss-inducing object. 9. the system of claim 8 , wherein the loss-inducing object is completely covered by the magnetic material. 10. the system of claim 8 , wherein the loss-inducing object is partially covered by the magnetic material. 11. the system of claim 8 , wherein the loss-inducing object is nearer to at least one of the source resonator and the second resonator, and wherein a portion of the loss-inducing object facing the nearer resonator is partially covered by the magnetic material. 12. the system of claim 8 , wherein the loss-inducing object is a mobile electronic device. 13. a method, comprising: providing a source resonator optionally coupled to an energy source and a second resonator located a distance from the source resonator, near-field wireless energy transfer among the source resonator and the second resonator and shaping the field of at least one of the source resonator and the second resonator using a magnetic material. 14. the method claim 13 , wherein at least one of the source resonator and the second resonator have a quality factor, q>100. 15. the method of claim 13 , wherein the source resonator q is greater than 100 and the second resonator q is greater than 100. 16. the method of claim 13 , wherein the square root of the source resonator q times the second resonator q is greater than 100. 17. the method of claim 13 , comprising more than one source resonator. 18. the method of claim 13 , comprising more than one second resonator. 19. the method of claim 13 , comprising more than three resonators. 20. the method of claim 13 , wherein the step of shaping is to avoid a loss-inducing object. 21. a system, comprising: a resonator coupled to power and control circuitry; wherein the resonator and the power and control circuitry are configured to provide near-field wireless energy transfer among other resonators, and wherein the power and control circuitry is at least partially covered by high permeability materials to shape magnetic fields of the resonator around the power and control circuitry.
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cross-reference to related applications this application is a continuation-in-part of the following u.s. patent application, u.s. ser. no. 12/567,716 filed sep. 25, 2009 which claims the benefit of the following u.s. provisional applications, u.s. app. no. 61/100,721 filed sep. 27, 2008; u.s. app. no. 61/108,743 filed oct. 27, 2008; u.s. app. no. 61/147,386 filed jan. 26, 2009; u.s. app. no. 61/152,086 filed feb. 12, 2009; u.s. app. no. 61/178,508 filed may 15, 2009; u.s. app. no. 61/182,768 filed jun. 1, 2009; u.s. app. no. 61/121,159 filed dec. 9, 2008; u.s. app. no. 61/142,977 filed jan. 7, 2009; u.s. app. no. 61/142,885 filed jan. 6, 2009; u.s. app. no. 61/142,796 filed jan. 6, 2009; u.s. app. no. 61/142,889 filed jan. 6, 2009; u.s. app. no. 61/142,880 filed jan. 6, 2009; u.s. app. no. 61/142,818 filed jan. 6, 2009; u.s. app. no. 61/142,887 filed jan. 6, 2009; u.s. app. no. 61/156,764 filed mar. 2, 2009; u.s. app. no. 61/143,058 filed jan. 7, 2009; u.s. app. no. 61/152,390 filed feb. 13, 2009; u.s. app. no. 61/163,695 filed mar. 26, 2009; u.s. app. no. 61/172,633 filed apr. 24, 2009; u.s. app. no. 61/169,240 filed apr. 14, 2009, u.s. app. no. 61/173,747 filed apr. 29, 2009. each of the foregoing applications is incorporated herein by reference in its entirety. background 1. field this disclosure relates to wireless energy transfer, also referred to as wireless power transmission. 2. description of the related art energy or power may be transferred wirelessly using a variety of known radiative, or far-field, and non-radiative, or near-field, techniques. for example, radiative wireless information transfer using low-directionality antennas, such as those used in radio and cellular communications systems and home computer networks, may be considered wireless energy transfer. however, this type of radiative transfer is very inefficient because only a tiny portion of the supplied or radiated power, namely, that portion in the direction of, and overlapping with, the receiver is picked up. the vast majority of the power is radiated away in all the other directions and lost in free space. such inefficient power transfer may be acceptable for data transmission, but is not practical for transferring useful amounts of electrical energy for the purpose of doing work, such as for powering or charging electrical devices. one way to improve the transfer efficiency of some radiative energy transfer schemes is to use directional antennas to confine and preferentially direct the radiated energy towards a receiver. however, these directed radiation schemes may require an uninterruptible line-of-sight and potentially complicated tracking and steering mechanisms in the case of mobile transmitters and/or receivers. in addition, such schemes may pose hazards to objects or people that cross or intersect the beam when modest to high amounts of power are being transmitted. a known non-radiative, or near-field, wireless energy transfer scheme, often referred to as either induction or traditional induction, does not (intentionally) radiate power, but uses an oscillating current passing through a primary coil, to generate an oscillating magnetic near-field that induces currents in a near-by receiving or secondary coil. traditional induction schemes have demonstrated the transmission of modest to large amounts of power, however only over very short distances, and with very small offset tolerances between the primary power supply unit and the secondary receiver unit. electric transformers and proximity chargers are examples of devices that utilize this known short range, near-field energy transfer scheme. therefore a need exists for a wireless power transfer scheme that is capable of transferring useful amounts of electrical power over mid-range distances or alignment offsets. such a wireless power transfer scheme should enable useful energy transfer over greater distances and alignment offsets than those realized with traditional induction schemes, but without the limitations and risks inherent in radiative transmission schemes. summary there is disclosed herein a non-radiative or near-field wireless energy transfer scheme that is capable of transmitting useful amounts of power over mid-range distances and alignment offsets. this inventive technique uses coupled electromagnetic resonators with long-lived oscillatory resonant modes to transfer power from a power supply to a power drain. the technique is general and may be applied to a wide range of resonators, even where the specific examples disclosed herein relate to electromagnetic resonators. if the resonators are designed such that the energy stored by the electric field is primarily confined within the structure and that the energy stored by the magnetic field is primarily in the region surrounding the resonator. then, the energy exchange is mediated primarily by the resonant magnetic near-field. these types of resonators may be referred to as magnetic resonators. if the resonators are designed such that the energy stored by the magnetic field is primarily confined within the structure and that the energy stored by the electric field is primarily in the region surrounding the resonator. then, the energy exchange is mediated primarily by the resonant electric near-field. these types of resonators may be referred to as electric resonators. either type of resonator may also be referred to as an electromagnetic resonator. both types of resonators are disclosed herein. the omni-directional but stationary (non-lossy) nature of the near-fields of the resonators we disclose enables efficient wireless energy transfer over mid-range distances, over a wide range of directions and resonator orientations, suitable for charging, powering, or simultaneously powering and charging a variety of electronic devices. as a result, a system may have a wide variety of possible applications where a first resonator, connected to a power source, is in one location, and a second resonator, potentially connected to electrical/electronic devices, batteries, powering or charging circuits, and the like, is at a second location, and where the distance from the first resonator to the second resonator is on the order of centimeters to meters. for example, a first resonator connected to the wired electricity grid could be placed on the ceiling of a room, while other resonators connected to devices, such as robots, vehicles, computers, communication devices, medical devices, and the like, move about within the room, and where these devices are constantly or intermittently receiving power wirelessly from the source resonator. from this one example, one can imagine many applications where the systems and methods disclosed herein could provide wireless power across mid-range distances, including consumer electronics, industrial applications, infrastructure power and lighting, transportation vehicles, electronic games, military applications, and the like. energy exchange between two electromagnetic resonators can be optimized when the resonators are tuned to substantially the same frequency and when the losses in the system are minimal. wireless energy transfer systems may be designed so that the “coupling-time” between resonators is much shorter than the resonators' “loss-times”. therefore, the systems and methods described herein may utilize high quality factor (high-q) resonators with low intrinsic-loss rates. in addition, the systems and methods described herein may use sub-wavelength resonators with near-fields that extend significantly longer than the characteristic sizes of the resonators, so that the near-fields of the resonators that exchange energy overlap at mid-range distances. this is a regime of operation that has not been practiced before and that differs significantly from traditional induction designs. it is important to appreciate the difference between the high-q magnetic resonator scheme disclosed here and the known close-range or proximity inductive schemes, namely, that those known schemes do not conventionally utilize high-q resonators. using coupled-mode theory (cmt), (see, for example, waves and fields in optoelectronics , h. a. haus, prentice hall, 1984), one may show that a high-q resonator-coupling mechanism can enable orders of magnitude more efficient power delivery between resonators spaced by mid-range distances than is enabled by traditional inductive schemes. coupled high-q resonators have demonstrated efficient energy transfer over mid-range distances and improved efficiencies and offset tolerances in short range energy transfer applications. the systems and methods described herein may provide for near-field wireless energy transfer via strongly coupled high-q resonators, a technique with the potential to transfer power levels from picowatts to kilowatts, safely, and over distances much larger than have been achieved using traditional induction techniques. efficient energy transfer may be realized for a variety of general systems of strongly coupled resonators, such as systems of strongly coupled acoustic resonators, nuclear resonators, mechanical resonators, and the like, as originally described by researchers at m.i.t. in their publications, “efficient wireless non-radiative mid-range energy transfer”, annals of physics , vol. 323, issue 1, p. 34 (2008) and “wireless power transfer via strongly coupled magnetic resonances”, science , vol. 317, no. 5834, p. 83, (2007). disclosed herein are electromagnetic resonators and systems of coupled electromagnetic resonators, also referred to more specifically as coupled magnetic resonators and coupled electric resonators, with operating frequencies below 10 ghz. this disclosure describes wireless energy transfer technologies, also referred to as wireless power transmission technologies. throughout this disclosure, we may use the terms wireless energy transfer, wireless power transfer, wireless power transmission, and the like, interchangeably. we may refer to supplying energy or power from a source, an ac or dc source, a battery, a source resonator, a power supply, a generator, a solar panel, and thermal collector, and the like, to a device, a remote device, to multiple remote devices, to a device resonator or resonators, and the like. we may describe intermediate resonators that extend the range of the wireless energy transfer system by allowing energy to hop, transfer through, be temporarily stored, be partially dissipated, or for the transfer to be mediated in any way, from a source resonator to any combination of other device and intermediate resonators, so that energy transfer networks, or strings, or extended paths may be realized. device resonators may receive energy from a source resonator, convert a portion of that energy to electric power for powering or charging a device, and simultaneously pass a portion of the received energy onto other device or mobile device resonators. energy may be transferred from a source resonator to multiple device resonators, significantly extending the distance over which energy may be wirelessly transferred. the wireless power transmission systems may be implemented using a variety of system architectures and resonator designs. the systems may include a single source or multiple sources transmitting power to a single device or multiple devices. the resonators may be designed to be source or device resonators, or they may be designed to be repeaters. in some cases, a resonator may be a device and source resonator simultaneously, or it may be switched from operating as a source to operating as a device or a repeater. one skilled in the art will understand that a variety of system architectures may be supported by the wide range of resonator designs and functionalities described in this application. in the wireless energy transfer systems we describe, remote devices may be powered directly, using the wirelessly supplied power or energy, or the devices may be coupled to an energy storage unit such as a battery, a super-capacitor, an ultra-capacitor, or the like (or other kind of power drain), where the energy storage unit may be charged or re-charged wirelessly, and/or where the wireless power transfer mechanism is simply supplementary to the main power source of the device. the devices may be powered by hybrid battery/energy storage devices such as batteries with integrated storage capacitors and the like. furthermore, novel battery and energy storage devices may be designed to take advantage of the operational improvements enabled by wireless power transmission systems. other power management scenarios include using wirelessly supplied power to recharge batteries or charge energy storage units while the devices they power are turned off, in an idle state, in a sleep mode, and the like. batteries or energy storage units may be charged or recharged at high (fast) or low (slow) rates. batteries or energy storage units may be trickle charged or float charged. multiple devices may be charged or powered simultaneously in parallel or power delivery to multiple devices may be serialized such that one or more devices receive power for a period of time after which other power delivery is switched to other devices. multiple devices may share power from one or more sources with one or more other devices either simultaneously, or in a time multiplexed manner, or in a frequency multiplexed manner, or in a spatially multiplexed manner, or in an orientation multiplexed manner, or in any combination of time and frequency and spatial and orientation multiplexing. multiple devices may share power with each other, with at least one device being reconfigured continuously, intermittently, periodically, occasionally, or temporarily, to operate as wireless power sources. it would be understood by one of ordinary skill in the art that there are a variety of ways to power and/or charge devices, and the variety of ways could be applied to the technologies and applications described herein. wireless energy transfer has a variety of possible applications including for example, placing a source (e.g. one connected to the wired electricity grid) on the ceiling, under the floor, or in the walls of a room, while devices such as robots, vehicles, computers, pdas or similar are placed or move freely within the room. other applications may include powering or recharging electric-engine vehicles, such as buses and/or hybrid cars and medical devices, such as wearable or implantable devices. additional example applications include the ability to power or recharge autonomous electronics (e.g. laptops, cell-phones, portable music players, household robots, gps navigation systems, displays, etc), sensors, industrial and manufacturing equipment, medical devices and monitors, home appliances and tools (e.g. lights, fans, drills, saws, heaters, displays, televisions, counter-top appliances, etc.), military devices, heated or illuminated clothing, communications and navigation equipment, including equipment built into vehicles, clothing and protective-wear such as helmets, body armor and vests, and the like, and the ability to transmit power to physically isolated devices such as to implanted medical devices, to hidden, buried, implanted or embedded sensors or tags, to and/or from roof-top solar panels to indoor distribution panels, and the like. in one aspect, disclosed herein is a system including a source resonator having a q-factor q 1 and a characteristic size x1 , coupled to a power generator with direct electrical connections; and a second resonator having a q-factor q 2 and a characteristic size x 2 , coupled to a load with direct electrical connections, and located a distance d from the source resonator, wherein the source resonator and the second resonator are coupled to exchange energy wirelessly among the source resonator and the second resonator in order to transmit power from the power generator to the load, and wherein √{square root over (q 1 q 2 )} is greater than 100. q 1 may be greater than 100 and q 2 may be less than 100. q 1 may be greater than 100 and q 2 may be greater than 100. a useful energy exchange may be maintained over an operating distance from 0 to d, where d is larger than the smaller of x 1 and x 2 . at least one of the source resonator and the second resonator may be a coil of at least one turn of a conducting material connected to a first network of capacitors. the first network of capacitors may include at least one tunable capacitor. the direct electrical connections of at least one of the source resonator to the ground terminal of the power generator and the second resonator to the ground terminal of the load may be made at a point on an axis of electrical symmetry of the first network of capacitors. the first network of capacitors may include at least one tunable butterfly-type capacitor, wherein the direct electrical connection to the ground terminal is made on a center terminal of the at least one tunable butterfly-type capacitor. the direct electrical connection of at least one of the source resonator to the power generator and the second resonator to the load may be made via a second network of capacitors, wherein the first network of capacitors and the second network of capacitors form an impedance matching network. the impedance matching network may be designed to match the coil to a characteristic impedance of the power generator or the load at a driving frequency of the power generator. at least one of the first network of capacitors and the second network of capacitors may include at least one tunable capacitor. the first network of capacitors and the second network of capacitors may be adjustable to change an impedance of the impedance matching network at a driving frequency of the power generator. the first network of capacitors and the second network of capacitors may be adjustable to match the coil to the characteristic impedance of the power generator or the load at a driving frequency of the power generator. at least one of the first network of capacitors and the second network of capacitors may include at least one fixed capacitor that reduces a voltage across the at least one tunable capacitor. the direct electrical connections of at least one of the source resonator to the power generator and the second resonator to the load may be configured to substantially preserve a resonant mode. at least one of the source resonator and the second resonator may be a tunable resonator. the source resonator may be physically separated from the power generator and the second resonator may be physically separated from the load. the second resonator may be coupled to a power conversion circuit to deliver dc power to the load. the second resonator may be coupled to a power conversion circuit to deliver ac power to the load. the second resonator may be coupled to a power conversion circuit to deliver both ac and dc power to the load. the second resonator may be coupled to a power conversion circuit to deliver power to a plurality of loads. in another aspect, a system disclosed herein includes a source resonator having a q-factor q 1 and a characteristic size x 1 , and a second resonator having a q-factor q 2 and a characteristic size x 2 , and located a distance d from the source resonator; wherein the source resonator and the second resonator are coupled to exchange energy wirelessly among the source resonator and the second resonator; and wherein √{square root over (q 1 q 2 )} is greater than 100, and wherein at least one of the resonators is enclosed in a low loss tangent material. in another aspect, a system disclosed herein includes a source resonator having a q-factor q 1 and a characteristic size x 1 , and a second resonator having a q-factor q 2 and a characteristic size x 2 , and located a distance d from the source resonator; wherein the source resonator and the second resonator are coupled to exchange energy wirelessly among the source resonator and the second resonator, and wherein √{square root over (q 1 q 2 )} is greater than 100; and wherein at least one of the resonators includes a coil of a plurality of turns of a conducting material connected to a network of capacitors, wherein the plurality of turns are in a common plane, and wherein a characteristic thickness of the at least one of the resonators is much less than a characteristic size of the at least one of the resonators. in embodiments, the present invention may provide for a method and system comprising a source resonator optionally coupled to an energy source and a second resonator located a distance from the source resonator, where the source resonator and the second resonator may be coupled to provide near-field wireless energy transfer among the source resonator and the second resonator and where the field of at least one of the source resonator and the second resonator may be shaped using a magnetic material to avoid a loss-inducing object. in embodiments, at least one of the source resonator and the second resonator may have a quality factor, q>100. the source resonator q may be greater than 100 and the second resonator q may be greater than 100. the square root of the source resonator q times the second resonator q may be greater than 100. in embodiments, there may be more than one source resonator, more than one second resonator, more than three resonators, and the like. throughout this disclosure we may refer to the certain circuit components such as capacitors, inductors, resistors, diodes, switches and the like as circuit components or elements. we may also refer to series and parallel combinations of these components as elements, networks, topologies, circuits, and the like. we may describe combinations of capacitors, diodes, varactors, transistors, and/or switches as adjustable impedance networks, tuning networks, matching networks, adjusting elements, and the like. we may also refer to “self-resonant” objects that have both capacitance, and inductance distributed (or partially distributed, as opposed to solely lumped) throughout the entire object. it would be understood by one of ordinary skill in the art that adjusting and controlling variable components within a circuit or network may adjust the performance of that circuit or network and that those adjustments may be described generally as tuning, adjusting, matching, correcting, and the like. other methods to tune or adjust the operating point of the wireless power transfer system may be used alone, or in addition to adjusting tunable components such as inductors and capacitors, or banks of inductors and capacitors. unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. in case of conflict with publications, patent applications, patents, and other references mentioned or incorporated herein by reference, the present specification, including definitions, will control. any of the features described above may be used, alone or in combination, without departing from the scope of this disclosure. other features, objects, and advantages of the systems and methods disclosed herein will be apparent from the following detailed description and figures. brief description of figures figs. 1 ( a ) and ( b ) depict exemplary wireless power systems containing a source resonator 1 and device resonator 2 separated by a distance d. fig. 2 shows an exemplary resonator labeled according to the labeling convention described in this disclosure. note that there are no extraneous objects or additional resonators shown in the vicinity of resonator 1 . fig. 3 shows an exemplary resonator in the presence of a “loading” object, labeled according to the labeling convention described in this disclosure. fig. 4 shows an exemplary resonator in the presence of a “perturbing” object, labeled according to the labeling convention described in this disclosure. fig. 5 shows a plot of efficiency, η, vs. strong coupling factor, u=κ/√{square root over (γ s γ d )}=k√{square root over (q s q d )}. fig. 6 ( a ) shows a circuit diagram of one example of a resonator (b) shows a diagram of one example of a capacitively-loaded inductor loop magnetic resonator, (c) shows a drawing of a self-resonant coil with distributed capacitance and inductance, (d) shows a simplified drawing of the electric and magnetic field lines associated with an exemplary magnetic resonator of the current disclosure, and (e) shows a diagram of one example of an electric resonator. fig. 7 shows a plot of the “quality factor”, q (solid line), as a function of frequency, of an exemplary resonator that may be used for wireless power transmission at mhz frequencies. the absorptive q (dashed line) increases with frequency, while the radiative q (dotted line) decreases with frequency, thus leading the overall q to peak at a particular frequency. fig. 8 shows a drawing of a resonator structure with its characteristic size, thickness and width indicated. figs. 9 ( a ) and ( b ) show drawings of exemplary inductive loop elements. figs. 10 ( a ) and ( b ) show two examples of trace structures formed on printed circuit boards and used to realize the inductive element in magnetic resonator structures. fig. 11 ( a ) shows a perspective view diagram of a planar magnetic resonator, (b) shows a perspective view diagram of a two planar magnetic resonator with various geometries, and c) shows is a perspective view diagram of a two planar magnetic resonators separated by a distance d. fig. 12 is a perspective view of an example of a planar magnetic resonator. fig. 13 is a perspective view of a planar magnetic resonator arrangement with a circular resonator coil. fig. 14 is a perspective view of an active area of a planar magnetic resonator. fig. 15 is a perspective view of an application of the wireless power transfer system with a source at the center of a table powering several devices placed around the source. fig. 16( a ) shows a 3d finite element model of a copper and magnetic material structure driven by a square loop of current around the choke point at its center. in this example, a structure may be composed of two boxes made of a conducting material such as copper, covered by a layer of magnetic material, and connected by a block of magnetic material. the inside of the two conducting boxes in this example would be shielded from ac electromagnetic fields generated outside the boxes and may house lossy objects that might lower the q of the resonator or sensitive components that might be adversely affected by the ac electromagnetic fields. also shown are the calculated magnetic field streamlines generated by this structure, indicating that the magnetic field lines tend to follow the lower reluctance path in the magnetic material. fig. 16( b ) shows interaction, as indicated by the calculated magnetic field streamlines, between two identical structures as shown in (a). because of symmetry, and to reduce computational complexity, only one half of the system is modeled (but the computation assumes the symmetrical arrangement of the other half). fig. 17 shows an equivalent circuit representation of a magnetic resonator including a conducting wire wrapped n times around a structure, possibly containing magnetically permeable material. the inductance is realized using conducting loops wrapped around a structure comprising a magnetic material and the resistors represent loss mechanisms in the system (r wire for resistive losses in the loop, r μ denoting the equivalent series resistance of the structure surrounded by the loop). losses may be minimized to realize high-q resonators. fig. 18 shows a finite element method (fem) simulation of two high conductivity surfaces above and below a disk composed of lossy dielectric material, in an external magnetic field of frequency 6.78 mhz. note that the magnetic field was uniform before the disk and conducting materials were introduced to the simulated environment. this simulation is performed in cylindrical coordinates. the image is azimuthally symmetric around the r=0 axis. the lossy dielectric disk has ∈ r =1 and σ=10 s/m. fig. 19 shows a drawing of a magnetic resonator with a lossy object in its vicinity completely covered by a high-conductivity surface. fig. 20 shows a drawing of a magnetic resonator with a lossy object in its vicinity partially covered by a high-conductivity surface. fig. 21 shows a drawing of a magnetic resonator with a lossy object in its vicinity placed on top of a high-conductivity surface. fig. 22 shows a diagram of a completely wireless projector. fig. 23 shows the magnitude of the electric and magnetic fields along a line that contains the diameter of the circular loop inductor and along the axis of the loop inductor. fig. 24 shows a drawing of a magnetic resonator and its enclosure along with a necessary but lossy object placed either (a) in the corner of the enclosure, as far away from the resonator structure as possible or (b) in the center of the surface enclosed by the inductive element in the magnetic resonator. fig. 25 shows a drawing of a magnetic resonator with a high-conductivity surface above it and a lossy object, which may be brought into the vicinity of the resonator, but above the high-conductivity sheet. fig. 26( a ) shows an axially symmetric fem simulation of a thin conducting (copper) cylinder or disk (20 cm in diameter, 2 cm in height) exposed to an initially uniform, externally applied magnetic field (gray flux lines) along the z-axis. the axis of symmetry is at r=0. the magnetic streamlines shown originate at z=−∞, where they are spaced from r=3 cm to r=10 cm in intervals of 1 cm. the axes scales are in meters. fig. 26 ( b ) shows the same structure and externally applied field as in (a), except that the conducting cylinder has been modified to include a 0.25 mm layer of magnetic material (not visible) with μ′ r =40, on its outside surface. note that the magnetic streamlines are deflected away from the cylinder significantly less than in (a). fig. 27 shows an axi-symmetric view of a variation based on the system shown in fig. 26 . only one surface of the lossy material is covered by a layered structure of copper and magnetic materials. the inductor loop is placed on the side of the copper and magnetic material structure opposite to the lossy material as shown. fig. 28 ( a ) depicts a general topology of a matching circuit including an indirect coupling to a high-q inductive element. fig. 28 ( b ) shows a block diagram of a magnetic resonator that includes a conductor loop inductor and a tunable impedance network. physical electrical connections to this resonator may be made to the terminal connections. fig. 28 ( c ) depicts a general topology of a matching circuit directly coupled to a high-q inductive element. fig. 28 ( d ) depicts a general topology of a symmetric matching circuit directly coupled to a high-q inductive element and driven anti-symmetrically (balanced drive). fig. 28 ( e ) depicts a general topology of a matching circuit directly coupled to a high-q inductive element and connected to ground at a point of symmetry of the main resonator (unbalanced drive). figs. 29( a ) and 29 ( b ) depict two topologies of matching circuits transformer-coupled (i.e. indirectly or inductively) to a high-q inductive element. the highlighted portion of the smith chart in (c) depicts the complex impedances (arising from l and r of the inductive element) that may be matched to an arbitrary real impedance z 0 by the topology of fig. 31( b ) in the case ωl 2 =1/ωc 2 . figs. 30( a ),( b ),( c ),( d ),( e ),( f ) depict six topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in series with z 0 . the topologies shown in figs. 30( a ),( b ),( c ) are driven with a common-mode signal at the input terminals, while the topologies shown in figs. 30( d ),( e ),( f ) are symmetric and receive a balanced drive. the highlighted portion of the smith chart in 30 ( g ) depicts the complex impedances that may be matched by these topologies. figs. 30( h ),( i ),( j ),( k ),( l ),( m ) depict six topologies of matching circuits directly coupled to a high-q inductive element and including inductors in series with z 0 . figs. 31( a ),( b ),( c ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in series with z 0 . they are connected to ground at the center point of a capacitor and receive an unbalanced drive. the highlighted portion of the smith chart in fig. 31( d ) depicts the complex impedances that may be matched by these topologies. figs. 31( e ),( f ),( g ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including inductors in series with z 0 . figs. 32( a ),( b ),( c ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in series with z 0 . they are connected to ground by tapping at the center point of the inductor loop and receive an unbalanced drive. the highlighted portion of the smith chart in (d) depicts the complex impedances that may be matched by these topologies, (e),(f),(g) depict three topologies of matching circuits directly coupled to a high-q inductive element and including inductors in series with z 0 . figs. 33( a ),( b ),( c ),( d ),( e ),( f ) depict six topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in parallel with z 0 . the topologies shown in figs. 33( a ),( b ),( c ) are driven with a common-mode signal at the input terminals, while the topologies shown in figs. 33( d ),( e ),( f ) are symmetric and receive a balanced drive. the highlighted portion of the smith chart in fig. 33( g ) depicts the complex impedances that may be matched by these topologies. figs. 33( h ),( i ),( j ),( k ),( l ),( m ) depict six topologies of matching circuits directly coupled to a high-q inductive element and including inductors in parallel with z 0 . figs. 34( a ),( b ),( c ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in parallel with z 0 . they are connected to ground at the center point of a capacitor and receive an unbalanced drive. the highlighted portion of the smith chart in (d) depicts the complex impedances that may be matched by these topologies. figs. 34( e ),( f ),( g ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including inductors in parallel with z 0 . figs. 35( a ),( b ),( c ) depict three topologies of matching circuits directly coupled to a high-q inductive element and including capacitors in parallel with z 0 . they are connected to ground by tapping at the center point of the inductor loop and receive an unbalanced drive. the highlighted portion of the smith chart in figs. 35( d ),( e ), and ( f ) depict the complex impedances that may be matched by these topologies. figs. 36( a ),( b ),( c ),( d ) depict four topologies of networks of fixed and variable capacitors designed to produce an overall variable capacitance with finer tuning resolution and some with reduced voltage on the variable capacitor. figs. 37( a ) and 37 ( b ) depict two topologies of networks of fixed capacitors and a variable inductor designed to produce an overall variable capacitance. fig. 38 depicts a high level block diagram of a wireless power transmission system. fig. 39 depicts a block diagram of an exemplary wirelessly powered device. fig. 40 depicts a block diagram of the source of an exemplary wireless power transfer system. fig. 41 shows an equivalent circuit diagram of a magnetic resonator. the slash through the capacitor symbol indicates that the represented capacitor may be fixed or variable. the port parameter measurement circuitry may be configured to measure certain electrical signals and may measure the magnitude and phase of signals. fig. 42 shows a circuit diagram of a magnetic resonator where the tunable impedance network is realized with voltage controlled capacitors. such an implementation may be adjusted, tuned or controlled by electrical circuits including programmable or controllable voltage sources and/or computer processors. the voltage controlled capacitors may be adjusted in response to data measured by the port parameter measurement circuitry and processed by measurement analysis and control algorithms and hardware. the voltage controlled capacitors may be a switched bank of capacitors. fig. 43 shows an end-to-end wireless power transmission system. in this example, both the source and the device contain port measurement circuitry and a processor. the box labeled “coupler/switch” indicates that the port measurement circuitry may be connected to the resonator by a directional coupler or a switch, enabling the measurement, adjustment and control of the source and device resonators to take place in conjunction with, or separate from, the power transfer functionality. fig. 44 shows an end-to-end wireless power transmission system. in this example, only the source contains port measurement circuitry and a processor. in this case, the device resonator operating characteristics may be fixed or may be adjusted by analog control circuitry and without the need for control signals generated by a processor. fig. 45 shows an end-to-end wireless power transmission system. in this example, both the source and the device contain port measurement circuitry but only the source contains a processor. data from the device is transmitted through a wireless communication channel, which could be implemented either with a separate antenna, or through some modulation of the source drive signal. fig. 46 shows an end-to-end wireless power transmission system. in this example, only the source contains port measurement circuitry and a processor. data from the device is transmitted through a wireless communication channel, which could be implemented either with a separate antenna, or through some modulation of the source drive signal. fig. 47 shows coupled magnetic resonators whose frequency and impedance may be automatically adjusted using algorithms implemented using a processor or a computer. fig. 48 shows a varactor array. fig. 49 shows a device (laptop computer) being wirelessly powered or charged by a source, where both the source and device resonator are physically separated from, but electrically connected to, the source and device. fig. 50 ( a ) is an illustration of a wirelessly powered or charged laptop application where the device resonator is inside the laptop case and is not visible. fig. 50 ( b ) is an illustration of a wirelessly powered or charged laptop application where the resonator is underneath the laptop base and is electrically connected to the laptop power input by an electrical cable. fig. 50 ( c ) is an illustration of a wirelessly powered or charged laptop application where the resonator is attached to the laptop base. fig. 50 ( d ) is an illustration of a wirelessly powered or charged laptop application where the resonator is attached to the laptop display. fig. 51 is a diagram of rooftop pv panels with wireless power transfer. detailed description as described above, this disclosure relates to coupled electromagnetic resonators with long-lived oscillatory resonant modes that may wirelessly transfer power from a power supply to a power drain. however, the technique is not restricted to electromagnetic resonators, but is general and may be applied to a wide variety of resonators and resonant objects. therefore, we first describe the general technique, and then disclose electromagnetic examples for wireless energy transfer. resonators a resonator may be defined as a system that can store energy in at least two different forms, and where the stored energy is oscillating between the two forms. the resonance has a specific oscillation mode with a resonant (modal) frequency, f, and a resonant (modal) field. the angular resonant frequency, ω, may be defined as ω=2πf, the resonant wavelength, λ, may be defined as λ=c/f, where c is the speed of light, and the resonant period, t, may be defined as t=1/f=2π/ω. in the absence of loss mechanisms, coupling mechanisms or external energy supplying or draining mechanisms, the total resonator stored energy, w, would stay fixed and the two forms of energy would oscillate, wherein one would be maximum when the other is minimum and vice versa. in the absence of extraneous materials or objects, the energy in the resonator 102 shown in fig. 1 may decay or be lost by intrinsic losses. the resonator fields then obey the following linear equation: where the variable a(t) is the resonant field amplitude, defined so that the energy contained within the resonator is given by |a(t)| 2 . γ is the intrinsic energy decay or loss rate (e.g. due to absorption and radiation losses). the quality factor, or q-factor, or q, of the resonator, which characterizes the energy decay, is inversely proportional to these energy losses. it may be defined as q=ω*w/p, where p is the time-averaged power lost at steady state. that is, a resonator 102 with a high-q has relatively low intrinsic losses and can store energy for a relatively long time. since the resonator loses energy at its intrinsic decay rate, 2γ, its q, also referred to as its intrinsic q, is given by q=ω/2γ. the quality factor also represents the number of oscillation periods, t, it takes for the energy in the resonator to decay by a factor of e. as described above, we define the quality factor or q of the resonator as that due only to intrinsic loss mechanisms. a subscript index such as q 1 , indicates the resonator (resonator 1 in this case) to which the q refers. fig. 2 shows an electromagnetic resonator 102 labeled according to this convention. note that in this figure, there are no extraneous objects or additional resonators in the vicinity of resonator 1 . extraneous objects and/or additional resonators in the vicinity of a first resonator may perturb or load the first resonator, thereby perturbing or loading the q of the first resonator, depending on a variety of factors such as the distance between the resonator and object or other resonator, the material composition of the object or other resonator, the structure of the first resonator, the power in the first resonator, and the like. unintended external energy losses or coupling mechanisms to extraneous materials and objects in the vicinity of the resonators may be referred to as “perturbing” the q of a resonator, and may be indicated by a subscript within rounded parentheses, ( ). intended external energy losses, associated with energy transfer via coupling to other resonators and to generators and loads in the wireless energy transfer system may be referred to as “loading” the q of the resonator, and may be indicated by a subscript within square brackets, [ ]. the q of a resonator 102 connected or coupled to a power generator, g, or load 302 , l, may be called the “loaded quality factor” or the “loaded q” and may be denoted by q [g] or q [l] , as illustrated in fig. 3 . in general, there may be more than one generator or load 302 connected to a resonator 102 . however, we do not list those generators or loads separately but rather use “g” and “l” to refer to the equivalent circuit loading imposed by the combinations of generators and loads. in general descriptions, we may use the subscript “1” to refer to either generators or loads connected to the resonators. in some of the discussion herein, we define the “loading quality factor” or the “loading q” due to a power generator or load connected to the resonator, as δq [l] , where, 1/δq [l] ≡1/q [l] −1/q. note that the larger the loading q, δq [l] , of a generator or load, the less the loaded q, q [l] , deviates from the unloaded q of the resonator. the q of a resonator in the presence of an extraneous object 402 , p, that is not intended to be part of the energy transfer system may be called the “perturbed quality factor” or the “perturbed q” and may be denoted by q (p) , as illustrated in fig. 4 . in general, there may be many extraneous objects, denoted as p1, p2, etc., or a set of extraneous objects {p}, that perturb the q of the resonator 102 . in this case, the perturbed q may be denoted q p1+p2+ . . . ) or q ({p}) . for example, q 1(brick+wood) may denote the perturbed quality factor of a first resonator in a system for wireless power exchange in the presence of a brick and a piece of wood, and q 2({office}) may denote the perturbed quality factor of a second resonator in a system for wireless power exchange in an office environment. in some of the discussion herein, we define the “perturbing quality factor” or the “perturbing q” due to an extraneous object, p, as δq (p) , where 1/δq (p) ≡1/q (p) −1/q. as stated before, the perturbing quality factor may be due to multiple extraneous objects, p1, p2, etc. or a set of extraneous objects, {p}. the larger the perturbing q, δq (p) , of an object, the less the perturbed q, q (p) , deviates from the unperturbed q of the resonator. in some of the discussion herein, we also define θ (p) ≡q (p) /q and call it the “quality factor insensitivity” or the “q-insensitivity” of the resonator in the presence of an extraneous object. a subscript index, such as θ 1(p) , indicates the resonator to which the perturbed and unperturbed quality factors are referring, namely, θ 1(p) ≡q 1(p) /q 1 . note that the quality factor, q, may also be characterized as “unperturbed”, when necessary to distinguish it from the perturbed quality factor, q (p) , and “unloaded”, when necessary to distinguish it from the loaded quality factor, q [l] . similarly, the perturbed quality factor, q (p) , may also be characterized as “unloaded”, when necessary to distinguish them from the loaded perturbed quality factor, q (p)[l] . coupled resonators resonators having substantially the same resonant frequency, coupled through any portion of their near-fields may interact and exchange energy. there are a variety of physical pictures and models that may be employed to understand, design, optimize and characterize this energy exchange. one way to describe and model the energy exchange between two coupled resonators is using coupled mode theory (cmt). in coupled mode theory, the resonator fields obey the following set of linear equations: where the indices denote different resonators and κ mn are the coupling coefficients between the resonators. for a reciprocal system, the coupling coefficients may obey the relation κ mn =κ nm . note that, for the purposes of the present specification, far-field radiation interference effects will be ignored and thus the coupling coefficients will be considered real. furthermore, since in all subsequent calculations of system performance in this specification the coupling coefficients appear only with their square, κ mn 2 , we use κ mn to denote the absolute value of the real coupling coefficients. note that the coupling coefficient, κ mn , from the cmt described above is related to the so-called coupling factor, k mn , between resonators m and n by k mn =2κ mn /√{square root over (ω m ω n )}. we define a “strong-coupling factor”, u mn , as the ratio of the coupling and loss rates between resonators m and n, by u mn =κ mn /√{square root over (γ m γ n )}=k mn √{square root over (q m q n )}. the quality factor of a resonator m, in the presence of a similar frequency resonator n or additional resonators, may be loaded by that resonator n or additional resonators, in a fashion similar to the resonator being loaded by a connected power generating or consuming device. the fact that resonator m may be loaded by resonator n and vice versa is simply a different way to see that the resonators are coupled. the loaded q's of the resonators in these cases may be denoted as q m[n] and q n[m] . for multiple resonators or loading supplies or devices, the total loading of a resonator may be determined by modeling each load as a resistive loss, and adding the multiple loads in the appropriate parallel and/or series combination to determine the equivalent load of the ensemble. in some of the discussion herein, we define the “loading quality factor” or the “loading q m ” of resonator m due to resonator n as δq m[n] , where 1/δq m[n] ≡1/q m[n] −1/q m . note that resonator n is also loaded by resonator m and its “loading q n ” is given by 1/δq n[m] ≡1/q n[m] −1/q n . when one or more of the resonators are connected to power generators or loads, the set of linear equations is modified to: where s +m (t) and s −m (t) are respectively the amplitudes of the fields coming from a generator into the resonator m and going out of the resonator m either back towards the generator or into a load, defined so that the power they carry is given by |s +m (t)| 2 and |s −m (t)| 2 . the loading coefficients κ m relate to the rate at which energy is exchanged between the resonator m and the generator or load connected to it. note that the loading coefficient, κ m , from the cmt described above is related to the loading quality factor, δq m[l] , defined earlier, by δq m[l] =ω m /2κ m . we define a “strong-loading factor”, u m[l] , as the ratio of the loading and loss rates of resonator m, u m[l] =κ m /γ m =q m /δq m[l] . fig. 1( a ) shows an example of two coupled resonators 1000 , a first resonator 102 s, configured as a source resonator and a second resonator 102 d, configured as a device resonator. energy may be transferred over a distance d between the resonators. the source resonator 102 s may be driven by a power supply or generator (not shown). work may be extracted from the device resonator 102 d by a power consuming drain or load (e.g. a load resistor, not shown). let us use the subscripts “s” for the source, “d” for the device, “g” for the generator, and “1” for the load, and, since in this example there are only two resonators and κ sd =κ ds , let us drop the indices on κ sd , k sd , and u sd , and denote them as κ, k, and u, respectively. the power generator may be constantly driving the source resonator at a constant driving frequency, f, corresponding to an angular driving frequency, ω, where ω=2πf. in this case, the efficiency, η=|s −d | 2 /|s +s | 2 , of the power transmission from the generator to the load (via the source and device resonators) is maximized under the following conditions: the source resonant frequency, the device resonant frequency and the generator driving frequency have to be matched, namely ω s =ω d =ω. furthermore, the loading q of the source resonator due to the generator, δq s[g] , has to be matched (equal) to the loaded q of the source resonator due to the device resonator and the load, q s[dl] , and inversely the loading q of the device resonator due to the load, δq d[l] , has to be matched (equal) to the loaded q of the device resonator due to the source resonator and the generator, q d[sg] , namely δq s[g] =q s[dl] and δq d[l] =q d[sg] . these equations determine the optimal loading rates of the source resonator by the generator and of the device resonator by the load as note that the above frequency matching and q matching conditions are together known as “impedance matching” in electrical engineering. under the above conditions, the maximized efficiency is a monotonically increasing function of only the strong-coupling factor, u=κ/√{square root over (γ s γ d )}=k√{square root over (q s q d )}, between the source and device resonators and is given by, η=u 2 /(1+√{square root over (1+u 2 )}) 2 , as shown in fig. 5 . note that the coupling efficiency, η, is greater than 1% when u is greater than 0.2, is greater than 10% when u is greater than 0.7, is greater than 17% when u is greater than 1, is greater than 52% when u is greater than 3, is greater than 80% when u is greater than 9, is greater than 90% when u is greater than 19, and is greater than 95% when u is greater than 45. in some applications, the regime of operation where u>1 may be referred to as the “strong-coupling” regime. since a large u=κ√{square root over (γ s γ d )}=(2κ/√{square root over (ω s ω d )})√{square root over (q s q d )} is desired in certain circumstances, resonators may be used that are high-q. the q of each resonator may be high. the geometric mean of the resonator q's, √{square root over (q s q d )} may also or instead be high. the coupling factor, k, is a number between 0≦k≦1, and it may be independent (or nearly independent) of the resonant frequencies of the source and device resonators, rather it may determined mostly by their relative geometry and the physical decay-law of the field mediating their coupling. in contrast, the coupling coefficient, κ=k√{square root over (ω s ω d )}/2, may be a strong function of the resonant frequencies. the resonant frequencies of the resonators may be chosen preferably to achieve a high q rather than to achieve a low γ, as these two goals may be achievable at two separate resonant frequency regimes. a high-q resonator may be defined as one with q>100. two coupled resonators may be referred to as a system of high-q resonators when each resonator has a q greater than 100, q s >100 and q d >100. in other implementations, two coupled resonators may be referred to as a system of high-q resonators when the geometric mean of the resonator q's is greater than 100, √{square root over (q s q d )}>100. the resonators may be named or numbered. they may be referred to as source resonators, device resonators, first resonators, second resonators, repeater resonators, and the like. it is to be understood that while two resonators are shown in fig. 1 , and in many of the examples below, other implementations may include three (3) or more resonators. for example, a single source resonator 102 s may transfer energy to multiple device resonators 102 d or multiple devices. energy may be transferred from a first device to a second, and then from the second device to the third, and so forth. multiple sources may transfer energy to a single device or to multiple devices connected to a single device resonator or to multiple devices connected to multiple device resonators. resonators 102 may serve alternately or simultaneously as sources, devices, or they may be used to relay power from a source in one location to a device in another location. intermediate electromagnetic resonators 102 may be used to extend the distance range of wireless energy transfer systems. multiple resonators 102 may be daisy chained together, exchanging energy over extended distances and with a wide range of sources and devices. high power levels may be split between multiple sources 102 s, transferred to multiple devices and recombined at a distant location. the analysis of a single source and a single device resonator may be extended to multiple source resonators and/or multiple device resonators and/or multiple intermediate resonators. in such an analysis, the conclusion may be that large strong-coupling factors, u mn , between at least some or all of the multiple resonators is preferred for a high system efficiency in the wireless energy transfer. again, implementations may use source, device and intermediate resonators that have a high q. the q of each resonator may be high. the geometric mean √{square root over (q m q n )} of the q's for pairs of resonators m and n, for which a large u mn is desired, may also or instead be high. note that since the strong-coupling factor of two resonators may be determined by the relative magnitudes of the loss mechanisms of each resonator and the coupling mechanism between the two resonators, the strength of any or all of these mechanisms may be perturbed in the presence of extraneous objects in the vicinity of the resonators as described above. continuing the conventions for labeling from the previous sections, we describe k as the coupling factor in the absence of extraneous objects or materials. we denote the coupling factor in the presence of an extraneous object, p, as k (p) , and call it the “perturbed coupling factor” or the “perturbed k”. note that the coupling factor, k, may also be characterized as “unperturbed”, when necessary to distinguish from the perturbed coupling factor k (p) . we define δk (p) ≡k (p) −k and we call it the “perturbation on the coupling factor” or the “perturbation on k” due to an extraneous object, p. we also define β (p) ≡k (p) /k and we call it the “coupling factor insensitivity” or the “k-insensitivity”. lower indices, such as β 12(p) , indicate the resonators to which the perturbed and unperturbed coupling factor is referred to, namely β 12(p) ≡k 12(p) /k 12 . similarly, we describe u as the strong-coupling factor in the absence of extraneous objects. we denote the strong-coupling factor in the presence of an extraneous object, p, as u (p) , u (p) =k (p) √{square root over (q 1(p) q 2(p) )}{square root over (q 1(p) q 2(p) )}, and call it the “perturbed strong-coupling factor” or the “perturbed u”. note that the strong-coupling factor u may also be characterized as “unperturbed”, when necessary to distinguish from the perturbed strong-coupling factor u (p) . note that the strong-coupling factor u may also be characterized as “unperturbed”, when necessary to distinguish from the perturbed strong-coupling factor u (p) . we define δu (p) ≡u (p) −u and call it the “perturbation on the strong-coupling factor” or the “perturbation on u” due to an extraneous object, p. we also define ξ (p) ≡u (p) /u and call it the “strong-coupling factor insensitivity” or the “u-insensitivity”. lower indices, such as ξ 12(p) , indicate the resonators to which the perturbed and unperturbed coupling factor refers, namely ξ 12(p) ≡u 12(p) /u 12 . the efficiency of the energy exchange in a perturbed system may be given by the same formula giving the efficiency of the unperturbed system, where all parameters such as strong-coupling factors, coupling factors, and quality factors are replaced by their perturbed equivalents. for example, in a system of wireless energy transfer including one source and one device resonator, the optimal efficiency may calculated as η (p) =[u (p) /(1+√{square root over (1+u (p) 2 )})] 2 . therefore, in a system of wireless energy exchange which is perturbed by extraneous objects, large perturbed strong-coupling factors, u mn(p) , between at least some or all of the multiple resonators may be desired for a high system efficiency in the wireless energy transfer. source, device and/or intermediate resonators may have a high q (p) . some extraneous perturbations may sometimes be detrimental for the perturbed strong-coupling factors (via large perturbations on the coupling factors or the quality factors). therefore, techniques may be used to reduce the effect of extraneous perturbations on the system and preserve large strong-coupling factor insensitivites. efficiency of energy exchange the so-called “useful” energy in a useful energy exchange is the energy or power that must be delivered to a device (or devices) in order to power or charge the device. the transfer efficiency that corresponds to a useful energy exchange may be system or application dependent. for example, high power vehicle charging applications that transfer kilowatts of power may need to be at least 80% efficient in order to supply useful amounts of power resulting in a useful energy exchange sufficient to recharge a vehicle battery, without significantly heating up various components of the transfer system. in some consumer electronics applications, a useful energy exchange may include any energy transfer efficiencies greater than 10%, or any other amount acceptable to keep rechargeable batteries “topped off” and running for long periods of time. for some wireless sensor applications, transfer efficiencies that are much less than 1% may be adequate for powering multiple low power sensors from a single source located a significant distance from the sensors. for still other applications, where wired power transfer is either impossible or impractical, a wide range of transfer efficiencies may be acceptable for a useful energy exchange and may be said to supply useful power to devices in those applications. in general, an operating distance is any distance over which a useful energy exchange is or can be maintained according to the principles disclosed herein. a useful energy exchange for a wireless energy transfer in a powering or recharging application may be efficient, highly efficient, or efficient enough, as long as the wasted energy levels, heat dissipation, and associated field strengths are within tolerable limits. the tolerable limits may depend on the application, the environment and the system location. wireless energy transfer for powering or recharging applications may be efficient, highly efficient, or efficient enough, as long as the desired system performance may be attained for the reasonable cost restrictions, weight restrictions, size restrictions, and the like. efficient energy transfer may be determined relative to that which could be achieved using traditional inductive techniques that are not high-q systems. then, the energy transfer may be defined as being efficient, highly efficient, or efficient enough, if more energy is delivered than could be delivered by similarly sized coil structures in traditional inductive schemes over similar distances or alignment offsets. note that, even though certain frequency and q matching conditions may optimize the system efficiency of energy transfer, these conditions may not need to be exactly met in order to have efficient enough energy transfer for a useful energy exchange. efficient energy exchange may be realized so long as the relative offset of the resonant frequencies (|ω m −ω n |/√{square root over (ω m ω n )}) is less than approximately the maximum among 1/q m(p) , 1/q n(p) and k mn(p) . the q matching condition may be less critical than the frequency matching condition for efficient energy exchange. the degree by which the strong-loading factors, u n[l] , of the resonators due to generators and/or loads may be away from their optimal values and still have efficient enough energy exchange depends on the particular system, whether all or some of the generators and/or loads are q-mismatched and so on. therefore, the resonant frequencies of the resonators may not be exactly matched, but may be matched within the above tolerances. the strong-loading factors of at least some of the resonators due to generators and/or loads may not be exactly matched to their optimal value. the voltage levels, current levels, impedance values, material parameters, and the like may not be at the exact values described in the disclosure but will be within some acceptable tolerance of those values. the system optimization may include cost, size, weight, complexity, and the like, considerations, in addition to efficiency, q, frequency, strong coupling factor, and the like, considerations. some system performance parameters, specifications, and designs may be far from optimal in order to optimize other system performance parameters, specifications and designs. in some applications, at least some of the system parameters may be varying in time, for example because components, such as sources or devices, may be mobile or aging or because the loads may be variable or because the perturbations or the environmental conditions are changing etc. in these cases, in order to achieve acceptable matching conditions, at least some of the system parameters may need to be dynamically adjustable or tunable. all the system parameters may be dynamically adjustable or tunable to achieve approximately the optimal operating conditions. however, based on the discussion above, efficient enough energy exchange may be realized even if some system parameters are not variable. in some examples, at least some of the devices may not be dynamically adjusted. in some examples, at least some of the sources may not be dynamically adjusted. in some examples, at least some of the intermediate resonators may not be dynamically adjusted. in some examples, none of the system parameters may be dynamically adjusted. electromagnetic resonators the resonators used to exchange energy may be electromagnetic resonators. in such resonators, the intrinsic energy decay rates, γ m , are given by the absorption (or resistive) losses and the radiation losses of the resonator. the resonator may be constructed such that the energy stored by the electric field is primarily confined within the structure and that the energy stored by the magnetic field is primarily in the region surrounding the resonator. then, the energy exchange is mediated primarily by the resonant magnetic near-field. these types of resonators may be referred to as magnetic resonators. the resonator may be constructed such that the energy stored by the magnetic field is primarily confined within the structure and that the energy stored by the electric field is primarily in the region surrounding the resonator. then, the energy exchange is mediated primarily by the resonant electric near-field. these types of resonators may be referred to as electric resonators. note that the total electric and magnetic energies stored by the resonator have to be equal, but their localizations may be quite different. in some cases, the ratio of the average electric field energy to the average magnetic field energy specified at a distance from a resonator may be used to characterize or describe the resonator. electromagnetic resonators may include an inductive element, a distributed inductance, or a combination of inductances with inductance, l, and a capacitive element, a distributed capacitance, or a combination of capacitances, with capacitance, c. a minimal circuit model of an electromagnetic resonator 102 is shown in fig. 6 a . the resonator may include an inductive element 108 and a capacitive element 104 . provided with initial energy, such as electric field energy stored in the capacitor 104 , the system will oscillate as the capacitor discharges transferring energy into magnetic field energy stored in the inductor 108 which in turn transfers energy back into electric field energy stored in the capacitor 104 . the resonators 102 shown in figs. 6( b )( c )( d ) may be referred to as magnetic resonators. magnetic resonators may be preferred for wireless energy transfer applications in populated environments because most everyday materials including animals, plants, and humans are non-magnetic (i.e., μ r ≈1), so their interaction with magnetic fields is minimal and due primarily to eddy currents induced by the time-variation of the magnetic fields, which is a second-order effect. this characteristic is important both for safety reasons and because it reduces the potential for interactions with extraneous environmental objects and materials that could alter system performance. fig. 6 d shows a simplified drawing of some of the electric and magnetic field lines associated with an exemplary magnetic resonator 102 b. the magnetic resonator 102 b may include a loop of conductor acting as an inductive element 108 and a capacitive element 104 at the ends of the conductor loop. note that this drawing depicts most of the energy in the region surrounding the resonator being stored in the magnetic field, and most of the energy in the resonator (between the capacitor plates) stored in the electric field. some electric field, owing to fringing fields, free charges, and the time varying magnetic field, may be stored in the region around the resonator, but the magnetic resonator may be designed to confine the electric fields to be close to or within the resonator itself, as much as possible. the inductor 108 and capacitor 104 of an electromagnetic resonator 102 may be bulk circuit elements, or the inductance and capacitance may be distributed and may result from the way the conductors are formed, shaped, or positioned, in the structure. for example, the inductor 108 may be realized by shaping a conductor to enclose a surface area, as shown in figs. 6( b )( c )( d ). this type of resonator 102 may be referred to as a capacitively-loaded loop inductor. note that we may use the terms “loop” or “coil” to indicate generally a conducting structure (wire, tube, strip, etc.), enclosing a surface of any shape and dimension, with any number of turns. in fig. 6 b , the enclosed surface area is circular, but the surface may be any of a wide variety of other shapes and sizes and may be designed to achieve certain system performance specifications. as an example to indicate how inductance scales with physical dimensions, the inductance for a length of circular conductor arranged to form a circular single-turn loop is approximately, where μ 0 is the magnetic permeability of free space, x, is the radius of the enclosed circular surface area and, a, is the radius of the conductor used to form the inductor loop. a more precise value of the inductance of the loop may be calculated analytically or numerically. the inductance for other cross-section conductors, arranged to form other enclosed surface shapes, areas, sizes, and the like, and of any number of wire turns, may be calculated analytically, numerically or it may be determined by measurement. the inductance may be realized using inductor elements, distributed inductance, networks, arrays, series and parallel combinations of inductors and inductances, and the like. the inductance may be fixed or variable and may be used to vary impedance matching as well as resonant frequency operating conditions. there are a variety of ways to realize the capacitance required to achieve the desired resonant frequency for a resonator structure. capacitor plates 110 may be formed and utilized as shown in fig. 6 b , or the capacitance may be distributed and be realized between adjacent windings of a multi-loop conductor 114 , as shown in fig. 6 c . the capacitance may be realized using capacitor elements, distributed capacitance, networks, arrays, series and parallel combinations of capacitances, and the like. the capacitance may be fixed or variable and may be used to vary impedance matching as well as resonant frequency operating conditions. it is to be understood that the inductance and capacitance in an electromagnetic resonator 102 may be lumped, distributed, or a combination of lumped and distributed inductance and capacitance and that electromagnetic resonators may be realized by combinations of the various elements, techniques and effects described herein. electromagnetic resonators 102 may be include inductors, inductances, capacitors, capacitances, as well as additional circuit elements such as resistors, diodes, switches, amplifiers, diodes, transistors, transformers, conductors, connectors and the like. resonant frequency of an electromagnetic resonator an electromagnetic resonator 102 may have a characteristic, natural, or resonant frequency determined by its physical properties. this resonant frequency is the frequency at which the energy stored by the resonator oscillates between that stored by the electric field, w e , (w e =q 2 /2c, where q is the charge on the capacitor, c) and that stored by the magnetic field, w b , (w b =li 2 /2, where i is the current through the inductor, l) of the resonator. in the absence of any losses in the system, energy would continually be exchanged between the electric field in the capacitor 104 and the magnetic field in the inductor 108 . the frequency at which this energy is exchanged may be called the characteristic frequency, the natural frequency, or the resonant frequency of the resonator, and is given by ω, the resonant frequency of the resonator may be changed by tuning the inductance, l, and/or the capacitance, c, of the resonator. the resonator frequency may be design to operate at the so-called ism (industrial, scientific and medical) frequencies as specified by the fcc. the resonator frequency may be chosen to meet certain field limit specifications, specific absorption rate (sar) limit specifications, electromagnetic compatibility (emc) specifications, electromagnetic interference (emi) specifications, component size, cost or performance specifications, and the like. quality factor of an electromagnetic resonator the energy in the resonators 102 shown in fig. 6 may decay or be lost by intrinsic losses including absorptive losses (also called ohmic or resistive losses) and/or radiative losses. the quality factor, or q, of the resonator, which characterizes the energy decay, is inversely proportional to these losses. absorptive losses may be caused by the finite conductivity of the conductor used to form the inductor as well as by losses in other elements, components, connectors, and the like, in the resonator. an inductor formed from low loss materials may be referred to as a “high-q inductive element” and elements, components, connectors and the like with low losses may be referred to as having “high resistive q's”. in general, the total absorptive loss for a resonator may be calculated as the appropriate series and/or parallel combination of resistive losses for the various elements and components that make up the resonator. that is, in the absence of any significant radiative or component/connection losses, the q of the resonator may be given by, q abs , where ω, is the resonant frequency, l, is the total inductance of the resonator and the resistance for the conductor used to form the inductor, for example, may be given by r abs =lρ/a, (l is the length of the wire, ρ is the resistivity of the conductor material, and a is the cross-sectional area over which current flows in the wire). for alternating currents, the cross-sectional area over which current flows may be less than the physical cross-sectional area of the conductor owing to the skin effect. therefore, high-q magnetic resonators may be composed of conductors with high conductivity, relatively large surface areas and/or with specially designed profiles (e.g. litz wire) to minimize proximity effects and reduce the ac resistance. the magnetic resonator structures may include high-q inductive elements composed of high conductivity wire, coated wire, litz wire, ribbon, strapping or plates, tubing, paint, gels, traces, and the like. the magnetic resonators may be self-resonant, or they may include external coupled elements such as capacitors, inductors, switches, diodes, transistors, transformers, and the like. the magnetic resonators may include distributed and lumped capacitance and inductance. in general, the q of the resonators will be determined by the q's of all the individual components of the resonator. because q is proportional to inductance, l, resonators may be designed to increase l, within certain other constraints. one way to increase l, for example, is to use more than one turn of the conductor to form the inductor in the resonator. design techniques and trade-offs may depend on the application, and a wide variety of structures, conductors, components, and resonant frequencies may be chosen in the design of high-q magnetic resonators. in the absence of significant absorption losses, the q of the resonator may be determined primarily by the radiation losses, and given by, q rad =ωl/r rad , where r rad is the radiative loss of the resonator and may depend on the size of the resonator relative to the frequency, ω, or wavelength, λ, of operation. for the magnetic resonators discussed above, radiative losses may scale as r rad ˜(s/λ) 4 (characteristic of magnetic dipole radiation), where x is a characteristic dimension of the resonator, such as the radius of the inductive element shown in fig. 6 b , and where λ=c/f, where c is the speed of light and f is as defined above. the size of the magnetic resonator may be much less than the wavelength of operation so radiation losses may be very small. such structures may be referred to as sub-wavelength resonators. radiation may be a loss mechanism for non-radiative wireless energy transfer systems and designs may be chosen to reduce or minimize r rad . note that a high-q rad may be desirable for non-radiative wireless energy transfer schemes. note too that the design of resonators for non-radiative wireless energy transfer differs from antennas designed for communication or far-field energy transmission purposes. specifically, capacitively-loaded conductive loops may be used as resonant antennas (for example in cell phones), but those operate in the far-field regime where the radiation q's are intentionally designed to be small to make the antenna efficient at radiating energy. such designs are not appropriate for the efficient near-field wireless energy transfer technique disclosed in this application. the quality factor of a resonator including both radiative and absorption losses is q=ωl/(r abs +r rad ). note that there may be a maximum q value for a particular resonator and that resonators may be designed with special consideration given to the size of the resonator, the materials and elements used to construct the resonator, the operating frequency, the connection mechanisms, and the like, in order to achieve a high-q resonator. fig. 7 shows a plot of q of an exemplary magnetic resonator (in this case a coil with a diameter of 60 cm made of copper pipe with an outside diameter (od) of 4 cm) that may be used for wireless power transmission at mhz frequencies. the absorptive q (dashed line) 702 increases with frequency, while the radiative q (dotted line) 704 decreases with frequency, thus leading the overall q to peak 708 at a particular frequency. note that the q of this exemplary resonator is greater than 100 over a wide frequency range. magnetic resonators may be designed to have high-q over a range of frequencies and system operating frequency may set to any frequency in that range. when the resonator is being described in terms of loss rates, the q may be defined using the intrinsic decay rate, 2γ, as described previously. the intrinsic decay rate is the rate at which an uncoupled and undriven resonator loses energy. for the magnetic resonators described above, the intrinsic loss rate may be given by γ=(r abs +r rad )/2 l, and the quality factor, q, of the resonator is given by q=ω/2γ. note that a quality factor related only to a specific loss mechanism may be denoted as q mechanism , if the resonator is not specified, or as q 1,mechanism , if the resonator is specified (e.g. resonator 1 ). for example, q 1,rad is the quality factor for resonator 1 related to its radiation losses. electromagnetic resonator near-fields the high-q electromagnetic resonators used in the near-field wireless energy transfer system disclosed here may be sub-wavelength objects. that is, the physical dimensions of the resonator may be much smaller than the wavelength corresponding to the resonant frequency. sub-wavelength magnetic resonators may have most of the energy in the region surrounding the resonator stored in their magnetic near-fields, and these fields may also be described as stationary or non-propagating because they do not radiate away from the resonator. the extent of the near-field in the area surrounding the resonator is typically set by the wavelength, so it may extend well beyond the resonator itself for a sub-wavelength resonator. the limiting surface, where the field behavior changes from near-field behavior to far-field behavior may be called the “radiation caustic”. the strength of the near-field is reduced the farther one gets away from the resonator. while the field strength of the resonator near-fields decays away from the resonator, the fields may still interact with objects brought into the general vicinity of the resonator. the degree to which the fields interact depends on a variety of factors, some of which may be controlled and designed, and some of which may not. the wireless energy transfer schemes described herein may be realized when the distance between coupled resonators is such that one resonator lies within the radiation caustic of the other. the near-field profiles of the electromagnetic resonators may be similar to those commonly associated with dipole resonators or oscillators. such field profiles may be described as omni-directional, meaning the magnitudes of the fields are non-zero in all directions away from the object. characteristic size of an electromagnetic resonator spatially separated and/or offset magnetic resonators of sufficient q may achieve efficient wireless energy transfer over distances that are much larger than have been seen in the prior art, even if the sizes and shapes of the resonator structures are different. such resonators may also be operated to achieve more efficient energy transfer than was achievable with previous techniques over shorter range distances. we describe such resonators as being capable of mid-range energy transfer. mid-range distances may be defined as distances that are larger than the characteristic dimension of the smallest of the resonators involved in the transfer, where the distance is measured from the center of one resonator structure to the center of a spatially separated second resonator structure. in this definition, two-dimensional resonators are spatially separated when the areas circumscribed by their inductive elements do not intersect and three-dimensional resonators are spatially separated when their volumes do not intersect. a two-dimensional resonator is spatially separated from a three-dimensional resonator when the area circumscribed by the former is outside the volume of the latter. fig. 8 shows some example resonators with their characteristic dimensions labeled. it is to be understood that the characteristic sizes 802 of resonators 102 may be defined in terms of the size of the conductor and the area circumscribed or enclosed by the inductive element in a magnetic resonator and the length of the conductor forming the capacitive element of an electric resonator. then, the characteristic size 802 of a resonator 102 , x char , may be equal to the radius of the smallest sphere that can fit around the inductive or capacitive element of the magnetic or electric resonator respectively, and the center of the resonator structure is the center of the sphere. the characteristic thickness 804 , t char , of a resonator 102 may be the smallest possible height of the highest point of the inductive or capacitive element in the magnetic or capacitive resonator respectively, measured from a flat surface on which it is placed. the characteristic width 808 of a resonator 102 , w char , may be the radius of the smallest possible circle through which the inductive or capacitive element of the magnetic or electric resonator respectively, may pass while traveling in a straight line. for example, the characteristic width 808 of a cylindrical resonator may be the radius of the cylinder. in this inventive wireless energy transfer technique, energy may be exchanged efficiently over a wide range of distances, but the technique is distinguished by the ability to exchange useful energy for powering or recharging devices over mid-range distances and between resonators with different physical dimensions, components and orientations. note that while k may be small in these circumstances, strong coupling and efficient energy transfer may be realized by using high-q resonators to achieve a high u, u=k√{square root over (q s q d )}. that is, increases in q may be used to at least partially overcome decreases in k, to maintain useful energy transfer efficiencies. note too that while the near-field of a single resonator may be described as omni-directional, the efficiency of the energy exchange between two resonators may depend on the relative position and orientation of the resonators. that is, the efficiency of the energy exchange may be maximized for particular relative orientations of the resonators. the sensitivity of the transfer efficiency to the relative position and orientation of two uncompensated resonators may be captured in the calculation of either k or κ. while coupling may be achieved between resonators that are offset and/or rotated relative to each other, the efficiency of the exchange may depend on the details of the positioning and on any feedback, tuning, and compensation techniques implemented during operation. high-q magnetic resonators in the near-field regime of a sub-wavelength capacitively-loaded loop magnetic resonator (x<<λ), the resistances associated with a circular conducting loop inductor composed of n turns of wire whose radius is larger than the skin depth, are approximately r abs =√{square root over (μ o ρω/2)}·nx/a and r rad =π6·η o n 2 (ωx/c) 4 , where ρ is the resistivity of the conductor material and η o ≈120πω is the impedance of free space. the inductance, l, for such a n-turn loop is approximately n 2 times the inductance of a single-turn loop given previously. the quality factor of such a resonator, q=ωl/(r abs +r rad ), is highest for a particular frequency determined by the system parameters ( fig. 4 ). as described previously, at lower frequencies the q is determined primarily by absorption losses and at higher frequencies the q is determined primarily by radiation losses. note that the formulas given above are approximate and intended to illustrate the functional dependence of r abs , r rad and l on the physical parameters of the structure. more accurate numerical calculations of these parameters that take into account deviations from the strict quasi-static limit, for example a non-uniform current/charge distribution along the conductor, may be useful for the precise design of a resonator structure. note that the absorptive losses may be minimized by using low loss conductors to form the inductive elements. the loss of the conductors may be minimized by using large surface area conductors such as conductive tubing, strapping, strips, machined objects, plates, and the like, by using specially designed conductors such as litz wire, braided wires, wires of any cross-section, and other conductors with low proximity losses, in which case the frequency scaled behavior described above may be different, and by using low resistivity materials such as high-purity copper and silver, for example. one advantage of using conductive tubing as the conductor at higher operating frequencies is that it may be cheaper and lighter than a similar diameter solid conductor, and may have similar resistance because most of the current is traveling along the outer surface of the conductor owing to the skin effect. to get a rough estimate of achievable resonator designs made from copper wire or copper tubing and appropriate for operation in the microwave regime, one may calculate the optimum q and resonant frequency for a resonator composed of one circular inductive element (n=1) of copper wire (ρ=1.69·10 −8 ωm) with various cross sections. then for an inductive element with characteristic size x=1 cm and conductor diameter a=1 mm, appropriate for a cell phone for example, the quality factor peaks at q=1225 when f=380 mhz. for x=30 cm and a=2 mm, an inductive element size that might be appropriate for a laptop or a household robot, q=1103 at f=17 mhz. for a larger source inductive element that might be located in the ceiling for example, x=1 m and a=4 mm, q may be as high as q=1315 at f=5 mhz. note that a number of practical examples yield expected quality factors of q≈1000−1500 at λ/x≈50-80. measurements of a wider variety of coil shapes, sizes, materials and operating frequencies than described above show that q's>100 may be realized for a variety of magnetic resonator structures using commonly available materials. as described above, the rate for energy transfer between two resonators of characteristic size x 1 and x 2 , and separated by a distance d between their centers, may be given by κ. to give an example of how the defined parameters scale, consider the cell phone, laptop, and ceiling resonator examples from above, at three (3) distances; d/x=10, 8, 6. in the examples considered here, the source and device resonators are the same size, x 1 =x 2 , and shape, and are oriented as shown in fig. 1( b ). in the cell phone example, ω/2κ=3033, 1553, 655 respectively. in the laptop example, ω/2κ=7131, 3651, 1540 respectively and for the ceiling resonator example, ω/2κ=6481, 3318, 1400. the corresponding coupling-to-loss ratios peak at the frequency where the inductive element q peaks and are κ/γ=0.4, 0.79, 1.97 and 0.15, 0.3, 0.72 and 0.2, 0.4, 0.94 for the three inductive element sizes and distances described above. an example using different sized inductive elements is that of an x 1 =1 m inductor (e.g. source in the ceiling) and an x 2 =30 cm inductor (e.g. household robot on the floor) at a distance d=3 m apart (e.g. room height). in this example, the strong-coupling figure of merit, u=κ/√{square root over (γ 1 γ 2 )}=0.88, for an efficiency of approximately 14%, at the optimal operating frequency of f=6.4 mhz. here, the optimal system operating frequency lies between the peaks of the individual resonator q's. inductive elements may be formed for use in high-q magnetic resonators. we have demonstrated a variety of high-q magnetic resonators based on copper conductors that are formed into inductive elements that enclose a surface. inductive elements may be formed using a variety of conductors arranged in a variety of shapes, enclosing any size or shaped area, and they may be single turn or multiple turn elements. drawings of exemplary inductive elements 900 a-b are shown in fig. 9 . the inductive elements may be formed to enclose a circle, a rectangle, a square, a triangle, a shape with rounded corners, a shape that follows the contour of a particular structure or device, a shape that follows, fills, or utilizes, a dedicated space within a structure or device, and the like. the designs may be optimized for size, cost, weight, appearance, performance, and the like. these conductors may be bent or formed into the desired size, shape, and number of turns. however, it may be difficult to accurately reproduce conductor shapes and sizes using manual techniques. in addition, it may be difficult to maintain uniform or desired center-to-center spacings between the conductor segments in adjacent turns of the inductive elements. accurate or uniform spacing may be important in determining the self capacitance of the structure as well as any proximity effect induced increases in ac resistance, for example. molds may be used to replicate inductor elements for high-q resonator designs. in addition, molds may be used to accurately shape conductors into any kind of shape without creating kinks, buckles or other potentially deleterious effects in the conductor. molds may be used to form the inductor elements and then the inductor elements may be removed from the forms. once removed, these inductive elements may be built into enclosures or devices that may house the high-q magnetic resonator. the formed elements may also or instead remain in the mold used to form them. the molds may be formed using standard cnc (computer numerical control) routing or milling tools or any other known techniques for cutting or forming grooves in blocks. the molds may also or instead be formed using machining techniques, injection molding techniques, casting techniques, pouring techniques, vacuum techniques, thermoforming techniques, cut-in-place techniques, compression forming techniques and the like. the formed element may be removed from the mold or it may remain in the mold. the mold may be altered with the inductive element inside. the mold may be covered, machined, attached, painted and the like. the mold and conductor combination may be integrated into another housing, structure or device. the grooves cut into the molds may be any dimension and may be designed to form conducting tubing, wire, strapping, strips, blocks, and the like into the desired inductor shapes and sizes. the inductive elements used in magnetic resonators may contain more than one loop and may spiral inward or outward or up or down or in some combination of directions. in general, the magnetic resonators may have a variety of shapes, sizes and number of turns and they may be composed of a variety of conducing materials. the magnetic resonators may be free standing or they may be enclosed in an enclosure, container, sleeve or housing. the magnetic resonators may include the form used to make the inductive element. these various forms and enclosures may be composed of almost any kind of material. low loss materials such as teflon, rexolite, styrene, and the like may be preferable for some applications. these enclosures may contain fixtures that hold the inductive elements. magnetic resonators may be composed of self-resonant coils of copper wire or copper tubing. magnetic resonators composed of self resonant conductive wire coils may include a wire of length l, and cross section radius a, wound into a helical coil of radius x, height h, and number of turns n, which may for example be characterized as n=√{square root over (l 2 −h 2 )}/2πx. a magnetic resonator structure may be configured so that x is about 30 cm, h is about 20 cm, a is about 3 mm and n is about 5.25, and, during operation, a power source coupled to the magnetic resonator may drive the resonator at a resonant frequency, f, where f is about 10.6 mhz. where x is about 30 cm, h is about 20 cm, a is about 1 cm and n is about 4, the resonator may be driven at a frequency, f, where f is about 13.4 mhz. where x is about 10 cm, h is about 3 cm, a is about 2 mm and n is about 6, the resonator may be driven at a frequency, f, where f is about 21.4 mhz. high-q inductive elements may be designed using printed circuit board traces. printed circuit board traces may have a variety of advantages compared to mechanically formed inductive elements including that they may be accurately reproduced and easily integrated using established printed circuit board fabrication techniques, that their ac resistance may be lowered using custom designed conductor traces, and that the cost of mass-producing them may be significantly reduced. high-q inductive elements may be fabricated using standard pcb techniques on any pcb material such as fr-4 (epoxy e-glass), multi-functional epoxy, high performance epoxy, bismalaimide triazine/epoxy, polyimide, cyanate ester, polytetraflouroethylene (teflon), fr-2, fr-3, cem-1, cem-2, rogers, resolute, and the like. the conductor traces may be formed on printed circuit board materials with lower loss tangents. the conducting traces may be composed of copper, silver, gold, aluminum, nickel and the like, and they may be composed of paints, inks, or other cured materials. the circuit board may be flexible and it may be a flex-circuit. the conducting traces may be formed by chemical deposition, etching, lithography, spray deposition, cutting, and the like. the conducting traces may be applied to form the desired patterns and they may be formed using crystal and structure growth techniques. the dimensions of the conducting traces, as well as the number of layers containing conducting traces, the position, size and shape of those traces and the architecture for interconnecting them may be designed to achieve or optimize certain system specifications such as resonator q, q (p) , resonator size, resonator material and fabrication costs, u, u (p) , and the like. as an example, a three-turn high-q inductive element 1001 a was fabricated on a four-layer printed circuit board using the rectangular copper trace pattern as shown in fig. 10( a ). the copper trace is shown in black and the pcb in white. the width and thickness of the copper traces in this example was approximately 1 cm (400 mils) and 43 μm (1.7 mils) respectively. the edge-to-edge spacing between turns of the conducting trace on a single layer was approximately 0.75 cm (300 mils) and each board layer thickness was approximately 100 μm (4 mils). the pattern shown in fig. 10( a ) was repeated on each layer of the board and the conductors were connected in parallel. the outer dimensions of the 3-loop structure were approximately 30 cm by 20 cm. the measured inductance of this pcb loop was 5.3 μh. a magnetic resonator using this inductor element and tunable capacitors had a quality factor, q, of 550 at its designed resonance frequency of 6.78 mhz. the resonant frequency could be tuned by changing the inductance and capacitance values in the magnetic resonator. as another example, a two-turn inductor 1001 b was fabricated on a four-layer printed circuit board using the rectangular copper trace pattern shown in fig. 10( b ). the copper trace is shown in black and the pcb in white. the width and height of the copper traces in this example were approximately 0.75 cm (300 mils) and 43 μm (1.7 mils) respectively. the edge-to-edge spacing between turns of the conducting trace on a single layer was approximately 0.635 cm (250 mils) and each board layer thickness was approximately 100 μm (4 mils). the pattern shown in fig. 10( b ) was repeated on each layer of the board and the conductors were connected in parallel. the outer dimensions of the two-loop structure were approximately 7.62 cm by 26.7 cm. the measured inductance of this pcb loop was 1.3 μh. stacking two boards together with a vertical separation of approximately 0.635 cm (250 mils) and connecting the two boards in series produced a pcb inductor with an inductance of approximately 3.4 μh. a magnetic resonator using this stacked inductor loop and tunable capacitors had a quality factor, q, of 390 at its designed resonance frequency of 6.78 mhz. the resonant frequency could be tuned by changing the inductance and capacitance values in the magnetic resonator. the inductive elements may be formed using magnetic materials of any size, shape thickness, and the like, and of materials with a wide range of permeability and loss values. these magnetic materials may be solid blocks, they may enclose hollow volumes, they may be formed from many smaller pieces of magnetic material tiled and or stacked together, and they may be integrated with conducting sheets or enclosures made from highly conducting materials. wires may be wrapped around the magnetic materials to generate the magnetic near-field. these wires may be wrapped around one or more than one axis of the structure. multiple wires may be wrapped around the magnetic materials and combined in parallel, or in series, or via a switch to form customized near-field patterns. the magnetic resonator may include 15 turns of litz wire wound around a 19.2 cm×10 cm×5 mm tiled block of 3f3 ferrite material. the litz wire may be wound around the ferrite material in any direction or combination of directions to achieve the desire resonator performance. the number of turns of wire, the spacing between the turns, the type of wire, the size and shape of the magnetic materials and the type of magnetic material are all design parameters that may be varied or optimized for different application scenarios. high-q magnetic resonators using magnetic material structures it may be possible to use magnetic materials assembled to form an open magnetic circuit, albeit one with an air gap on the order of the size of the whole structure, to realize a magnetic resonator structure. in these structures, high conductivity materials are wound around a structure made from magnetic material to form the inductive element of the magnetic resonator. capacitive elements may be connected to the high conductivity materials, with the resonant frequency then determined as described above. these magnetic resonators have their dipole moment in the plane of the two dimensional resonator structures, rather than perpendicular to it, as is the case for the capacitively-loaded inductor loop resonators. a diagram of a single planar resonator structure is shown in fig. 11( a ). the planar resonator structure is constructed of a core of magnetic material 1121 , such as ferrite with a loop or loops of conducting material 1122 wrapped around the core 1121 . the structure may be used as the source resonator that transfers power and the device resonator that captures energy. when used as a source, the ends of the conductor may be coupled to a power source. alternating electrical current flowing through the conductor loops excites alternating magnetic fields. when the structure is being used to receive power, the ends of the conductor may be coupled to a power drain or load. changing magnetic fields induce an electromotive force in the loop or loops of the conductor wound around the core magnetic material. the dipole moment of these types of structures is in the plane of the structures and is, for example, directed along the y axis for the structure in fig. 11( a ). two such structures have strong coupling when placed substantially in the same plane (i.e. the x,y plane of fig. 11) . the structures of fig. 11( a ) have the most favorable orientation when the resonators are aligned in the same plane along their y axis. the geometry and the coupling orientations of the described planar resonators may be preferable for some applications. the planar or flat resonator shape may be easier to integrate into many electronic devices that are relatively flat and planar. the planar resonators may be integrated into the whole back or side of a device without requiring a change in geometry of the device. due to the flat shape of many devices, the natural position of the devices when placed on a surface is to lay with their largest dimension being parallel to the surface they are placed on. a planar resonator integrated into a flat device is naturally parallel to the plane of the surface and is in a favorable coupling orientation relative to the resonators of other devices or planar resonator sources placed on a flat surface. as mentioned, the geometry of the planar resonators may allow easier integration into devices. their low profile may allow a resonator to be integrated into or as part of a complete side of a device. when a whole side of a device is covered by the resonator, magnetic flux can flow through the resonator core without being obstructed by lossy material that may be part of the device or device circuitry. the core of the planar resonator structure may be of a variety of shapes and thicknesses and may be flat or planar such that the minimum dimension does not exceed 30% of the largest dimension of the structure. the core may have complex geometries and may have indentations, notches, ridges, and the like. geometric enhancements may be used to reduce the coupling dependence on orientation and they may be used to facilitate integration into devices, packaging, packages, enclosures, covers, skins, and the like. two exemplary variations of core geometries are shown in fig. 11( b ). for example, the planar core 1131 may be shaped such that the ends are substantially wider than the middle of the structure to create an indentation for the conductor winding. the core material may be of varying thickness with ends that are thicker and wider than the middle. the core material 1132 may have any number of notches or cutouts 1133 of various depths, width, and shapes to accommodate conductor loops, housing, packaging, and the like. the shape and dimensions of the core may be further dictated by the dimensions and characteristics of the device that they are integrated into. the core material may curve to follow the contours of the device, or may require non-symmetric notches or cutouts to allow clearance for parts of the device. the core structure may be a single monolithic piece of magnetic material or may be composed of a plurality of tiles, blocks, or pieces that are arranged together to form the larger structure. the different layers, tiles, blocks, or pieces of the structure may be of similar or may be of different materials. it may be desirable to use materials with different magnetic permeability in different locations of the structure. core structures with different magnetic permeability may be useful for guiding the magnetic flux, improving coupling, and affecting the shape or extent of the active area of a system. the conductor of the planar resonator structure may be wound at least once around the core. in certain circumstances, it may be preferred to wind at least three loops. the conductor can be any good conductor including conducting wire, litz wire, conducting tubing, sheets, strips, gels, inks, traces and the like. the size, shape, or dimensions of the active area of source may be further enhanced, altered, or modified with the use of materials that block, shield, or guide magnetic fields. to create non-symmetric active area around a source once side of the source may be covered with a magnetic shield to reduce the strength of the magnetic fields in a specific direction. the shield may be a conductor or a layered combination of conductor and magnetic material which can be used to guide magnetic fields away from a specific direction. structures composed of layers of conductors and magnetic materials may be used to reduce energy losses that may occur due to shielding of the source. the plurality of planar resonators may be integrated or combined into one planar resonator structure. a conductor or conductors may be wound around a core structure such that the loops formed by the two conductors are not coaxial. an example of such a structure is shown in fig. 12 where two conductors 1201 , 1202 are wrapped around a planar rectangular core 1203 at orthogonal angles. the core may be rectangular or it may have various geometries with several extensions or protrusions. the protrusions may be useful for wrapping of a conductor, reducing the weight, size, or mass of the core, or may be used to enhance the directionality or omni-directionality of the resonator. a multi wrapped planar resonator with four protrusions is shown by the inner structure 1310 in fig. 13 , where four conductors 1301 , 1302 , 1303 , 1304 are wrapped around the core. the core may have extensions 1305 , 1306 , 1307 , 1308 with one or more conductor loops. a single conductor may be wrapped around a core to form loops that are not coaxial. the four conductor loops of fig. 13 , for example, may be formed with one continuous piece of conductor, or using two conductors where a single conductor is used to make all coaxial loops. non-uniform or asymmetric field profiles around the resonator comprising a plurality of conductor loops may be generated by driving some conductor loops with non-identical parameters. some conductor loops of a source resonator with a plurality of conductor loops may be driven by a power source with a different frequency, voltage, power level, duty cycle, and the like all of which may be used to affect the strength of the magnetic field generated by each conductor. the planar resonator structures may be combined with a capacitively-loaded inductor resonator coil to provide an omni-directional active area all around, including above and below the source while maintaining a flat resonator structure. as shown in fig. 13 , an additional resonator loop coil 1309 comprising of a loop or loops of a conductor, may be placed in a common plane as the planar resonator structure 1310 . the outer resonator coil provides an active area that is substantially above and below the source. the resonator coil can be arranged with any number of planar resonator structures and arrangements described herein. the planar resonator structures may be enclosed in magnetically permeable packaging or integrated into other devices. the planar profile of the resonators within a single, common plane allows packaging and integration into flat devices. a diagram illustrating the application of the resonators is shown in fig. 14 . a flat source 1411 comprising one or more planar resonators 1414 each with one or more conductor loops may transfer power to devices 1412 , 1413 that are integrated with other planar resonators 1415 , 1416 and placed within an active area 1417 of the source. the devices may comprise a plurality of planar resonators such that regardless of the orientation of the device with respect to the source the active area of the source does not change. in addition to invariance to rotational misalignment, a flat device comprising of planar resonators may be turned upside down without substantially affecting the active area since the planar resonator is still in the plane of the source. another diagram illustrating a possible use of a power transfer system using the planar resonator structures is shown in fig. 15 . a planar source 1521 placed on top of a surface 1525 may create an active area that covers a substantial surface area creating an “energized surface” area. devices such as computers 1524 , mobile handsets 1522 , games, and other electronics 1523 that are coupled to their respective planar device resonators may receive energy from the source when placed within the active area of the source, which may be anywhere on top of the surface. several devices with different dimensions may be placed in the active area and used normally while charging or being powered from the source without having strict placement or alignment constraints. the source may be placed under the surface of a table, countertop, desk, cabinet, and the like, allowing it to be completely hidden while energizing the top surface of the table, countertop, desk, cabinet and the like, creating an active area on the surface that is much larger than the source. the source may include a display or other visual, auditory, or vibration indicators to show the direction of charging devices or what devices are being charged, error or problems with charging, power levels, charging time, and the like. the source resonators and circuitry may be integrated into any number of other devices. the source may be integrated into devices such as clocks, keyboards, monitors, picture frames, and the like. for example, a keyboard integrated with the planar resonators and appropriate power and control circuitry may be used as a source for devices placed around the keyboard such as computer mice, webcams, mobile handsets, and the like without occupying any additional desk space. while the planar resonator structures have been described in the context of mobile devices it should be clear to those skilled in the art that a flat planar source for wireless power transfer with an active area that extends beyond its physical dimensions has many other consumer and industrial applications. the structures and configuration may be useful for a large number of applications where electronic or electric devices and a power source are typically located, positioned, or manipulated in substantially the same plane and alignment. some of the possible application scenarios include devices on walls, floor, ceilings or any other substantially planar surfaces. flat source resonators may be integrated into a picture frame or hung on a wall thereby providing an active area within the plane of the wall where other electronic devices such as digital picture frames, televisions, lights, and the like can be mounted and powered without wires. planar resonators may be integrated into a floor resulting in an energized floor or active area on the floor on which devices can be placed to receive power. audio speakers, lamps, heaters, and the like can be placed within the active are and receive power wirelessly. the planar resonator may have additional components coupled to the conductor. components such as capacitors, inductors, resistors, diodes, and the like may be coupled to the conductor and may be used to adjust or tune the resonant frequency and the impedance matching for the resonators. a planar resonator structure of the type described above and shown in fig. 11( a ), may be created, for example, with a quality factor, q, of 100 or higher and even q of 1,000 or higher. energy may be wirelessly transferred from one planar resonator structure to another over a distance larger than the characteristic size of the resonators, as shown in fig. 11( c ). in addition to utilizing magnetic materials to realize a structure with properties similar to the inductive element in the magnetic resonators, it may be possible to use a combination of good conductor materials and magnetic material to realize such inductive structures. fig. 16( a ) shows a magnetic resonator structure 1602 that may include one or more enclosures made of high-conductivity materials (the inside of which would be shielded from ac electromagnetic fields generated outside) surrounded by at least one layer of magnetic material and linked by blocks of magnetic material 1604 . a structure may include a high-conductivity sheet of material covered on one side by a layer of magnetic material. the layered structure may instead be applied conformally to an electronic device, so that parts of the device may be covered by the high-conductivity and magnetic material layers, while other parts that need to be easily accessed (such as buttons or screens) may be left uncovered. the structure may also or instead include only layers or bulk pieces of magnetic material. thus, a magnetic resonator may be incorporated into an existing device without significantly interfering with its existing functions and with little or no need for extensive redesign. moreover, the layers of good conductor and/or magnetic material may be made thin enough (of the order of a millimeter or less) that they would add little extra weight and volume to the completed device. an oscillating current applied to a length of conductor wound around the structure, as shown by the square loop in the center of the structure in fig. 16 may be used to excite the electromagnetic fields associated with this structure. quality factor of the structure a structure of the type described above may be created with a quality factor, q, of the order of 1,000 or higher. this high-q is possible even if the losses in the magnetic material are high, if the fraction of magnetic energy within the magnetic material is small compared to the total magnetic energy associated with the object. for structures composed of layers conducting materials and magnetic materials, the losses in the conducting materials may be reduced by the presence of the magnetic materials as described previously. in structures where the magnetic material layer's thickness is of the order of 1/100 of the largest dimension of the system (e.g., the magnetic material may be of the order of 1 mm thick, while the area of the structure is of the order of 10 cm×10 cm), and the relative permeability is of the order of 1,000, it is possible to make the fraction of magnetic energy contained within the magnetic material only a few hundredths of the total magnetic energy associated with the object or resonator. to see how that comes about, note that the expression for the magnetic energy contained in a volume is u m =∫ v drb(r) 2 /(2μ r ,μ 0 ), so as long as b (rather than 1/) is the main field conserved across the magnetic material-air interface (which is typically the case in open magnetic circuits), the fraction of magnetic energy contained in the high-μ r region may be significantly reduced compared to what it is in air. if the fraction of magnetic energy in the magnetic material is denoted by frac, and the loss tangent of the material is tanδ, then the q of the resonator, assuming the magnetic material is the only source of losses, is q=1/(frac×tanδ). thus, even for loss tangents as high as 0.1, it is possible to achieve q's of the order of 1,000 for these types of resonator structures. if the structure is driven with n turns of wire wound around it, the losses in the excitation inductor loop can be ignored if n is sufficiently high. fig. 17 shows an equivalent circuit 1700 schematic for these structures and the scaling of the loss mechanisms and inductance with the number of turns, n, wound around a structure made of conducting and magnetic material. if proximity effects can be neglected (by using an appropriate winding, or a wire designed to minimize proximity effects, such as litz wire and the like), the resistance 1702 due to the wire in the looped conductor scales linearly with the length of the loop, which is in turn proportional to the number of turns. on the other hand, both the equivalent resistance 1708 and equivalent inductance 1704 of these special structures are proportional to the square of the magnetic field inside the structure. since this magnetic field is proportional to n, the equivalent resistance 1708 and equivalent inductance 1704 are both proportional to n 2 . thus, for large enough n, the resistance 1702 of the wire is much smaller than the equivalent resistance 1708 of the magnetic structure, and the q of the resonator asymptotes to q max =ωl μ /r μ . fig. 16 ( a ) shows a drawing of a copper and magnetic material structure 1602 driven by a square loop of current around the narrowed segment at the center of the structure 1604 and the magnetic field streamlines generated by this structure 1608 . this exemplary structure includes two 20 cm×8 cm×2 cm hollow regions enclosed with copper and then completely covered with a 2 mm layer of magnetic material having the properties μ r ′=1,400, μ r ″=5, and σ=0.5 s/m. these two parallelepipeds are spaced 4 cm apart and are connected by a 2 cm×4 cm×2 cm block of the same magnetic material. the excitation loop is wound around the center of this block. at a frequency of 300 khz, this structure has a calculated q of 890. the conductor and magnetic material structure may be shaped to optimize certain system parameters. for example, the size of the structure enclosed by the excitation loop may be small to reduce the resistance of the excitation loop, or it may be large to mitigate losses in the magnetic material associated with large magnetic fields. note that the magnetic streamlines and q's associated with the same structure composed of magnetic material only would be similar to the layer conductor and magnetic material design shown here. electromagnetic resonators interacting with other objects for electromagnetic resonators, extrinsic loss mechanisms that perturb the intrinsic q may include absorption losses inside the materials of nearby extraneous objects and radiation losses related to scattering of the resonant fields from nearby extraneous objects. absorption losses may be associated with materials that, over the frequency range of interest, have non-zero, but finite, conductivity, σ, (or equivalently a non-zero and finite imaginary part of the dielectric permittivity), such that electromagnetic fields can penetrate it and induce currents in it, which then dissipate energy through resistive losses. an object may be described as lossy if it at least partly includes lossy materials. consider an object including a homogeneous isotropic material of conductivity, σ and magnetic permeability, μ. the penetration depth of electromagnetic fields inside this object is given by the skin depth, δ=√{square root over (2/ωμσ)}. the power dissipated inside the object, p d , can be determined from p d =∫ v drσ|e| 2 =∫ v dr|j| 2 /σ where we made use of ohm's law, j=σe, and where e is the electric field and j is the current density. if over the frequency range of interest, the conductivity, σ, of the material that composes the object is low enough that the material's skin depth, δ, may be considered long, (i.e. δ is longer than the objects' characteristic size, or δ is longer than the characteristic size of the portion of the object that is lossy) then the electromagnetic fields, e and h, where h is the magnetic field, may penetrate significantly into the object. then, these finite-valued fields may give rise to a dissipated power that scales as p d ˜σv ol |e| 2 where v ol is the volume of the object that is lossy and |e| 2 is the spatial average of the electric-field squared, in the volume under consideration. therefore, in the low-conductivity limit, the dissipated power scales proportionally to the conductivity and goes to zero in the limit of a non-conducting (purely dielectric) material. if over the frequency range of interest, the conductivity, σ, of the material that composes the object is high enough that the material's skin depth may be considered short, then the electromagnetic fields, e and h, may penetrate only a short distance into the object (namely they stay close to the ‘skin’ of the material, where δ is smaller than the characteristic thickness of the portion of the object that is lossy). in this case, the currents induced inside the material may be concentrated very close to the material surface, approximately within a skin depth, and their magnitude may be approximated by the product of a surface current density (mostly determined by the shape of the incident electromagnetic fields and, as long as the thickness of the conductor is much larger than the skin-depth, independent of frequency and conductivity to first order) k(x,y) (where x and y are coordinates parameterizing the surface) and a function decaying exponentially into the surface: exp(−z/δ)/δ (where z denotes the coordinate locally normal to the surface): j(x,y,z)=k(x,y) exp(−z/δ)/δ. then, the dissipated power, p d , may be estimated by, p d = ,v dr|j ( r )| 2 /σ≃( s dxdy|k ( x,y )| 2 )( 28 0 dz exp(2 z /δ)/(σδ 2 ))=√{square root over (μω/8σ)} s dxdy|k ( x,y )| 2 ) therefore, in the high-conductivity limit, the dissipated power scales inverse proportionally to the square-root of the conductivity and goes to zero in the limit of a perfectly-conducting material. if over the frequency range of interest, the conductivity, σ, of the material that composes the object is finite, then the material's skin depth, δ, may penetrate some distance into the object and some amount of power may be dissipated inside the object, depending also on the size of the object and the strength of the electromagnetic fields. this description can be generalized to also describe the general case of an object including multiple different materials with different properties and conductivities, such as an object with an arbitrary inhomogeneous and anisotropic distribution of the conductivity inside the object. note that the magnitude of the loss mechanisms described above may depend on the location and orientation of the extraneous objects relative to the resonator fields as well as the material composition of the extraneous objects. for example, high-conductivity materials may shift the resonant frequency of a resonator and detune it from other resonant objects. this frequency shift may be fixed by applying a feedback mechanism to a resonator that corrects its frequency, such as through changes in the inductance and/or capacitance of the resonator. these changes may be realized using variable capacitors and inductors, in some cases achieved by changes in the geometry of components in the resonators. other novel tuning mechanisms, described below, may also be used to change the resonator frequency. where external losses are high, the perturbed q may be low and steps may be taken to limit the absorption of resonator energy inside such extraneous objects and materials. because of the functional dependence of the dissipated power on the strength of the electric and magnetic fields, one might optimize system performance by designing a system so that the desired coupling is achieved with shorter evanescent resonant field tails at the source resonator and longer at the device resonator, so that the perturbed q of the source in the presence of other objects is optimized (or vice versa if the perturbed q of the device needs to be optimized). note that many common extraneous materials and objects such as people, animals, plants, building materials, and the like, may have low conductivities and therefore may have little impact on the wireless energy transfer scheme disclosed here. an important fact related to the magnetic resonator designs we describe is that their electric fields may be confined primarily within the resonator structure itself, so it should be possible to operate within the commonly accepted guidelines for human safety while providing wireless power exchange over mid range distances. electromagnetic resonators with reduced interactions one frequency range of interest for near-field wireless power transmission is between 10 khz and 100 mhz. in this frequency range, a large variety of ordinary non-metallic materials, such as for example several types of wood and plastic may have relatively low conductivity, such that only small amounts of power may be dissipated inside them. in addition, materials with low loss tangents, tan δ, where tan δ=∈″/∈′, and ∈″ and ∈′ are the imaginary and real parts of the permittivity respectively, may also have only small amounts of power dissipated inside them. metallic materials, such as copper, silver, gold, and the like, with relatively high conductivity, may also have little power dissipated in them, because electromagnetic fields are not able to significantly penetrate these materials, as discussed earlier. these very high and very low conductivity materials, and low loss tangent materials and objects may have a negligible impact on the losses of a magnetic resonator. however, in the frequency range of interest, there are materials and objects such as some electronic circuits and some lower-conductivity metals, which may have moderate (in general inhomogeneous and anisotropic) conductivity, and/or moderate to high loss tangents, and which may have relatively high dissipative losses. relatively larger amounts of power may be dissipated inside them. these materials and objects may dissipate enough energy to reduce q (p) by non-trivial amounts, and may be referred to as “lossy objects”. one way to reduce the impact of lossy materials on the q (p) of a resonator is to use high-conductivity materials to shape the resonator fields such that they avoid the lossy objects. the process of using high-conductivity materials to tailor electromagnetic fields so that they avoid lossy objects in their vicinity may be understood by visualizing high-conductivity materials as materials that deflect or reshape the fields. this picture is qualitatively correct as long as the thickness of the conductor is larger than the skin-depth because the boundary conditions for electromagnetic fields at the surface of a good conductor force the electric field to be nearly completely perpendicular to, and the magnetic field to be nearly completely tangential to, the conductor surface. therefore, a perpendicular magnetic field or a tangential electric field will be “deflected away” from the conducting surface. furthermore, even a tangential magnetic field or a perpendicular electric field may be forced to decrease in magnitude on one side and/or in particular locations of the conducting surface, depending on the relative position of the sources of the fields and the conductive surface. as an example, fig. 18 shows a finite element method (fem) simulation of two high conductivity surfaces 1802 above and below a lossy dielectric material 1804 in an external, initially uniform, magnetic field of frequency f=6.78 mhz. the system is azimuthally symmetric around the r=0 axis. in this simulation, the lossy dielectric material 1804 is sandwiched between two conductors 1802 , shown as the white lines at approximately z=±0.01 m. in the absence of the conducting surfaces above and below the dielectric disk, the magnetic field (represented by the drawn magnetic field lines) would have remained essentially uniform (field lines straight and parallel with the z-axis), indicating that the magnetic field would have passed straight through the lossy dielectric material. in this case, power would have been dissipated in the lossy dielectric disk. in the presence of conducting surfaces, however, this simulation shows the magnetic field is reshaped. the magnetic field is forced to be tangential to surface of the conductor and so is deflected around those conducting surfaces 1802 , minimizing the amount of power that may be dissipated in the lossy dielectric material 1804 behind or between the conducting surfaces. as used herein, an axis of electrical symmetry refers to any axis about which a fixed or time-varying electrical or magnetic field is substantially symmetric during an exchange of energy as disclosed herein. a similar effect is observed even if only one conducting surface, above or below, the dielectric disk, is used. if the dielectric disk is thin, the fact that the electric field is essentially zero at the surface, and continuous and smooth close to it, means that the electric field is very low everywhere close to the surface (i.e. within the dielectric disk). a single surface implementation for deflecting resonator fields away from lossy objects may be preferred for applications where one is not allowed to cover both sides of the lossy material or object (e.g. an lcd screen). note that even a very thin surface of conducting material, on the order of a few skin-depths, may be sufficient (the skin depth in pure copper at 6.78 mhz is ˜20 μm, and at 250 khz is ˜100 μm) to significantly improve the q (p) of a resonator in the presence of lossy materials. lossy extraneous materials and objects may be parts of an apparatus, in which a high-q resonator is to be integrated. the dissipation of energy in these lossy materials and objects may be reduced by a number of techniques including: by positioning the lossy materials and objects away from the resonator, or, in special positions and orientations relative to the resonator.by using a high conductivity material or structure to partly or entirely cover lossy materials and objects in the vicinity of a resonatorby placing a closed surface (such as a sheet or a mesh) of high-conductivity material around a lossy object to completely cover the lossy object and shape the resonator fields such that they avoid the lossy object.by placing a surface (such as a sheet or a mesh) of a high-conductivity material around only a portion of a lossy object, such as along the top, the bottom, along the side, and the like, of an object or material.by placing even a single surface (such as a sheet or a mesh) of high-conductivity material above or below or on one side of a lossy object to reduce the strength of the fields at the location of the lossy object. fig. 19 shows a capacitively-loaded loop inductor forming a magnetic resonator 102 and a disk-shaped surface of high-conductivity material 1802 that completely surrounds a lossy object 1804 placed inside the loop inductor. note that some lossy objects may be components, such as electronic circuits, that may need to interact with, communicate with, or be connected to the outside environment and thus cannot be completely electromagnetically isolated. partially covering a lossy material with high conductivity materials may still reduce extraneous losses while enabling the lossy material or object to function properly. fig. 20 shows a capacitively-loaded loop inductor that is used as the resonator 102 and a surface of high-conductivity material 1802 , surrounding only a portion of a lossy object 1804 , that is placed inside the inductor loop. extraneous losses may be reduced, but may not be completely eliminated, by placing a single surface of high-conductivity material above, below, on the side, and the like, of a lossy object or material. an example is shown in fig. 21 , where a capacitively-loaded loop inductor is used as the resonator 102 and a surface of high-conductivity material 1802 is placed inside the inductor loop under a lossy object 1804 to reduce the strength of the fields at the location of the lossy object. it may be preferable to cover only one side of a material or object because of considerations of cost, weight, assembly complications, air flow, visual access, physical access, and the like. a single surface of high-conductivity material may be used to avoid objects that cannot or should not be covered from both sides (e.g. lcd or plasma screens). such lossy objects may be avoided using optically transparent conductors. high-conductivity optically opaque materials may instead be placed on only a portion of the lossy object, instead of, or in addition to, optically transparent conductors. the adequacy of single-sided vs. multi-sided covering implementations, and the design trade-offs inherent therein may depend on the details of the wireless energy transfer scenario and the properties of the lossy materials and objects. below we describe an example using high-conductivity surfaces to improve the q-insensitivity, θ (p) , of an integrated magnetic resonator used in a wireless energy-transfer system. fig. 22 shows a wireless projector 2200 . the wireless projector may include a device resonator 102 c, a projector 2202 , a wireless network/video adapter 2204 , and power conversion circuits 2208 , arranged as shown. the device resonator 102 c may include a three-turn conductor loop, arranged to enclose a surface, and a capacitor network 2210 . the conductor loop may be designed so that the device resonator 102 c has a high q (e.g., >100) at its operating resonant frequency. prior to integration in the completely wireless projector 2200 , this device resonator 102 c has a q of approximately 477 at the designed operating resonant frequency of 6.78 mhz. upon integration, and placing the wireless network/video adapter card 2204 in the center of the resonator loop inductor, the resonator q (integrated) was decreased to approximately 347. at least some of the reduction from q to q (integrated) was attributed to losses in the perturbing wireless network/video adapter card. as described above, electromagnetic fields associated with the magnetic resonator 102 c may induce currents in and on the wireless network/video adapter card 2204 , which may be dissipated in resistive losses in the lossy materials that compose the card. we observed that q (integrated) of the resonator may be impacted differently depending on the composition, position, and orientation, of objects and materials placed in its vicinity. in a completely wireless projector example, covering the network/video adapter card with a thin copper pocket (a folded sheet of copper that covered the top and the bottom of the wireless network/video adapter card, but not the communication antenna) improved the q (integrated) of the magnetic resonator to a q (integrated+copper pocket) of approximately 444. in other words, most of the reduction in q (integrated) due to the perturbation caused by the extraneous network/video adapter card could be eliminated using a copper pocket to deflect the resonator fields away from the lossy materials. in another completely wireless projector example, covering the network/video adapter card with a single copper sheet placed beneath the card provided a q (integrated+copper sheet) approximately equal to q (integrated+copper pocket) . in that example, the high perturbed q of the system could be maintained with a single high-conductivity sheet used to deflect the resonator fields away from the lossy adapter card. it may be advantageous to position or orient lossy materials or objects, which are part of an apparatus including a high-q electromagnetic resonator, in places where the fields produced by the resonator are relatively weak, so that little or no power may be dissipated in these objects and so that the q-insensitivity, θ (p) , may be large. as was shown earlier, materials of different conductivity may respond differently to electric versus magnetic fields. therefore, according to the conductivity of the extraneous object, the positioning technique may be specialized to one or the other field. fig. 23 shows the magnitude of the electric 2312 and magnetic fields 2314 along a line that contains the diameter of the circular loop inductor and the electric 2318 and magnetic fields 2320 along the axis of the loop inductor for a capacitively-loaded circular loop inductor of wire of radius 30 cm, resonant at 10 mhz. it can be seen that the amplitude of the resonant near-fields reach their maxima close to the wire and decay away from the loop, 2312 , 2314 . in the plane of the loop inductor 2318 , 2320 , the fields reach a local minimum at the center of the loop. therefore, given the finite size of the apparatus, it may be that the fields are weakest at the extrema of the apparatus or it may be that the field magnitudes have local minima somewhere within the apparatus. this argument holds for any other type of electromagnetic resonator 102 and any type of apparatus. examples are shown in figs. 24 a and 24 b , where a capacitively-loaded inductor loop forms a magnetic resonator 102 and an extraneous lossy object 1804 is positioned where the electromagnetic fields have minimum magnitude. in a demonstration example, a magnetic resonator was formed using a three-turn conductor loop, arranged to enclose a square surface (with rounded corners), and a capacitor network. the q of the resonator was approximately 619 at the designed operating resonant frequency of 6.78 mhz. the perturbed q of this resonator depended on the placement of the perturbing object, in this case a pocket projector, relative to the resonator. when the perturbing projector was located inside the inductor loop and at its center or on top of the inductor wire turns, q (projector) was approximately 96, lower than when the perturbing projector was placed outside of the resonator, in which case q (projector) was approximately 513. these measurements support the analysis that shows the fields inside the inductor loop may be larger than those outside it, so lossy objects placed inside such a loop inductor may yield lower perturbed q's for the system than when the lossy object is placed outside the loop inductor. depending on the resonator designs and the material composition and orientation of the lossy object, the arrangement shown in fig. 24 b may yield a higher q-insensitivity, θ (projector) , than the arrangement shown in fig. 24 a. high-q resonators may be integrated inside an apparatus. extraneous materials and objects of high dielectric permittivity, magnetic permeability, or electric conductivity may be part of the apparatus into which a high-q resonator is to be integrated. for these extraneous materials and objects in the vicinity of a high-q electromagnetic resonator, depending on their size, position and orientation relative to the resonator, the resonator field-profile may be distorted and deviate significantly from the original unperturbed field-profile of the resonator. such a distortion of the unperturbed fields of the resonator may significantly decrease the q to a lower q (p) , even if the extraneous objects and materials are lossless. it may be advantageous to position high-conductivity objects, which are part of an apparatus including a high-q electromagnetic resonator, at orientations such that the surfaces of these objects are, as much as possible, perpendicular to the electric field lines produced by the unperturbed resonator and parallel to the magnetic field lines produced by the unperturbed resonator, thus distorting the resonant field profiles by the smallest amount possible. other common objects that may be positioned perpendicular to the plane of a magnetic resonator loop include screens (lcd, plasma, etc), batteries, cases, connectors, radiative antennas, and the like. the q-insensitivity, θ (p) , of the resonator may be much larger than if the objects were positioned at a different orientation with respect to the resonator fields. lossy extraneous materials and objects, which are not part of the integrated apparatus including a high-q resonator, may be located or brought in the vicinity of the resonator, for example, during the use of the apparatus. it may be advantageous in certain circumstances to use high conductivity materials to tailor the resonator fields so that they avoid the regions where lossy extraneous objects may be located or introduced to reduce power dissipation in these materials and objects and to increase q-insensitivity, θ (p) . an example is shown in fig. 25 , where a capacitively-loaded loop inductor and capacitor are used as the resonator 102 and a surface of high-conductivity material 1802 is placed above the inductor loop to reduce the magnitude of the fields in the region above the resonator, where lossy extraneous objects 1804 may be located or introduced. note that a high-conductivity surface brought in the vicinity of a resonator to reshape the fields may also lead to q (cond. surface) <q. the reduction in the perturbed q may be due to the dissipation of energy inside the lossy conductor or to the distortion of the unperturbed resonator field profiles associated with matching the field boundary conditions at the surface of the conductor. therefore, while a high-conductivity surface may be used to reduce the extraneous losses due to dissipation inside an extraneous lossy object, in some cases, especially in some of those where this is achieved by significantly reshaping the electromagnetic fields, using such a high-conductivity surface so that the fields avoid the lossy object may result effectively in q (p+cond. surface) <q (p) rather than the desired result q (p+cond. surface) >q (p) . as described above, in the presence of loss inducing objects, the perturbed quality factor of a magnetic resonator may be improved if the electromagnetic fields associated with the magnetic resonator are reshaped to avoid the loss inducing objects. another way to reshape the unperturbed resonator fields is to use high permeability materials to completely or partially enclose or cover the loss inducing objects, thereby reducing the interaction of the magnetic field with the loss inducing objects. magnetic field shielding has been described previously, for example in electrodynamics 3 rd ed., jackson, pp. 201-203. there, a spherical shell of magnetically permeable material was shown to shield its interior from external magnetic fields. for example, if a shell of inner radius a, outer radius b, and relative permeability μ r , is placed in an initially uniform magnetic field h 0 , then the field inside the shell will have a constant magnitude, 9μ r h 0 /[(2μ r +1)(μ r +2)−2(a/b) 3 (μ r −1) 2 ], which tends to 9h 0 /2μ r (1−(a/b) 3 ) if μ r >>1. this result shows that an incident magnetic field (but not necessarily an incident electric field) may be greatly attenuated inside the shell, even if the shell is quite thin, provided the magnetic permeability is high enough. it may be advantageous in certain circumstances to use high permeability materials to partly or entirely cover lossy materials and objects so that they are avoided by the resonator magnetic fields and so that little or no power is dissipated in these materials and objects. in such an approach, the q-insensitivity, θ (p) , may be larger than if the materials and objects were not covered, possibly larger than 1. it may be desirable to keep both the electric and magnetic fields away from loss inducing objects. as described above, one way to shape the fields in such a manner is to use high-conductivity surfaces to either completely or partially enclose or cover the loss inducing objects. a layer of magnetically permeable material, also referred to as magnetic material, (any material or meta-material having a non-trivial magnetic permeability), may be placed on or around the high-conductivity surfaces. the additional layer of magnetic material may present a lower reluctance path (compared to free space) for the deflected magnetic field to follow and may partially shield the electric conductor underneath it from the incident magnetic flux. this arrangement may reduce the losses due to induced currents in the high-conductivity surface. under some circumstances the lower reluctance path presented by the magnetic material may improve the perturbed q of the structure. fig. 26 a shows an axially symmetric fem simulation of a thin conducting 2604 (copper) disk (20 cm in diameter, 2 cm in height) exposed to an initially uniform, externally applied magnetic field (gray flux lines) along the z-axis. the axis of symmetry is at r=0. the magnetic streamlines shown originate at z=−∞, where they are spaced from r=3 cm to r=10 cm in intervals of 1 cm. the axes scales are in meters. imagine, for example, that this conducing cylinder encloses loss-inducing objects within an area circumscribed by a magnetic resonator in a wireless energy transfer system such as shown in fig. 19 . this high-conductivity enclosure may increase the perturbing q of the lossy objects and therefore the overall perturbed q of the system, but the perturbed q may still be less than the unperturbed q because of induced losses in the conducting surface and changes to the profile of the electromagnetic fields. decreases in the perturbed q associated with the high-conductivity enclosure may be at least partially recovered by including a layer of magnetic material along the outer surface or surfaces of the high-conductivity enclosure. fig. 26 b shows an axially symmetric fem simulation of the thin conducting 2604 a (copper) disk (20 cm in diameter, 2 cm in height) from fig. 26 a , but with an additional layer of magnetic material placed directly on the outer surface of the high-conductivity enclosure. note that the presence of the magnetic material may provide a lower reluctance path for the magnetic field, thereby at least partially shielding the underlying conductor and reducing losses due to induced eddy currents in the conductor. fig. 27 depicts a variation (in axi-symmetric view) to the system shown in fig. 26 where not all of the lossy material 2708 may be covered by a high-conductivity surface 2706 . in certain circumstances it may be useful to cover only one side of a material or object, such as due to considerations of cost, weight, assembly complications, air flow, visual access, physical access, and the like. in the exemplary arrangement shown in fig. 27 , only one surface of the lossy material 2708 is covered and the resonator inductor loop is placed on the opposite side of the high-conductivity surface. mathematical models were used to simulate a high-conductivity enclosure made of copper and shaped like a 20 cm diameter by 2 cm high cylindrical disk placed within an area circumscribed by a magnetic resonator whose inductive element was a single-turn wire loop with loop radius r=11 cm and wire radius a=1 mm. simulations for an applied 6.78 mhz electromagnetic field suggest that the perturbing quality factor of this high-conductivity enclosure, δq (enclosure) , is 1,870. when the high-conductivity enclosure was modified to include a 0.25 cm-thick layer of magnetic material with real relative permeability, μ′ r =40, and imaginary relative permeability, μ″ r =10 −2 , simulations suggest the perturbing quality factor is increased to δq (enclosure+magnetic material) =5,060. the improvement in performance due to the addition of thin layers of magnetic material 2702 may be even more dramatic if the high-conductivity enclosure fills a larger portion of the area circumscribed by the resonator's loop inductor 2704 . in the example above, if the radius of the inductor loop 2704 is reduced so that it is only 3 mm away from the surface of the high-conductivity enclosure, the perturbing quality factor may be improved from 670 (conducting enclosure only) to 2,730 (conducting enclosure with a thin layer of magnetic material) by the addition of a thin layer of magnetic material 2702 around the outside of the enclosure. the resonator structure may be designed to have highly confined electric fields, using shielding, or distributed capacitors, for example, which may yield high, even when the resonator is very close to materials that would typically induce loss. coupled electromagnetic resonators the efficiency of energy transfer between two resonators may be determined by the strong-coupling figure-of-merit, u=κ/√{square root over (γ s γ d )}=(2κ/√{square root over (ω s ω d )})√{square root over (q s q d )}. in magnetic resonator implementations the coupling factor between the two resonators may be related to the inductance of the inductive elements in each of the resonators, l 1 and l 2 , and the mutual inductance, m, between them by κ 12 =ωm/2√{square root over (l 1 l 2 )}. note that this expression assumes there is negligible coupling through electric-dipole coupling. for capacitively-loaded inductor loop resonators where the inductor loops are formed by circular conducting loops with n turns, separated by a distance d, and oriented as shown in fig. 1( b ), the mutual inductance is m=π/4·μ o n 1 n 2 (x 1 x 2 ) 2 /d 3 where x 1 , n 1 and x 2 , n 2 are the characteristic size and number of turns of the conductor loop of the first and second resonators respectively. note that this is a quasi-static result, and so assumes that the resonator's size is much smaller than the wavelength and the resonators' distance is much smaller than the wavelength, but also that their distance is at least a few times their size. for these circular resonators operated in the quasi-static limit and at mid-range distances, as described above, k=2κ/√{square root over (ω 1 ω 2 )}˜(√{square root over (x 1 x 2 )}/d) 3 . strong coupling (a large u) between resonators at mid-range distances may be established when the quality factors of the resonators are large enough to compensate for the small k at mid-range distances for electromagnetic resonators, if the two resonators include conducting parts, the coupling mechanism may be that currents are induced on one resonator due to electric and magnetic fields generated from the other. the coupling factor may be proportional to the flux of the magnetic field produced from the high-q inductive element in one resonator crossing a closed area of the high-q inductive element of the second resonator. coupled electromagnetic resonators with reduced interactions as described earlier, a high-conductivity material surface may be used to shape resonator fields such that they avoid lossy objects, p, in the vicinity of a resonator, thereby reducing the overall extraneous losses and maintaining a high q-insensitivity θ (p+cond. surface) of the resonator. however, such a surface may also lead to a perturbed coupling factor, k (p+cond. surface) , between resonators that is smaller than the perturbed coupling factor, k (p) and depends on the size, position, and orientation of the high-conductivity material relative to the resonators. for example, if high-conductivity materials are placed in the plane and within the area circumscribed by the inductive element of at least one of the magnetic resonators in a wireless energy transfer system, some of the magnetic flux through the area of the resonator, mediating the coupling, may be blocked and k may be reduced. consider again the example of fig. 19 . in the absence of the high-conductivity disk enclosure, a certain amount of the external magnetic flux may cross the circumscribed area of the loop. in the presence of the high-conductivity disk enclosure, some of this magnetic flux may be deflected or blocked and may no longer cross the area of the loop, thus leading to a smaller perturbed coupling factor k 12(p+cond. surfaces) . however, because the deflected magnetic-field lines may follow the edges of the high-conductivity surfaces closely, the reduction in the flux through the loop circumscribing the disk may be less than the ratio of the areas of the face of the disk to the area of the loop. one may use high-conductivity material structures, either alone, or combined with magnetic materials to optimize perturbed quality factors, perturbed coupling factors, or perturbed efficiencies. consider the example of fig. 21 . let the lossy object have a size equal to the size of the capacitively-loaded inductor loop resonator, thus filling its area a 2102 . a high-conductivity surface 1802 may be placed under the lossy object 1804 . let this be resonator 1 in a system of two coupled resonators 1 and 2 , and let us consider how u 12(object+cond. surface) scales compared to u 12 as the area a s 2104 of the conducting surface increases. without the conducting surface 1802 below the lossy object 1804 , the k-insensitivity, β 12(object) , may be approximately one, but the q-insensitivity, θ 1(object) , may be small, so the u-insensitivity ξ 12(object) may be small. where the high-conductivity surface below the lossy object covers the entire area of the inductor loop resonator (a s =a), k 12(object+cond. surface) may approach zero, because little flux is allowed to cross the inductor loop, so u 12(object+cond. surface) may approach zero. for intermediate sizes of the high-conductivity surface, the suppression of extrinsic losses and the associated q-insensitivity, θ 1(object+cond. surface) , may be large enough compared to θ 1(object) , while the reduction in coupling may not be significant and the associated k-insensitivity, β 12(object+cond.surface) , may be not much smaller than β 12(object) , so that the overall u 12(object+cond. surface) may be increased compared to u 12(object) . the optimal degree of avoiding of extraneous lossy objects via high-conductivity surfaces in a system of wireless energy transfer may depend on the details of the system configuration and the application. we describe using high-conductivity materials to either completely or partially enclose or cover loss inducing objects in the vicinity of high-q resonators as one potential method to achieve high perturbed q's for a system. however, using a good conductor alone to cover the objects may reduce the coupling of the resonators as described above, thereby reducing the efficiency of wireless power transfer. as the area of the conducting surface approaches the area of the magnetic resonator, for example, the perturbed coupling factor, k (p) , may approach zero, making the use of the conducting surface incompatible with efficient wireless power transfer. one approach to addressing the aforementioned problem is to place a layer of magnetic material around the high-conductivity materials because the additional layer of permeable material may present a lower reluctance path (compared to free space) for the deflected magnetic field to follow and may partially shield the electric conductor underneath it from incident magnetic flux. under some circumstances the lower reluctance path presented by the magnetic material may improve the electromagnetic coupling of the resonator to other resonators. decreases in the perturbed coupling factor associated with using conducting materials to tailor resonator fields so that they avoid lossy objects in and around high-q magnetic resonators may be at least partially recovered by including a layer of magnetic material along the outer surface or surfaces of the conducting materials. the magnetic materials may increase the perturbed coupling factor relative to its initial unperturbed value. note that the simulation results in fig. 26 show that an incident magnetic field may be deflected less by a layered magnetic material and conducting structure than by a conducting structure alone. if a magnetic resonator loop with a radius only slightly larger than that of the disks shown in figs. 26( a ) and 26 ( b ) circumscribed the disks, it is clear that more flux lines would be captured in the case illustrated in fig. 26( b ) than in fig. 26( a ), and therefore k (disk) would be larger for the case illustrated in fig. 26( b ). therefore, including a layer of magnetic material on the conducting material may improve the overall system performance. system analyses may be performed to determine whether these materials should be partially, totally, or minimally integrated into the resonator. as described above, fig. 27 depicts a layered conductor 2706 and magnetic material 2702 structure that may be appropriate for use when not all of a lossy material 2708 may be covered by a conductor and/or magnetic material structure. it was shown earlier that for a copper conductor disk with a 20 cm diameter and a 2 cm height, circumscribed by a resonator with an inductor loop radius of 11 cm and a wire radius a=1 mm, the calculated perturbing q for the copper cylinder was 1,870. if the resonator and the conducting disk shell are placed in a uniform magnetic field (aligned along the axis of symmetry of the inductor loop), we calculate that the copper conductor has an associated coupling factor insensitivity of 0.34. for comparison, we model the same arrangement but include a 0.25 cm-thick layer of magnetic material with a real relative permeability, μ′ r =40, and an imaginary relative permeability, μ″ r =10 −2 . using the same model and parameters described above, we find that the coupling factor insensitivity is improved to 0.64 by the addition of the magnetic material to the surface of the conductor. magnetic materials may be placed within the area circumscribed by the magnetic resonator to increase the coupling in wireless energy transfer systems. consider a solid sphere of a magnetic material with relative permeability, μ r , placed in an initially uniform magnetic field. in this example, the lower reluctance path offered by the magnetic material may cause the magnetic field to concentrate in the volume of the sphere. we find that the magnetic flux through the area circumscribed by the equator of the sphere is enhanced by a factor of 3μ r /(μ r +2), by the addition of the magnetic material. if μ r >>1, this enhancement factor may be close to 3. one can also show that the dipole moment of a system comprising the magnetic sphere circumscribed by the inductive element in a magnetic resonator would have its magnetic dipole enhanced by the same factor. thus, the magnetic sphere with high permeability practically triples the dipole magnetic coupling of the resonator. it is possible to keep most of this increase in coupling if we use a spherical shell of magnetic material with inner radius a, and outer radius b, even if this shell is on top of block or enclosure made from highly conducting materials. in this case, the enhancement in the flux through the equator is for μ r =1,000 and (a/b)=0.99, this enhancement factor is still 2.73, so it possible to significantly improve the coupling even with thin layers of magnetic material. as described above, structures containing magnetic materials may be used to realize magnetic resonators. fig. 16( a ) shows a 3 dimensional model of a copper and magnetic material structure 1600 driven by a square loop of current around the choke point at its center. fig. 16( b ) shows the interaction, indicated by magnetic field streamlines, between two identical structures 1600 a-b with the same properties as the one shown in fig. 16( a ). because of symmetry, and to reduce computational complexity, only one half of the system is modeled. if we fix the relative orientation between the two objects and vary their center-to-center distance (the image shown is at a relative separation of 50 cm), we find that, at 300 khz, the coupling efficiency varies from 87% to 55% as the separation between the structures varies from 30 cm to 60 cm. each of the example structures shown 1600 a-b includes two 20 cm×8 cm×2 cm parallelepipeds made of copper joined by a 4 cm×4 cm×2 cm block of magnetic material and entirely covered with a 2 mm layer of the same magnetic material (assumed to have μ r =1,400+j5). resistive losses in the driving loop are ignored. each structure has a calculated q of 815. electromagnetic resonators and impedance matching impedance matching architectures for low-loss inductive elements for purposes of the present discussion, an inductive element may be any coil or loop structure (the ‘loop’) of any conducting material, with or without a (gapped or ungapped) core made of magnetic material, which may also be coupled inductively or in any other contactless way to other systems. the element is inductive because its impedance, including both the impedance of the loop and the so-called ‘reflected’ impedances of any potentially coupled systems, has positive reactance, x, and resistance, r. consider an external circuit, such as a driving circuit or a driven load or a transmission line, to which an inductive element may be connected. the external circuit (e.g. a driving circuit) may be delivering power to the inductive element and the inductive element may be delivering power to the external circuit (e.g. a driven load). the efficiency and amount of power delivered between the inductive element and the external circuit at a desired frequency may depend on the impedance of the inductive element relative to the properties of the external circuit. impedance-matching networks and external circuit control techniques may be used to regulate the power delivery between the external circuit and the inductive element, at a desired frequency, f. the external circuit may be a driving circuit configured to form a amplifier of class a, b, c, d, de, e, f and the like, and may deliver power at maximum efficiency (namely with minimum losses within the driving circuit) when it is driving a resonant network with specific impedance z* o , where z o may be complex and * denotes complex conjugation. the external circuit may be a driven load configured to form a rectifier of class a, b, c, d, de, e, f and the like, and may receive power at maximum efficiency (namely with minimum losses within the driven load) when it is driven by a resonant network with specific impedance z* o , where z o may be complex. the external circuit may be a transmission line with characteristic impedance, z o , and may exchange power at maximum efficiency (namely with zero reflections) when connected to an impedance z* o . we will call the characteristic impedance z o of an external circuit the complex conjugate of the impedance that may be connected to it for power exchange at maximum efficiency. typically the impedance of an inductive element, r+jx, may be much different from z* o . for example, if the inductive element has low loss (a high x/r), its resistance, r, may be much lower than the real part of the characteristic impedance, z 0 , of the external circuit. furthermore, an inductive element by itself may not be a resonant network. an impedance-matching network connected to an inductive element may typically create a resonant network, whose impedance may be regulated. therefore, an impedance-matching network may be designed to maximize the efficiency of the power delivered between the external circuit and the inductive element (including the reflected impedances of any coupled systems). the efficiency of delivered power may be maximized by matching the impedance of the combination of an impedance-matching network and an inductive element to the characteristic impedance of an external circuit (or transmission line) at the desired frequency. an impedance-matching network may be designed to deliver a specified amount of power between the external circuit and the inductive element (including the reflected impedances of any coupled systems). the delivered power may be determined by adjusting the complex ratio of the impedance of the combination of the impedance-matching network and the inductive element to the impedance of the external circuit (or transmission line) at the desired frequency. impedance-matching networks connected to inductive elements may create magnetic resonators. for some applications, such as wireless power transmission using strongly-coupled magnetic resonators, a high q may be desired for the resonators. therefore, the inductive element may be chosen to have low losses (high x/r). since the matching circuit may typically include additional sources of loss inside the resonator, the components of the matching circuit may also be chosen to have low losses. furthermore, in high-power applications and/or due to the high resonator q, large currents may run in parts of the resonator circuit and large voltages may be present across some circuit elements within the resonator. such currents and voltages may exceed the specified tolerances for particular circuit elements and may be too high for particular components to withstand. in some cases, it may be difficult to find or implement components, such as tunable capacitors for example, with size, cost and performance (loss and current/voltage-rating) specifications sufficient to realize high-q and high-power resonator designs for certain applications. we disclose matching circuit designs, methods, implementations and techniques that may preserve the high q for magnetic resonators, while reducing the component requirements for low loss and/or high current/voltage-rating. matching-circuit topologies may be designed that minimize the loss and current-rating requirements on some of the elements of the matching circuit. the topology of a circuit matching a low-loss inductive element to an impedance, z 0 , may be chosen so that some of its components lie outside the associated high-q resonator by being in series with the external circuit. the requirements for low series loss or high current-ratings for these components may be reduced. relieving the low series loss and/or high-current-rating requirement on a circuit element may be particularly useful when the element needs to be variable and/or to have a large voltage-rating and/or low parallel loss. matching-circuit topologies may be designed that minimize the voltage rating requirements on some of the elements of the matching circuit. the topology of a circuit matching a low-loss inductive element to an impedance, z 0 , may be chosen so that some of its components lie outside the associated high-q resonator by being in parallel with z 0 . the requirements for low parallel loss or high voltage-rating for these components may be reduced. relieving the low parallel loss and/or high-voltage requirement on a circuit element may be particularly useful when the element needs to be variable and/or to have a large current-rating and/or low series loss. the topology of the circuit matching a low-loss inductive element to an external characteristic impedance, z 0 , may be chosen so that the field pattern of the associated resonant mode and thus its high q are preserved upon coupling of the resonator to the external impedance. otherwise inefficient coupling to the desired resonant mode may occur (potentially due to coupling to other undesired resonant modes), resulting in an effective lowering of the resonator q. for applications where the low-loss inductive element or the external circuit, may exhibit variations, the matching circuit may need to be adjusted dynamically to match the inductive element to the external circuit impedance, z 0 , at the desired frequency, f. since there may typically be two tuning objectives, matching or controlling both the real and imaginary part of the impedance level, z 0 , at the desired frequency, f, there may be two variable elements in the matching circuit. for inductive elements, the matching circuit may need to include at least one variable capacitive element. a low-loss inductive element may be matched by topologies using two variable capacitors, or two networks of variable capacitors. a variable capacitor may, for example, be a tunable butterfly-type capacitor having, e.g., a center terminal for connection to a ground or other lead of a power source or load, and at least one other terminal across which a capacitance of the tunable butterfly-type capacitor can be varied or tuned, or any other capacitor having a user-configurable, variable capacitance. a low-loss inductive element may be matched by topologies using one, or a network of, variable capacitor(s) and one, or a network of, variable inductor(s). a low-loss inductive element may be matched by topologies using one, or a network of, variable capacitor(s) and one, or a network of, variable mutual inductance(s), which transformer-couple the inductive element either to an external circuit or to other systems. in some cases, it may be difficult to find or implement tunable lumped elements with size, cost and performance specifications sufficient to realize high-q, high-power, and potentially high-speed, tunable resonator designs. the topology of the circuit matching a variable inductive element to an external circuit may be designed so that some of the variability is assigned to the external circuit by varying the frequency, amplitude, phase, waveform, duty cycle, and the like, of the drive signals applied to transistors, diodes, switches and the like, in the external circuit. the variations in resistance, r, and inductance, l, of an inductive element at the resonant frequency may be only partially compensated or not compensated at all. adequate system performance may thus be preserved by tolerances designed into other system components or specifications. partial adjustments, realized using fewer tunable components or less capable tunable components, may be sufficient. matching-circuit architectures may be designed that achieve the desired variability of the impedance matching circuit under high-power conditions, while minimizing the voltage/current rating requirements on its tunable elements and achieving a finer (i.e. more precise, with higher resolution) overall tunability. the topology of the circuit matching a variable inductive element to an impedance, z 0 , may include appropriate combinations and placements of fixed and variable elements, so that the voltage/current requirements for the variable components may be reduced and the desired tuning range may be covered with finer tuning resolution. the voltage/current requirements may be reduced on components that are not variable. the disclosed impedance matching architectures and techniques may be used to achieve the following: to maximize the power delivered to, or to minimize impedance mismatches between, the source low-loss inductive elements (and any other systems wirelessly coupled to them) from the power driving generators.to maximize the power delivered from, or to minimize impedance mismatches between, the device low-loss inductive elements (and any other systems wirelessly coupled to them) to the power driven loads.to deliver a controlled amount of power to, or to achieve a certain impedance relationship between, the source low-loss inductive elements (and any other systems wirelessly coupled to them) from the power driving generators.to deliver a controlled amount of power from, or to achieve a certain impedance relationship between, the device low-loss inductive elements (and any other systems wirelessly coupled to them) to the power driven loads. topologies for preservation of mode profile (high-q) the resonator structure may be designed to be connected to the generator or the load wirelessly (indirectly) or with a hard-wired connection (directly). consider a general indirectly coupled matching topology such as that shown by the block diagram in fig. 28( a ). there, an inductive element 2802 , labeled as (r,l) and represented by the circuit symbol for an inductor, may be any of the inductive elements discussed in this disclosure or in the references provided herein, and where an impedance-matching circuit 2402 includes or consists of parts a and b. b may be the part of the matching circuit that connects the impedance 2804 , z 0 , to the rest of the circuit (the combination of a and the inductive element (a+(r,l)) via a wireless connection (an inductive or capacitive coupling mechanism). the combination of a and the inductive element 2802 may form a resonator 102 , which in isolation may support a high-q resonator electromagnetic mode, with an associated current and charge distribution. the lack of a wired connection between the external circuit, z 0 and b, and the resonator, a+(r,l), may ensure that the high-q resonator electromagnetic mode and its current/charge distributions may take the form of its intrinsic (in-isolation) profile, so long as the degree of wireless coupling is not too large. that is, the electromagnetic mode, current/charge distributions, and thus the high-q of the resonator may be automatically maintained using an indirectly coupled matching topology. this matching topology may be referred to as indirectly coupled, or transformer-coupled, or inductively-coupled, in the case where inductive coupling is used between the external circuit and the inductor loop. this type of coupling scenario was used to couple the power supply to the source resonator and the device resonator to the light bulb in the demonstration of wireless energy transfer over mid-range distances described in the referenced science article. next consider examples in which the inductive element may include the inductive element and any indirectly coupled systems. in this case, as disclosed above, and again because of the lack of a wired connection between the external circuit or the coupled systems and the resonator, the coupled systems may not, with good approximation for not-too-large degree of indirect coupling, affect the resonator electromagnetic mode profile and the current/charge distributions of the resonator. therefore, an indirectly-coupled matching circuit may work equally well for any general inductive element as part of a resonator as well as for inductive elements wirelessly-coupled to other systems, as defined herein. throughout this disclosure, the matching topologies we disclose refer to matching topologies for a general inductive element of this type, that is, where any additional systems may be indirectly coupled to the low-loss inductive element, and it is to be understood that those additional systems do not greatly affect the resonator electromagnetic mode profile and the current/charge distributions of the resonator. based on the argument above, in a wireless power transmission system of any number of coupled source resonators, device resonators and intermediate resonators the wireless magnetic (inductive) coupling between resonators does not affect the electromagnetic mode profile and the current/charge distributions of each one of the resonators. therefore, when these resonators have a high (unloaded and unperturbed) q, their (unloaded and unperturbed) q may be preserved in the presence of the wireless coupling. (note that the loaded q of a resonator may be reduced in the presence of wireless coupling to another resonator, but we may be interested in preserving the unloaded q, which relates only to loss mechanisms and not to coupling/loading mechanisms.) consider a matching topology such as is shown in fig. 28( b ). the capacitors shown in fig. 28( b ) may represent capacitor circuits or networks. the capacitors shown may be used to form the resonator 102 and to adjust the frequency and/or impedance of the source and device resonators. this resonator 102 may be directly coupled to an impedance, z 0 , using the ports labeled “terminal connections” 2808 . fig. 28( c ) shows a generalized directly coupled matching topology, where the impedance-matching circuit 2602 includes or consists of parts a, b and c. here, circuit elements in a, b and c may be considered part of the resonator 102 as well as part of the impedance matching 2402 (and frequency tuning) topology. b and c may be the parts of the matching circuit 2402 that connect the impedance z 0 2804 (or the network terminals) to the rest of the circuit (a and the inductive element) via a single wire connection each. note that b and c could be empty (short-circuits). if we disconnect or open circuit parts b and c (namely those single wire connections), then, the combination of a and the inductive element (r,l) may form the resonator. the high-q resonator electromagnetic mode may be such that the profile of the voltage distribution along the inductive element has nodes, namely positions where the voltage is zero. one node may be approximately at the center of the length of the inductive element, such as the center of the conductor used to form the inductive element, (with or without magnetic materials) and at least one other node may be within a. the voltage distribution may be approximately anti-symmetric along the inductive element with respect to its voltage node. a high q may be maintained by designing the matching topology (a, b, c) and/or the terminal voltages (v 1 , v 2 ) so that this high-q resonator electromagnetic mode distribution may be approximately preserved on the inductive element. this high-q resonator electromagnetic mode distribution may be approximately preserved on the inductive element by preserving the voltage node (approximately at the center) of the inductive element. examples that achieve these design goals are provided herein. a, b, and c may be arbitrary (namely not having any special symmetry), and v 1 and v 2 may be chosen so that the voltage across the inductive element is symmetric (voltage node at the center inductive). these results may be achieved using simple matching circuits but potentially complicated terminal voltages, because a topology-dependent common-mode signal (v 1 +v 2 )/2 may be required on both terminals. consider an ‘axis’ that connects all the voltage nodes of the resonator, where again one node is approximately at the center of the length of the inductive element and the others within a. (note that the ‘axis’ is really a set of points (the voltage nodes) within the electric-circuit topology and may not necessarily correspond to a linear axis of the actual physical structure. the ‘axis’ may align with a physical axis in cases where the physical structure has symmetry.) two points of the resonator are electrically symmetric with respect to the ‘axis’, if the impedances seen between each of the two points and a point on the ‘axis’, namely a voltage-node point of the resonator, are the same. b and c may be the same (c=b), and the two terminals may be connected to any two points of the resonator (a+(r,l)) that are electrically symmetric with respect to the ‘axis’ defined above and driven with opposite voltages (v 2 =−v 1 ) as shown in fig. 28( d ). the two electrically symmetric points of the resonator 102 may be two electrically symmetric points on the inductor loop. the two electrically symmetric points of the resonator may be two electrically symmetric points inside a. if the two electrically symmetric points, (to which each of the equal parts b and c is connected), are inside a, a may need to be designed so that these electrically-symmetric points are accessible as connection points within the circuit. this topology may be referred to as a ‘balanced drive’ topology. these balanced-drive examples may have the advantage that any common-mode signal that may be present on the ground line, due to perturbations at the external circuitry or the power network, for example, may be automatically rejected (and may not reach the resonator). in some balanced-drive examples, this topology may require more components than other topologies. in other examples, c may be chosen to be a short-circuit and the corresponding terminal to be connected to ground (v=0) and to any point on the electric-symmetry (zero-voltage) ‘axis’ of the resonator, and b to be connected to any other point of the resonator not on the electric-symmetry ‘axis’, as shown in fig. 28( e ). the ground-connected point on the electric-symmetry ‘axis’ may be the voltage node on the inductive element, approximately at the center of its conductor length. the ground-connected point on the electric-symmetry ‘axis’ may be inside the circuit a. where the ground-connected point on the electric-symmetry ‘axis’ is inside a, a may need to be designed to include one such point on the electrical-symmetric ‘axis’ that is electrically accessible, namely where connection is possible. this topology may be referred to as an ‘unbalanced drive’ topology. the approximately anti-symmetric voltage distribution of the electromagnetic mode along the inductive element may be approximately preserved, even though the resonator may not be driven exactly symmetrically. the reason is that the high q and the large associated r-vs.-z 0 mismatch necessitate that a small current may run through b and ground, compared to the much larger current that may flow inside the resonator, (a+(r,l)). in this scenario, the perturbation on the resonator mode may be weak and the location of the voltage node may stay at approximately the center location of the inductive element. these unbalanced-drive examples may have the advantage that they may be achieved using simple matching circuits and that there is no restriction on the driving voltage at the v 1 terminal. in some unbalanced-drive examples, additional designs may be required to reduce common-mode signals that may appear at the ground terminal. the directly-coupled impedance-matching circuit, generally including or consisting of parts a, b and c, as shown in fig. 28( c ), may be designed so that the wires and components of the circuit do not perturb the electric and magnetic field profiles of the electromagnetic mode of the inductive element and/or the resonator and thus preserve the high resonator q. the wires and metallic components of the circuit may be oriented to be perpendicular to the electric field lines of the electromagnetic mode. the wires and components of the circuit may be placed in regions where the electric and magnetic field of the electromagnetic mode are weak. topologies for alleviating low-series-loss and high-current-rating requirements on elements if the matching circuit used to match a small resistance, r, of a low-loss inductive element to a larger characteristic impedance, z 0 , of an external circuit may be considered lossless, then i z o 2 z o =i r 2 r i z o /i r =√{square root over (r/z o )} and the current flowing through the terminals is much smaller than the current flowing through the inductive element. therefore, elements connected immediately in series with the terminals (such as in directly-coupled b, c ( fig. 28( c ))) may not carry high currents. then, even if the matching circuit has lossy elements, the resistive loss present in the elements in series with the terminals may not result in a significant reduction in the high-q of the resonator. that is, resistive loss in those series elements may not significantly reduce the efficiency of power transmission from z 0 to the inductive element or vice versa. therefore, strict requirements for low-series-loss and/or high current-ratings may not be necessary for these components. in general, such reduced requirements may lead to a wider selection of components that may be designed into the high-q and/or high-power impedance matching and resonator topologies. these reduced requirements may be especially helpful in expanding the variety of variable and/or high voltage and/or low-parallel-loss components that may be used in these high-q and/or high-power impedance-matching circuits. topologies for alleviating low-parallel-loss and high-voltage-rating requirements on elements if, as above, the matching circuit used to match a small resistance, r, of a low-loss inductive element to a larger characteristic impedance, z 0 , of an external circuit is lossless, then using the previous analysis, | v z o /v load |=|i z o z o /i r ( r+jx )|≈√{square root over ( r/z o )}· z o /x= √{square root over ( z o /r )}/( x/r ), and, for a low-loss (high-x/r) inductive element, the voltage across the terminals may be typically much smaller than the voltage across the inductive element. therefore, elements connected immediately in parallel to the terminals may not need to withstand high voltages. then, even if the matching circuit has lossy elements, the resistive loss present in the elements in parallel with the terminals may not result in a significant reduction in the high-q of the resonator. that is, resistive loss in those parallel elements may not significantly reduce the efficiency of power transmission from z 0 to the inductive element or vice versa. therefore, strict requirements for low-parallel-loss and/or high voltage-ratings may not be necessary for these components. in general, such reduced requirements may lead to a wider selection of components that may be designed into the high-q and/or high-power impedance matching and resonator topologies. these reduced requirements may be especially helpful in expanding the variety of variable and/or high current and/or low-series-loss components that may be used in these high-q and/or high-power impedance-matching and resonator circuits. note that the design principles above may reduce currents and voltages on various elements differently, as they variously suggest the use of networks in series with z 0 (such as directly-coupled b, c) or the use of networks in parallel with z 0 . the preferred topology for a given application may depend on the availability of low-series-loss/high-current-rating or low-parallel-loss/high-voltage-rating elements. combinations of fixed and variable elements for achieving fine tunability and alleviating high-rating requirements on variable elements circuit topologies variable circuit elements with satisfactory low-loss and high-voltage or current ratings may be difficult or expensive to obtain. in this disclosure, we describe impedance-matching topologies that may incorporate combinations of fixed and variable elements, such that large voltages or currents may be assigned to fixed elements in the circuit, which may be more likely to have adequate voltage and current ratings, and alleviating the voltage and current rating requirements on the variable elements in the circuit. variable circuit elements may have tuning ranges larger than those required by a given impedance-matching application and, in those cases, fine tuning resolution may be difficult to obtain using only such large-range elements. in this disclosure, we describe impedance-matching topologies that incorporate combinations of both fixed and variable elements, such that finer tuning resolution may be accomplished with the same variable elements. therefore, topologies using combinations of both fixed and variable elements may bring two kinds of advantages simultaneously: reduced voltage across, or current through, sensitive tuning components in the circuit and finer tuning resolution. note that the maximum achievable tuning range may be related to the maximum reduction in voltage across, or current through, the tunable components in the circuit designs. element topologies a single variable circuit-element (as opposed to the network of elements discussed above) may be implemented by a topology using a combination of fixed and variable components, connected in series or in parallel, to achieve a reduction in the rating requirements of the variable components and a finer tuning resolution. this can be demonstrated mathematically by the fact that: if x |total| =x |fixed| +x |variable| , then δ x |total| /x |total| =δx |variable| /( x |fixed| +x |variable| ), and x variable /x total =x variable /( x fixed +x variable ), where x |subscript| is any element value (e.g. capacitance, inductance), x is voltage or current, and the “+ sign” denotes the appropriate (series-addition or parallel-addition) combination of elements. note that the subscript format for x |subscript| , is chosen to easily distinguish it from the radius of the area enclosed by a circular inductive element (e.g. x, x 1 , etc.). furthermore, this principle may be used to implement a variable electric element of a certain type (e.g. a capacitance or inductance) by using a variable element of a different type, if the latter is combined appropriately with other fixed elements. in conclusion, one may apply a topology optimization algorithm that decides on the required number, placement, type and values of fixed and variable elements with the required tunable range as an optimization constraint and the minimization of the currents and/or voltages on the variable elements as the optimization objective. examples in the following schematics, we show different specific topology implementations for impedance matching to and resonator designs for a low-loss inductive element. in addition, we indicate for each topology: which of the principles described above are used, the equations giving the values of the variable elements that may be used to achieve the matching, and the range of the complex impedances that may be matched (using both inequalities and a smith-chart description). for these examples, we assume that z 0 is real, but an extension to a characteristic impedance with a non-zero imaginary part is straightforward, as it implies only a small adjustment in the required values of the components of the matching network. we will use the convention that the subscript, n, on a quantity implies normalization to (division by) z 0 . fig. 29 shows two examples of a transformer-coupled impedance-matching circuit, where the two tunable elements are a capacitor and the mutual inductance between two inductive elements. if we define respectively x 2 =ωl 2 for fig. 29( a ) and x 2 =ωl 2 −1/ωc 2 for fig. 29( b ), and x≡ωl, then the required values of the tunable elements are: for the topology of fig. 29( b ), an especially straightforward design may be to choose x 2 =0. in that case, these topologies may match the impedances satisfying the inequalities: r n >0, x n >0, which are shown by the area enclosed by the bold lines on the smith chart of fig. 29( c ). given a well pre-chosen fixed m, one can also use the above matching topologies with a tunable c 2 instead. fig. 30 shows six examples (a)-(f) of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors, and six examples (h)-(m) of directly-coupled impedance-matching circuits, where the two tunable elements are one capacitor and one inductor. for the topologies of figs. 30( a ),( b ),( c ),( h ),( i ),( j ), a common-mode signal may be required at the two terminals to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( c ). for the symmetric topologies of figs. 30( d ),( e ),( f ),( k ),( l ),( m ), the two terminals may need to be driven anti-symmetrically (balanced drive) to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( d ). it will be appreciated that a network of capacitors, as used herein, may in general refer to any circuit topology including one or more capacitors, including without limitation any of the circuits specifically disclosed herein using capacitors, or any other equivalent or different circuit structure(s), unless another meaning is explicitly provided or otherwise clear from the context. let us define respectively z=r+jωl for figs. 30( a ),( d ),( h ),( k ), z=r+jωl+1/jωc 3 for figs. 30( b ),( e ),( i ),( l ), and z=(r+jωl)∥(1/jωc 3 ) for figs. 30( c ),( f ),( j ),( m ), where the symbol “∥” means “the parallel combination of”, and then r≡re{z}, x≡im{z}. then, for figs. 30( a )-( f ) the required values of the tunable elements may be given by: and these topologies can match the impedances satisfying the inequalities: r n ≦1, x n ≧√{square root over ( r n (1− r n ))} which are shown by the area enclosed by the bold lines on the smith chart of fig. 30( g ). for figs. 30( h )-( m ) the required values of the tunable elements may be given by: fig. 31 shows three examples (a)-(c) of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors, and three examples (e)-(g) of directly-coupled impedance-matching circuits, where the two tunable elements are one capacitor and one inductor. for the topologies of figs. 31( a ),( b ),( c ),( e ),( f ),( g ), the ground terminal is connected between two equal-value capacitors, 2 c 1 , (namely on the axis of symmetry of the main resonator) to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( e ). let us define respectively z=r+jωl for figs. 31( a ),( e ), z=r+jωl+1/jωc 3 for figs. 31( b ),( f ), and z=(r+jωl)∥(1/jωc 3 ) for fig. 31( c ),( g ), and then r≡re{z}, x≡im{z}. then, for figs. 31( a )-( c ) the required values of the tunable elements may be given by: and these topologies can match the impedances satisfying the inequalities: which are shown by the area enclosed by the bold lines on the smith chart of fig. 31( d ). for figs. 31( e )-( g ) the required values of the tunable elements may be given by: fig. 32 shows three examples (a)-(c) of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors, and three examples (e)-(g) of directly-coupled impedance-matching circuits, where the two tunable elements are one capacitor and one inductor. for the topologies of figs. 32( a ),( b ),( c ),( e ),( f ),( g ), the ground terminal may be connected at the center of the inductive element to preserve the voltage node of the resonator at that point and thus the high q. note that these example may be described as implementations of the general topology shown in fig. 28( e ). let us define respectively z=r+jωl for fig. 32( a ), z=r+jωl+1/jωc 3 for fig. 32( b ), and z=(r+jωl)∥(1/jωc 3 ) for fig. 32( c ), and then r≡re{z}, x≡im{z}. then, for figs. 32( a )-( c ) the required values of the tunable elements may be given by: where k is defined by m′=kl′, where l′ is the inductance of each half of the inductor loop and m′ is the mutual inductance between the two halves, and these topologies can match the impedances satisfying the inequalities: r n ≦2, x n ≧√{square root over (2 r n (2− r n ))} which are shown by the area enclosed by the bold lines on the smith chart of fig. 32( d ). for figs. 32( e )-( g ) the required values of the tunable elements may be given by: in the circuits of figs. 30 , 31 , 32 , the capacitor, c 2 , or the inductor, l 2 , is (or the two capacitors, 2 c 2 , or the two inductors, l 2 /2, are) in series with the terminals and may not need to have very low series-loss or withstand a large current. fig. 33 shows six examples (a)-(f) of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors, and six examples (h)-(m) of directly-coupled impedance-matching circuits, where the two tunable elements are one capacitor and one inductor. for the topologies of figs. 33( a ),( b ),( c ),( h ),( i ),( j ), a common-mode signal may be required at the two terminals to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( c ), where b and c are short-circuits and a is not balanced. for the symmetric topologies of figs. 33( d ),( e ),( f ),( k ),( l ),( m ), the two terminals may need to be driven anti-symmetrically (balanced drive) to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( d ), where b and c are short-circuits and a is balanced. let us define respectively z=r+jωl for figs. 33( a ),( d ),( h ),( k ), z=r+jωl+1/jωc 3 for figs. 33( b ),( e ),( i ),( l ), and z=(r+jωl)∥(1/jωc 3 ) for figs. 33( c ),( f ),( j ),( m ), and then r≡re{z}, x≡im{z}. then, for figs. 33( a )-( f ) the required values of the tunable elements may be given by: and these topologies can match the impedances satisfying the inequalities: r n ≦1, x n ≧√{square root over ( r n (1− r n ))} which are shown by the area enclosed by the bold lines on the smith chart of fig. 33( g ). for figs. 35( h )-( m ) the required values of the tunable elements may be given by: fig. 34 shows three examples (a)-(c) of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors, and three examples (e)-(g) of directly-coupled impedance-matching circuits, where the two tunable elements are one capacitor and one inductor. for the topologies of figs. 34( a ),( b ),( c ),( e ),( f ),( g ), the ground terminal is connected between two equal-value capacitors, 2 c 2 , (namely on the axis of symmetry of the main resonator) to preserve the voltage node of the resonator at the center of the inductive element and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( e ). let us define respectively z=r+jωl for fig. 34( a ),( e ), z=r+jωl+1/jωc 3 for fig. 34( b ),( f ), and z=(r+jωl)∥(1/jωc 3 ) for fig. 34( c ),( g ), and then r≡re{z}, x≡im{z}. then, for figs. 34( a )-( c ) the required values of the tunable elements may be given by: and these topologies can match the impedances satisfying the inequalities: which are shown by the area enclosed by the bold lines on the smith chart of fig. 34( d ). for figs. 34( e )-( g ) the required values of the tunable elements may be given by: fig. 35 shows three examples of directly-coupled impedance-matching circuits, where the two tunable elements are capacitors. for the topologies of figs. 35 , the ground terminal may be connected at the center of the inductive element to preserve the voltage node of the resonator at that point and thus the high q. note that these examples may be described as implementations of the general topology shown in fig. 28( e ). let us define respectively z=r+jωl for fig. 35( a ), z=r+jωl+1/jωc 3 for fig. 35( b ), and z=(r+jωl)∥(1/jωc 3 ) for fig. 35( c ), and then r≡re{z}, x≡im{z}. then, the required values of the tunable elements may be given by: where and k is defined by m′=kl′, where l′ is the inductance of each half of the inductive element and m′ is the mutual inductance between the two halves. these topologies can match the impedances satisfying the inequalities: which are shown by the area enclosed by the bold lines on the three smith charts shown in fig. 35( d ) for k=0, fig. 35( e ) for k=0.05, and fig. 35( f ) for k=1. note that for 0<k<1 there are two disconnected regions of the smith chart that this topology can match. in the circuits of figs. 33 , 34 , 35 , the capacitor, c 2 , or the inductor, l 2 , is (or one of the two capacitors, 2 c 2 , or one of the two inductors, 2 l 2 , are) in parallel with the terminals and thus may not need to have a high voltage-rating. in the case of two capacitors, 2 c 2 , or two inductors, 2 l 2 , both may not need to have a high voltage-rating, since approximately the same current flows through them and thus they experience approximately the same voltage across them. for the topologies of figs. 30-35 , where a capacitor, c 3 , is used, the use of the capacitor, c 3 , may lead to finer tuning of the frequency and the impedance. for the topologies of figs. 30-35 , the use of the fixed capacitor, c 3 , in series with the inductive element may ensure that a large percentage of the high inductive-element voltage will be across this fixed capacitor, c 3 , thus potentially alleviating the voltage rating requirements for the other elements of the impedance matching circuit, some of which may be variable. whether or not such topologies are preferred depends on the availability, cost and specifications of appropriate fixed and tunable components. in all the above examples, a pair of equal-value variable capacitors without a common terminal may be implemented using ganged-type capacitors or groups or arrays of varactors or diodes biased and controlled to tune their values as an ensemble. a pair of equal-value variable capacitors with one common terminal can be implemented using a tunable butterfly-type capacitor or any other tunable or variable capacitor or group or array of varactors or diodes biased and controlled to tune their capacitance values as an ensemble. another criterion which may be considered upon the choice of the impedance matching network is the response of the network to different frequencies than the desired operating frequency. the signals generated in the external circuit, to which the inductive element is coupled, may not be monochromatic at the desired frequency but periodic with the desired frequency, as for example the driving signal of a switching amplifier or the reflected signal of a switching rectifier. in some such cases, it may be desirable to suppress the amount of higher-order harmonics that enter the inductive element (for example, to reduce radiation of these harmonics from this element). then the choice of impedance matching network may be one that sufficiently suppresses the amount of such harmonics that enters the inductive element. the impedance matching network may be such that the impedance seen by the external circuit at frequencies higher than the fundamental harmonic is high, when the external periodic signal is a signal that can be considered to behave as a voltage-source signal (such as the driving signal of a class-d amplifier with a series resonant load), so that little current flows through the inductive element at higher frequencies. among the topologies of figs. 30-35 , those which use an inductor, l 2 , may then be preferable, as this inductor presents a high impedance at high frequencies. the impedance matching network may be such that the impedance seen by the external circuit at frequencies higher than the fundamental harmonic is low, when the external periodic signal is a signal that can be considered to behave as a current-source signal, so that little voltage is induced across the inductive element at higher frequencies. among the topologies of figs. 30-35 , those which use a capacitor, c 2 , are then preferable, as this capacitor presents a low impedance at high frequencies. fig. 36 shows four examples of a variable capacitance, using networks of one variable capacitor and the rest fixed capacitors. using these network topologies, fine tunability of the total capacitance value may be achieved. furthermore, the topologies of figs. 36( a ),( c ),( d ), may be used to reduce the voltage across the variable capacitor, since most of the voltage may be assigned across the fixed capacitors. fig. 37 shows two examples of a variable capacitance, using networks of one variable inductor and fixed capacitors. in particular, these networks may provide implementations for a variable reactance, and, at the frequency of interest, values for the variable inductor may be used such that each network corresponds to a net negative variable reactance, which may be effectively a variable capacitance. tunable elements such as tunable capacitors and tunable inductors may be mechanically-tunable, electrically-tunable, thermally-tunable and the like. the tunable elements may be variable capacitors or inductors, varactors, diodes, schottky diodes, reverse-biased pn diodes, varactor arrays, diode arrays, schottky diode arrays and the like. the diodes may be si diodes, gan diodes, sic diodes, and the like. gan and sic diodes may be particularly attractive for high power applications. the tunable elements may be electrically switched capacitor banks, electrically-switched mechanically-tunable capacitor banks, electrically-switched varactor-array banks, electrically-switched transformer-coupled inductor banks, and the like. the tunable elements may be combinations of the elements listed above. as described above, the efficiency of the power transmission between coupled high-q magnetic resonators may be impacted by how closely matched the resonators are in resonant frequency and how well their impedances are matched to the power supplies and power consumers in the system. because a variety of external factors including the relative position of extraneous objects or other resonators in the system, or the changing of those relative positions, may alter the resonant frequency and/or input impedance of a high-q magnetic resonator, tunable impedance networks may be required to maintain sufficient levels of power transmission in various environments or operating scenarios. the capacitance values of the capacitors shown may be adjusted to adjust the resonant frequency and/or the impedance of the magnetic resonator. the capacitors may be adjusted electrically, mechanically, thermally, or by any other known methods. they may be adjusted manually or automatically, such as in response to a feedback signal. they may be adjusted to achieve certain power transmission efficiencies or other operating characteristics between the power supply and the power consumer. the inductance values of the inductors and inductive elements in the resonator may be adjusted to adjust the frequency and/or impedance of the magnetic resonator. the inductance may be adjusted using coupled circuits that include adjustable components such as tunable capacitors, inductors and switches. the inductance may be adjusted using transformer coupled tuning circuits. the inductance may be adjusted by switching in and out different sections of conductor in the inductive elements and/or using ferro-magnetic tuning and/or mu-tuning, and the like. the resonant frequency of the resonators may be adjusted to or may be allowed to change to lower or higher frequencies. the input impedance of the resonator may be adjusted to or may be allowed to change to lower or higher impedance values. the amount of power delivered by the source and/or received by the devices may be adjusted to or may be allowed to change to lower or higher levels of power. the amount of power delivered to the source and/or received by the devices from the device resonator may be adjusted to or may be allowed to change to lower or higher levels of power. the resonator input impedances, resonant frequencies, and power levels may be adjusted depending on the power consumer or consumers in the system and depending on the objects or materials in the vicinity of the resonators. the resonator input impedances, frequencies, and power levels may be adjusted manually or automatically, and may be adjusted in response to feedback or control signals or algorithms. circuit elements may be connected directly to the resonator, that is, by physical electrical contact, for example to the ends of the conductor that forms the inductive element and/or the terminal connectors. the circuit elements may be soldered to, welded to, crimped to, glued to, pinched to, or closely position to the conductor or attached using a variety of electrical components, connectors or connection techniques. the power supplies and the power consumers may be connected to magnetic resonators directly or indirectly or inductively. electrical signals may be supplied to, or taken from, the resonators through the terminal connections. it is to be understood by one of ordinary skill in the art that in real implementations of the principles described herein, there may be an associated tolerance, or acceptable variation, to the values of real components (capacitors, inductors, resistors and the like) from the values calculated via the herein stated equations, to the values of real signals (voltages, currents and the like) from the values suggested by symmetry or anti-symmetry or otherwise, and to the values of real geometric locations of points (such as the point of connection of the ground terminal close to the center of the inductive element or the ‘axis’ points and the like) from the locations suggested by symmetry or otherwise. examples system block diagrams we disclose examples of high-q resonators for wireless power transmission systems that may wirelessly power or charge devices at mid-range distances. high-q resonator wireless power transmission systems also may wirelessly power or charge devices with magnetic resonators that are different in size, shape, composition, arrangement, and the like, from any source resonators in the system. fig. 1( a )(b) shows high level diagrams of two exemplary two-resonator systems. these exemplary systems each have a single source resonator 102 s or 104 s and a single device resonator 102 d or 104 d. fig. 38 shows a high level block diagram of a system with a few more features highlighted. the wirelessly powered or charged device 2310 may include or consist of a device resonator 102 d, device power and control circuitry 2304 , and the like, along with the device 2308 or devices, to which either dc or ac or both ac and dc power is transferred. the energy or power source for a system may include the source power and control circuitry 2302 , a source resonator 102 s, and the like. the device 2308 or devices that receive power from the device resonator 102 d and power and control circuitry 2304 may be any kind of device 2308 or devices as described previously. the device resonator 102 d and circuitry 2304 delivers power to the device/devices 2308 that may be used to recharge the battery of the device/devices, power the device/devices directly, or both when in the vicinity of the source resonator 102 s. the source and device resonators may be separated by many meters or they may be very close to each other or they may be separated by any distance in between. the source and device resonators may be offset from each other laterally or axially. the source and device resonators may be directly aligned (no lateral offset), or they may be offset by meters, or anything in between. the source and device resonators may be oriented so that the surface areas enclosed by their inductive elements are approximately parallel to each other. the source and device resonators may be oriented so that the surface areas enclosed by their inductive elements are approximately perpendicular to each other, or they may be oriented for any relative angle (0 to 360 degrees) between them. the source and device resonators may be free standing or they may be enclosed in an enclosure, container, sleeve or housing. these various enclosures may be composed of almost any kind of material. low loss tangent materials such as teflon, rexolite, styrene, and the like may be preferable for some applications. the source and device resonators may be integrated in the power supplies and power consumers. for example, the source and device resonators may be integrated into keyboards, computer mice, displays, cell phones, etc. so that they are not visible outside these devices. the source and device resonators may be separate from the power supplies and power consumers in the system and may be connected by a standard or custom wires, cables, connectors or plugs. the source 102 s may be powered from a number of dc or ac voltage, current or power sources including a usb port of a computer. the source 102 s may be powered from the electric grid, from a wall plug, from a battery, from a power supply, from an engine, from a solar cell, from a generator, from another source resonator, and the like. the source power and control circuitry 2302 may include circuits and components to isolate the source electronics from the power source, so that any reflected power or signals are not coupled out through the source input terminals. the source power and control circuits 2302 may include power factor correction circuits and may be configured to monitor power usage for monitoring accounting, billing, control, and like functionalities. the system may be operated bi-directionally. that is, energy or power that is generated or stored in a device resonator may be fed back to a power source including the electric grid, a battery, any kind of energy storage unit, and the like. the source power and control circuits may include power factor correction circuits and may be configured to monitor power usage for monitoring accounting, billing, control, and like functionalities for bi-directional energy flow. wireless energy transfer systems may enable or promote vehicle-to-grid (v2g) applications. the source and the device may have tuning capabilities that allow adjustment of operating points to compensate for changing environmental conditions, perturbations, and loading conditions that can affect the operation of the source and device resonators and the efficiency of the energy exchange. the tuning capability may also be used to multiplex power delivery to multiple devices, from multiple sources, to multiple systems, to multiple repeaters or relays, and the like. the tuning capability may be manually controlled, or automatically controlled and may be performed continuously, periodically, intermittently or at scheduled times or intervals. the device resonator and the device power and control circuitry may be integrated into any portion of the device, such as a battery compartment, or a device cover or sleeve, or on a mother board, for example, and may be integrated alongside standard rechargeable batteries or other energy storage units. the device resonator may include a device field reshaper which may shield any combination of the device resonator elements and the device power and control electronics from the electromagnetic fields used for the power transfer and which may deflect the resonator fields away from the lossy device resonator elements as well as the device power and control electronics. a magnetic material and/or high-conductivity field reshaper may be used to increase the perturbed quality factor q of the resonator and increase the perturbed coupling factor of the source and device resonators. the source resonator and the source power and control circuitry may be integrated into any type of furniture, structure, mat, rug, picture frame (including digital picture frames, electronic frames), plug-in modules, electronic devices, vehicles, and the like. the source resonator may include a source field reshaper which may shield any combination of the source resonator elements and the source power and control electronics from the electromagnetic fields used for the power transfer and which may deflect the resonator fields away from the lossy source resonator elements as well as the source power and control electronics. a magnetic material and/or high-conductivity field reshaper may be used to increase the perturbed quality factor q of the resonator and increase the perturbed coupling factor of the source and device resonators. a block diagram of the subsystems in an example of a wirelessly powered device is shown in fig. 39 . the power and control circuitry may be designed to transform the alternating current power from the device resonator 102 d and convert it to stable direct current power suitable for powering or charging a device. the power and control circuitry may be designed to transform an alternating current power at one frequency from the device resonator to alternating current power at a different frequency suitable for powering or charging a device. the power and control circuitry may include or consist of impedance matching circuitry 2402 d, rectification circuitry 2404 , voltage limiting circuitry (not shown), current limiting circuitry (not shown), ac-to-dc converter 2408 circuitry, dc-to-dc converter 2408 circuitry, dc-to-ac converter 2408 circuitry, ac-to-ac converter 2408 circuitry, battery charge control circuitry (not shown), and the like. the impedance-matching 2402 d network may be designed to maximize the power delivered between the device resonator 102 d and the device power and control circuitry 2304 at the desired frequency. the impedance matching elements may be chosen and connected such that the high-q of the resonators is preserved. depending on the operating conditions, the impedance matching circuitry 2402 d may be varied or tuned to control the power delivered from the source to the device, from the source to the device resonator, between the device resonator and the device power and control circuitry, and the like. the power, current and voltage signals may be monitored at any point in the device circuitry and feedback algorithms circuits, and techniques, may be used to control components to achieve desired signal levels and system operation. the feedback algorithms may be implemented using analog or digital circuit techniques and the circuits may include a microprocessor, a digital signal processor, a field programmable gate array processor and the like. the third block of fig. 39 shows a rectifier circuit 2404 that may rectify the ac voltage power from the device resonator into a dc voltage. in this configuration, the output of the rectifier 2404 may be the input to a voltage clamp circuit. the voltage clamp circuit (not shown) may limit the maximum voltage at the input to the dc-to-dc converter 2408 d or dc-to-ac converter 2408 d. in general, it may be desirable to use a dc-to-dc/ac converter with a large input voltage dynamic range so that large variations in device position and operation may be tolerated while adequate power is delivered to the device. for example, the voltage level at the output of the rectifier may fluctuate and reach high levels as the power input and load characteristics of the device change. as the device performs different tasks it may have varying power demands. the changing power demands can cause high voltages at the output of the rectifier as the load characteristics change. likewise as the device and the device resonator are brought closer and further away from the source, the power delivered to the device resonator may vary and cause changes in the voltage levels at the output of the rectifier. a voltage clamp circuit may prevent the voltage output from the rectifier circuit from exceeding a predetermined value which is within the operating range of the dc-to-dc/ac converter. the voltage clamp circuitry may be used to extend the operating modes and ranges of a wireless energy transfer system. the next block of the power and control circuitry of the device is the dc-to-dc converter 2408 d that may produce a stable dc output voltage. the dc-to-dc converter may be a boost converter, buck converter, boost-buck converter, single ended primary inductance converter (sepic), or any other dc-dc topology that fits the requirements of the particular application. if the device requires ac power, a dc-to-ac converter may be substituted for the dc-to-dc converter, or the dc-to-dc converter may be followed by a dc-to-ac converter. if the device contains a rechargeable battery, the final block of the device power and control circuitry may be a battery charge control unit which may manage the charging and maintenance of the battery in battery powered devices. the device power and control circuitry 2304 may contain a processor 2410 d, such as a microcontroller, a digital signal processor, a field programmable gate array processor, a microprocessor, or any other type of processor. the processor may be used to read or detect the state or the operating point of the power and control circuitry and the device resonator. the processor may implement algorithms to interpret and adjust the operating point of the circuits, elements, components, subsystems and resonator. the processor may be used to adjust the impedance matching, the resonator, the dc to dc converters, the dc to ac converters, the battery charging unit, the rectifier, and the like of the wirelessly powered device. the processor may have wireless or wired data communication links to other devices or sources and may transmit or receive data that can be used to adjust the operating point of the system. any combination of power, voltage, and current signals at a single, or over a range of frequencies, may be monitored at any point in the device circuitry. these signals may be monitored using analog or digital or combined analog and digital techniques. these monitored signals may be used in feedback loops or may be reported to the user in a variety of known ways or they may be stored and retrieved at later times. these signals may be used to alert a user of system failures, to indicate performance, or to provide audio, visual, vibrational, and the like, feedback to a user of the system. fig. 40 shows components of source power and control circuitry 2302 of an exemplary wireless power transfer system configured to supply power to a single or multiple devices. the source power and control circuitry 2302 of the exemplary system may be powered from an ac voltage source 2502 such as a home electrical outlet, a dc voltage source such as a battery, a usb port of a computer, a solar cell, another wireless power source, and the like. the source power and control circuitry 2302 may drive the source resonator 102 s with alternating current, such as with a frequency greater than 10 khz and less than 100 mhz. the source power and control circuitry 2302 may drive the source resonator 102 s with alternating current of frequency less than less than 10 ghz. the source power and control circuitry 2302 may include a dc-to-dc converter 2408 s, an ac-to-dc converter 2408 s, or both an ac-to-dc converter 2408 s and a dc-to-dc 2408 s converter, an oscillator 2508 , a power amplifier 2504 , an impedance matching network 2402 s, and the like. the source power and control circuitry 2302 may be powered from multiple ac-or-dc voltage sources 2502 and may contain ac-to-dc and dc-to-dc converters 2408 s to provide necessary voltage levels for the circuit components as well as dc voltages for the power amplifiers that may be used to drive the source resonator. the dc voltages may be adjustable and may be used to control the output power level of the power amplifier. the source may contain power factor correction circuitry. the oscillator 2508 output may be used as the input to a power amplifier 2504 that drives the source resonator 102 s. the oscillator frequency may be tunable and the amplitude of the oscillator signal may be varied as one means to control the output power level from the power amplifier. the frequency, amplitude, phase, waveform, and duty cycle of the oscillator signal may be controlled by analog circuitry, by digital circuitry or by a combination of analog and digital circuitry. the control circuitry may include a processor 2410 s, such as a microprocessor, a digital signal processor, a field programmable gate array processor, and the like. the impedance matching blocks 2402 of the source and device resonators may be used to tune the power and control circuits and the source and device resonators. for example, tuning of these circuits may adjust for perturbation of the quality factor q of the source or device resonators due to extraneous objects or changes in distance between the source and device in a system. tuning of these circuits may also be used to sense the operating environment, control power flow to one or more devices, to control power to a wireless power network, to reduce power when unsafe or failure mode conditions are detected, and the like. any combination of power, voltage, and current signals may be monitored at any point in the source circuitry. these signals may be monitored using analog or digital or combined analog and digital techniques. these monitored signals may be used in feedback circuits or may be reported to the user in a variety of known ways or they may be stored and retrieved at later times. these signals may be used to alert a user to system failures, to alert a user to exceeded safety thresholds, to indicate performance, or to provide audio, visual, vibrational, and the like, feedback to a user of the system. the source power and control circuitry may contain a processor. the processor may be used to read the state or the operating point of the power and control circuitry and the source resonator. the processor may implement algorithms to interpret and adjust the operating point of the circuits, elements, components, subsystems and resonator. the processor may be used to adjust the impedance matching, the resonator, the dc-to-dc converters, the ac-to-dc converters, the oscillator, the power amplifier of the source, and the like. the processor and adjustable components of the system may be used to implement frequency and/or time power delivery multiplexing schemes. the processor may have wireless or wired data communication links to devices and other sources and may transmit or receive data that can be used to adjust the operating point of the system. although detailed and specific designs are shown in these block diagrams, it should be clear to those skilled in the art that many different modifications and rearrangements of the components and building blocks are possible within the spirit of the exemplary system. the division of the circuitry was outlined for illustrative purposes and it should be clear to those skilled in the art that the components of each block may be further divided into smaller blocks or merged or shared. in equivalent examples the power and control circuitry may be composed of individual discrete components or larger integrated circuits. for example, the rectifier circuitry may be composed of discrete diodes, or use diodes integrated on a single chip. a multitude of other circuits and integrated devices can be substituted in the design depending on design criteria such as power or size or cost or application. the whole of the power and control circuitry or any portion of the source or device circuitry may be integrated into one chip. the impedance matching network of the device and or source may include a capacitor or networks of capacitors, an inductor or networks of inductors, or any combination of capacitors, inductors, diodes, switches, resistors, and the like. the components of the impedance matching network may be adjustable and variable and may be controlled to affect the efficiency and operating point of the system. the impedance matching may be performed by controlling the connection point of the resonator, adjusting the permeability of a magnetic material, controlling a bias field, adjusting the frequency of excitation, and the like. the impedance matching may use or include any number or combination of varactors, varactor arrays, switched elements, capacitor banks, switched and tunable elements, reverse bias diodes, air gap capacitors, compression capacitors, bzt electrically tuned capacitors, mems-tunable capacitors, voltage variable dielectrics, transformer coupled tuning circuits, and the like. the variable components may be mechanically tuned, thermally tuned, electrically tuned, piezo-electrically tuned, and the like. elements of the impedance matching may be silicon devices, gallium nitride devices, silicon carbide devices and the like. the elements may be chosen to withstand high currents, high voltages, high powers, or any combination of current, voltage and power. the elements may be chosen to be high-q elements. the matching and tuning calculations of the source may be performed on an external device through a usb port that powers the device. the device may be a computer a pda or other computational platform. a demonstration system used a source resonator, coupled to a device resonator, to wirelessly power/recharge multiple electronic consumer devices including, but not limited to, a laptop, a dvd player, a projector, a cell-phone, a display, a television, a projector, a digital picture frame, a light, a tv/dvd player, a portable music player, a circuit breaker, a hand-held tool, a personal digital assistant, an external battery charger, a mouse, a keyboard, a camera, an active load, and the like. a variety of devices may be powered simultaneously from a single device resonator. device resonators may be operated simultaneously as source resonators. the power supplied to a device resonator may pass through additional resonators before being delivered to its intended device resonator. monitoring, feedback and control so-called port parameter measurement circuitry may measure or monitor certain power, voltage, and current, signals in the system and processors or control circuits may adjust certain settings or operating parameters based on those measurements. in addition to these port parameter measurements, the magnitude and phase of voltage and current signals, and the magnitude of the power signals, throughout the system may be accessed to measure or monitor the system performance. the measured signals referred to throughout this disclosure may be any combination of the port parameter signals, as well as voltage signals, current signals, power signals, and the like. these parameters may be measured using analog or digital signals, they may be sampled and processed, and they may be digitized or converted using a number of known analog and digital processing techniques. measured or monitored signals may be used in feedback circuits or systems to control the operation of the resonators and/or the system. in general, we refer to these monitored or measured signals as reference signals, or port parameter measurements or signals, although they are sometimes also referred to as error signals, monitor signals, feedback signals, and the like. we will refer to the signals that are used to control circuit elements such as the voltages used to drive voltage controlled capacitors as the control signals. in some cases the circuit elements may be adjusted to achieve a specified or predetermined impedance value for the source and device resonators. in other cases the impedance may be adjusted to achieve a desired impedance value for the source and device resonators when the device resonator is connected to a power consumer or consumers. in other cases the impedance may be adjusted to mitigate changes in the resonant frequency, or impedance or power level changes owing to movement of the source and/or device resonators, or changes in the environment (such as the movement of interacting materials or objects) in the vicinity of the resonators. in other cases the impedance of the source and device resonators may be adjusted to different impedance values. the coupled resonators may be made of different materials and may include different circuits, components and structural designs or they may be the same. the coupled resonators may include performance monitoring and measurement circuitry, signal processing and control circuitry or a combination of measurement and control circuitry. some or all of the high-q magnetic resonators may include tunable impedance circuits. some or all of the high-q magnetic resonators may include automatically controlled tunable impedance circuits. fig. 41 shows a magnetic resonator with port parameter measurement circuitry 3802 configured to measure certain parameters of the resonator. the port parameter measurement circuitry may measure the input impedance of the structure, or the reflected power. port parameter measurement circuits may be included in the source and/or device resonator designs and may be used to measure two port circuit parameters such as s-parameters (scattering parameters), z-parameters (impedance parameters), y-parameters (admittance parameters), t-parameters (transmission parameters), h-parameters (hybrid parameters), abcd-parameters (chain, cascade or transmission parameters), and the like. these parameters may be used to describe the electrical behavior of linear electrical networks when various types of signals are applied. different parameters may be used to characterize the electrical network under different operating or coupling scenarios. for example, s-parameters may be used to measure matched and unmatched loads. in addition, the magnitude and phase of voltage and current signals within the magnetic resonators and/or within the sources and devices themselves may be monitored at a variety of points to yield system performance information. this information may be presented to users of the system via a user interface such as a light, a read-out, a beep, a noise, a vibration or the like, or it may be presented as a digital signal or it may be provided to a processor in the system and used in the automatic control of the system. this information may be logged, stored, or may be used by higher level monitoring and control systems. fig. 42 shows a circuit diagram of a magnetic resonator where the tunable impedance network may be realized with voltage controlled capacitors 3902 or capacitor networks. such an implementation may be adjusted, tuned or controlled by electrical circuits and/or computer processors, such as a programmable voltage source 3908 , and the like. for example, the voltage controlled capacitors may be adjusted in response to data acquired by the port parameter measurement circuitry 3802 and processed by a measurement analysis and control algorithm subsystem 3904 . reference signals may be derived from the port parameter measurement circuitry or other monitoring circuitry designed to measure the degree of deviation from a desired system operating point. the measured reference signals may include voltage, current, complex-impedance, reflection coefficient, power levels and the like, at one or several points in the system and at a single frequency or at multiple frequencies. the reference signals may be fed to measurement analysis and control algorithm subsystem modules that may generate control signals to change the values of various components in a tunable impedance matching network. the control signals may vary the resonant frequency and/or the input impedance of the magnetic resonator, or the power level supplied by the source, or the power level drawn by the device, to achieve the desired power exchange between power supplies/generators and power drains/loads. adjustment algorithms may be used to adjust the frequency and/or impedance of the magnetic resonators. the algorithms may take in reference signals related to the degree of deviation from a desired operating point for the system and output correction or control signals related to that deviation that control variable or tunable elements of the system to bring the system back towards the desired operating point or points. the reference signals for the magnetic resonators may be acquired while the resonators are exchanging power in a wireless power transmission system, or they may be switched out of the circuit during system operation. corrections to the system may be applied or performed continuously, periodically, upon a threshold crossing, digitally, using analog methods, and the like. fig. 43 shows an end-to-end wireless power transmission system. both the source and the device may include port measurement circuitry 3802 and a processor 2410 . the box labeled “coupler/switch” 4002 indicates that the port measurement circuitry 3802 may be connected to the resonator 102 by a directional coupler or a switch, enabling the measurement, adjustment and control of the source and device resonators to take place in conjunction with, or separate from, the power transfer functionality. the port parameter measurement and/or processing circuitry may reside with some, any, or all resonators in a system. the port parameter measurement circuitry may utilize portions of the power transmission signal or may utilize excitation signals over a range of frequencies to measure the source/device resonator response (i.e. transmission and reflection between any two ports in the system), and may contain amplitude and/or phase information. such measurements may be achieved with a swept single frequency signal or a multi-frequency signal. the signals used to measure and monitor the resonators and the wireless power transmission system may be generated by a processor or processors and standard input/output (i/o) circuitry including digital to analog converters (dacs), analog to digital converters (adcs), amplifiers, signal generation chips, passive components and the like. measurements may be achieved using test equipment such as a network analyzer or using customized circuitry. the measured reference signals may be digitized by adcs and processed using customized algorithms running on a computer, a microprocessor, a dsp chip, an asic, and the like. the measured reference signals may be processed in an analog control loop. the measurement circuitry may measure any set of two port parameters such as s-parameters, y-parameters, z-parameters, h-parameters, g-parameters, t-parameters, abcd-parameters, and the like. measurement circuitry may be used to characterize current and voltage signals at various points in the drive and resonator circuitry, the impedance and/or admittance of the source and device resonators at opposite ends of the system, i.e. looking into the source resonator matching network (“port 1” in fig. 43 ) towards the device and vice versa. the device may measure relevant signals and/or port parameters, interpret the measurement data, and adjust its matching network to optimize the impedance looking into the coupled system independently of the actions of the source. the source may measure relevant port parameters, interpret the measurement data, and adjust its matching network to optimize the impedance looking into the coupled system independently of the actions of the device. fig. 43 shows a block diagram of a source and device in a wireless power transmission system. the system may be configured to execute a control algorithm that actively adjusts the tuning/matching networks in either of or both the source and device resonators to optimize performance in the coupled system. port measurement circuitry 3802 s may measure signals in the source and communicate those signals to a processor 2410 . a processor 2410 may use the measured signals in a performance optimization or stabilization algorithm and generate control signals based on the outputs of those algorithms. control signals may be applied to variable circuit elements in the tuning/impedance matching circuits 2402 s to adjust the source's operating characteristics, such as power in the resonator and coupling to devices. control signals may be applied to the power supply or generator to turn the supply on or off, to increase or decrease the power level, to modulate the supply signal and the like. the power exchanged between sources and devices may depend on a variety of factors. these factors may include the effective impedance of the sources and devices, the q's of the sources and devices, the resonant frequencies of the sources and devices, the distances between sources and devices, the interaction of materials and objects in the vicinity of sources and devices and the like. the port measurement circuitry and processing algorithms may work in concert to adjust the resonator parameters to maximize power transfer, to hold the power transfer constant, to controllably adjust the power transfer, and the like, under both dynamic and steady state operating conditions. some, all or none of the sources and devices in a system implementation may include port measurement circuitry 3802 s and processing 2410 capabilities. fig. 44 shows an end-to-end wireless power transmission system in which only the source 102 s contains port measurement circuitry 3802 and a processor 2410 s. in this case, the device resonator 102 d operating characteristics may be fixed or may be adjusted by analog control circuitry and without the need for control signals generated by a processor. fig. 45 shows an end-to-end wireless power transmission system. both the source and the device may include port measurement circuitry 3802 but in the system of fig. 45 , only the source contains a processor 2410 s. the source and device may be in communication with each other and the adjustment of certain system parameters may be in response to control signals that have been wirelessly communicated, such as though wireless communications circuitry 4202 , between the source and the device. the wireless communication channel 4204 may be separate from the wireless power transfer channel 4208 , or it may be the same. that is, the resonators 102 used for power exchange may also be used to exchange information. in some cases, information may be exchanged by modulating a component a source or device circuit and sensing that change with port parameter or other monitoring equipment. implementations where only the source contains a processor 2410 may be beneficial for multi-device systems where the source can handle all of the tuning and adjustment “decisions” and simply communicate the control signals back to the device(s). this implementation may make the device smaller and cheaper because it may eliminate the need for, or reduce the required functionality of, a processor in the device. a portion of or an entire data set from each port measurement at each device may be sent back to the source microprocessor for analysis, and the control instructions may be sent back to the devices. these communications may be wireless communications. fig. 46 shows an end-to-end wireless power transmission system. in this example, only the source contains port measurement circuitry 3802 and a processor 2410 s. the source and device may be in communication, such as via wireless communication circuitry 4202 , with each other and the adjustment of certain system parameters may be in response to control signals that have been wirelessly communicated between the source and the device. fig. 47 shows coupled electromagnetic resonators 102 whose frequency and impedance may be automatically adjusted using a processor or a computer. resonant frequency tuning and continuous impedance adjustment of the source and device resonators may be implemented with reverse biased diodes, schottky diodes and/or varactor elements contained within the capacitor networks shown as c 1 , c 2 , and c 3 in fig. 47 . the circuit topology that was built and demonstrated and is described here is exemplary and is not meant to limit the discussion of automatic system tuning and control in any way. other circuit topologies could be utilized with the measurement and control architectures discussed in this disclosure. device and source resonator impedances and resonant frequencies may be measured with a network analyzer 4402 a-b, or by other means described above, and implemented with a controller, such as with lab view 4404 . the measurement circuitry or equipment may output data to a computer or a processor that implements feedback algorithms and dynamically adjusts the frequencies and impedances via a programmable dc voltage source. in one arrangement, the reverse biased diodes (schottky, semiconductor junction, and the like) used to realize the tunable capacitance drew very little dc current and could be reverse biased by amplifiers having large series output resistances. this implementation may enable dc control signals to be applied directly to the controllable circuit elements in the resonator circuit while maintaining a very high-q in the magnetic resonator. c 2 biasing signals may be isolated from c 1 and/or c 3 biasing signals with a dc blocking capacitor as shown in fig. 47 , if the required dc biasing voltages are different. the output of the biasing amplifiers may be bypassed to circuit ground to isolate rf voltages from the biasing amplifiers, and to keep non-fundamental rf voltages from being injected into the resonator. the reverse bias voltages for some of the capacitors may instead be applied through the inductive element in the resonator itself, because the inductive element acts as a short circuit at dc. the port parameter measurement circuitry may exchange signals with a processor (including any required adcs and dacs) as part of a feedback or control system that is used to automatically adjust the resonant frequency, input impedance, energy stored or captured by the resonator or power delivered by a source or to a device load. the processor may also send control signals to tuning or adjustment circuitry in or attached to the magnetic resonator. when utilizing varactors or diodes as tunable capacitors, it may be beneficial to place fixed capacitors in parallel and in series with the tunable capacitors operating at high reverse bias voltages in the tuning/matching circuits. this arrangement may yield improvements in circuit and system stability and in power handling capability by optimizing the operating voltages on the tunable capacitors. varactors or other reverse biased diodes may be used as a voltage controlled capacitor. arrays of varactors may be used when higher voltage compliance or different capacitance is required than that of a single varactor component. varactors may be arranged in an n by m array connected serially and in parallel and treated as a single two terminal component with different characteristics than the individual varactors in the array. for example, an n by n array of equal varactors where components in each row are connected in parallel and components in each column are connected in series may be used as a two terminal device with the same capacitance as any single varactor in the array but with a voltage compliance that is n times that of a single varactor in the array. depending on the variability and differences of parameters of the individual varactors in the array additional biasing circuits composed of resistors, inductors, and the like may be needed. a schematic of a four by four array of unbiased varactors 4502 that may be suitable for magnetic resonator applications is shown in fig. 48 . further improvements in system performance may be realized by careful selection of the fixed value capacitor(s) that are placed in parallel and/or in series with the tunable (varactor/diode/capacitor) elements. multiple fixed capacitors that are switched in or out of the circuit may be able to compensate for changes in resonator q's, impedances, resonant frequencies, power levels, coupling strengths, and the like, that might be encountered in test, development and operational wireless power transfer systems. switched capacitor banks and other switched element banks may be used to assure the convergence to the operating frequencies and impedance values required by the system design. an exemplary control algorithm for isolated and coupled magnetic resonators may be described for the circuit and system elements shown in fig. 47 . one control algorithm first adjusts each of the source and device resonator loops “in isolation”, that is, with the other resonators in the system “shorted out” or “removed” from the system. for practical purposes, a resonator can be “shorted out” by making it resonant at a much lower frequency such as by maximizing the value of c 1 and/or c 3 . this step effectively reduces the coupling between the resonators, thereby effectively reducing the system to a single resonator at a particular frequency and impedance. tuning a magnetic resonator in isolation includes varying the tunable elements in the tuning and matching circuits until the values measured by the port parameter measurement circuitry are at their predetermined, calculated or measured relative values. the desired values for the quantities measured by the port parameter measurement circuitry may be chosen based on the desired matching impedance, frequency, strong coupling parameter, and the like. for the exemplary algorithms disclosed below, the port parameter measurement circuitry measures s-parameters over a range of frequencies. the range of frequencies used to characterize the resonators may be a compromise between the system performance information obtained and computation/measurement speed. for the algorithms described below the frequency range may be approximately +/−20% of the operating resonant frequency. each isolated resonator may be tuned as follows. first, short out the resonator not being adjusted. next minimize c 1 , c 2 , and c 3 , in the resonator that is being characterized and adjusted. in most cases there will be fixed circuit elements in parallel with c 1 , c 2 , and c 3 , so this step does not reduce the capacitance values to zero. next, start increasing c 2 until the resonator impedance is matched to the “target” real impedance at any frequency in the range of measurement frequencies described above. the initial “target” impedance may be less than the expected operating impedance for the coupled system. c 2 may be adjusted until the initial “target” impedance is realized for a frequency in the measurement range. then c 1 and/or c 3 may be adjusted until the loop is resonant at the desired operating frequency. each resonator may be adjusted according to the above algorithm. after tuning each resonator in isolation, a second feedback algorithm may be applied to optimize the resonant frequencies and/or input impedances for wirelessly transferring power in the coupled system. the required adjustments to c 1 and/or c 2 and/or c 3 in each resonator in the coupled system may be determined by measuring and processing the values of the real and imaginary parts of the input impedance from either and/or both “port(s)” shown in fig. 43 . for coupled resonators, changing the input impedance of one resonator may change the input impedance of the other resonator. control and tracking algorithms may adjust one port to a desired operating point based on measurements at that port, and then adjust the other port based on measurements at that other port. these steps may be repeated until both sides converge to the desired operating point. s-parameters may be measured at both the source and device ports and the following series of measurements and adjustments may be made. in the description that follows, z 0 is an input impedance and may be the target impedance. in some cases z 0 is 50 ohms or is near 50 ohms. z 1 and z 2 are intermediate impedance values that may be the same value as z 0 or may be different than z 0 . re{value} means the real part of a value and im{value} means the imaginary part of a value. an algorithm that may be used to adjust the input impedance and resonant frequency of two coupled resonators is set forth below: 1) adjust each resonator “in isolation” as described above.2) adjust source c 1 /c 3 until, at ω o , re{s 11 }=(z 1 +/−∈ re ) as follows: if re{s 11 @ω o }>(z 1 +∈ re ), decrease c 1 /c 3 . if re{s 11 @ω o }<(zo−∈ re ), increase c 1 /c 3 .3) adjust source c 2 until, at ω o , im{s 11 }=(+/−∈ im ) as follows: if im{s 11 @ω o }>∈ im , decrease c 2 . if im{s 11 @ω o }<−∈ im , increase c 2 .4) adjust device c 1 /c 3 until, at ω 0 , re{s 22 }=(z 2 +/−∈ re ) as follows: if re{s 22 @ω o }>(z 2 +∈ re ), decrease c 1 /c 3 . if re{s 22 @ω o }<(zo−∈ re ), increase c 1 /c 3 .5) adjust device c 2 until, at ω o , im{s 22 }=0 as follows: if im{s 22 @ω o }>∈ im , decrease c 2 . if im{s 22 @ω o }<−∈ im , increase c 2 . we have achieved a working system by repeating steps 1-4 until both (re{s 11 }, im{s 11 }) and (re{s 22 }, im{s 22 }) converge to ((z 0 +/−∈ re ), (+/−∈ im )) at ω o , where z 0 is the desired matching impedance and ω o is the desired operating frequency. here, ∈ im represents the maximum deviation of the imaginary part, at ω o , from the desired value of 0, and ∈ re represents the maximum deviation of the real part from the desired value of z 0 . it is understood that ∈ im and ∈ re can be adjusted to increase or decrease the number of steps to convergence at the potential cost of system performance (efficiency). it is also understood that steps 1-4 can be performed in a variety of sequences and a variety of ways other than that outlined above (i.e. first adjust the source imaginary part, then the source real part; or first adjust the device real part, then the device imaginary part, etc.) the intermediate impedances z 1 and z 2 may be adjusted during steps 1-4 to reduce the number of steps required for convergence. the desire or target impedance value may be complex, and may vary in time or under different operating scenarios. steps 1-4 may be performed in any order, in any combination and any number of times. having described the above algorithm, variations to the steps or the described implementation may be apparent to one of ordinary skill in the art. the algorithm outlined above may be implemented with any equivalent linear network port parameter measurements (i.e., z-parameters, y-parameters, t-parameters, h-parameters, abcd-parameters, etc.) or other monitor signals described above, in the same way that impedance or admittance can be alternatively used to analyze a linear circuit to derive the same result. the resonators may need to be returned owing to changes in the “loaded” resistances, rs and rd, caused by changes in the mutual inductance m (coupling) between the source and device resonators. changes in the inductances, ls and ld, of the inductive elements themselves may be caused by the influence of external objects, as discussed earlier, and may also require compensation. such variations may be mitigated by the adjustment algorithm described above. a directional coupler or a switch may be used to connect the port parameter measurement circuitry to the source resonator and tuning/adjustment circuitry. the port parameter measurement circuitry may measure properties of the magnetic resonator while it is exchanging power in a wireless power transmission system, or it may be switched out of the circuit during system operation. the port parameter measurement circuitry may measure the parameters and the processor may control certain tunable elements of the magnetic resonator at start-up, or at certain intervals, or in response to changes in certain system operating parameters. a wireless power transmission system may include circuitry to vary or tune the impedance and/or resonant frequency of source and device resonators. note that while tuning circuitry is shown in both the source and device resonators, the circuitry may instead be included in only the source or the device resonators, or the circuitry may be included in only some of the source and/or device resonators. note too that while we may refer to the circuitry as “tuning” the impedance and or resonant frequency of the resonators, this tuning operation simply means that various electrical parameters such as the inductance or capacitance of the structure are being varied. in some cases, these parameters may be varied to achieve a specific predetermined value, in other cases they may be varied in response to a control algorithm or to stabilize a target performance value that is changing. in some cases, the parameters are varied as a function of temperature, of other sources or devices in the area, of the environment, at the like. applications for each listed application, it will be understood by one of ordinary skill-in-the-art that there are a variety of ways that the resonator structures used to enable wireless power transmission may be connected or integrated with the objects that are supplying or being powered. the resonator may be physically separate from the source and device objects. the resonator may supply or remove power from an object using traditional inductive techniques or through direct electrical connection, with a wire or cable for example. the electrical connection may be from the resonator output to the ac or dc power input port on the object. the electrical connection may be from the output power port of an object to the resonator input. fig. 49 shows a source resonator 4904 that is physically separated from a power supply and a device resonator 4902 that is physically separated from the device 4900 , in this illustration a laptop computer. power may be supplied to the source resonator, and power may be taken from the device resonator directly, by an electrical connection. one of ordinary skill in the art will understand from the materials incorporated by reference that the shape, size, material composition, arrangement, position and orientation of the resonators above are provided by way of non-limiting example, and that a wide variation in any and all of these parameters could be supported by the disclosed technology for a variety of applications. continuing with the example of the laptop, and without limitation, the device resonator may be physically connected to the device it is powering or charging. for example, as shown in fig. 50 a and fig. 50 b , the device resonator 5002 may be (a) integrated into the housing of the device 5000 or (b) it may be attached by an adapter. the resonator 5002 may ( fig. 50 b - d ) or may not ( fig. 50 a ) be visible on the device. the resonator may be affixed to the device, integrated into the device, plugged into the device, and the like. the source resonator may be physically connected to the source supplying the power to the system. as described above for the devices and device resonators, there are a variety of ways the resonators may be attached to, connected to or integrated with the power supply. one of ordinary skill in the art will understand that there are a variety of ways the resonators may be integrated in the wireless power transmission system, and that the sources and devices may utilize similar or different integration techniques. continuing again with the example of the laptop computer, and without limitation, the laptop computer may be powered, charged or recharged by a wireless power transmission system. a source resonator may be used to supply wireless power and a device resonator may be used to capture the wireless power. a device resonator 5002 may be integrated into the edge of the screen (display) as illustrated in fig. 50 d , and/or into the base of the laptop as illustrated in fig. 50 c . the source resonator 5002 may be integrated into the base of the laptop and the device resonator may be integrated into the edge of the screen. the resonators may also or instead be affixed to the power source and/or the laptop. the source and device resonators may also or instead be physically separated from the power supply and the laptop and may be electrically connected by a cable. the source and device resonators may also or instead be physically separated from the power supply and the laptop and may be electrically coupled using a traditional inductive technique. one of ordinary skill in the art will understand that, while the preceding examples relate to wireless power transmission to a laptop, that the methods and systems disclosed for this application may be suitably adapted for use with other electrical or electronic devices. in general, the source resonator may be external to the source and supplying power to a device resonator that in turn supplies power the device, or the source resonator may be connected to the source and supplying power to a device resonator that in turn supplies power to a portion of the device, or the source resonator may internal to the source and supplying power to a device resonator that in turn supplies power to a portion of the device, as well as any combination of these. a system or method disclosed herein may provide power to an electrical or electronics device, such as, and not limited to, phones, cell phones, cordless phones, smart phones, pdas, audio devices, music players, mp3 players, radios, portable radios and players, wireless headphones, wireless headsets, computers, laptop computers, wireless keyboards, wireless mouse, televisions, displays, flat screen displays, computer displays, displays embedded in furniture, digital picture frames, electronic books, (e.g. the kindle, e-ink books, magazines, and the like), remote control units (also referred to as controllers, game controllers, commanders, clickers, and the like, and used for the remote control of a plurality of electronics devices, such as televisions, video games, displays, computers, audio visual equipment, lights, and the like), lighting devices, cooling devices, air circulation devices, purification devices, personal hearing aids, power tools, security systems, alarms, bells, flashing lights, sirens, sensors, loudspeakers, electronic locks, electronic keypads, light switches, other electrical switches, and the like. here the term electronic lock is used to indicate a door lock which operates electronically (e.g. with electronic combo-key, magnetic card, rfid card, and the like) which is placed on a door instead of a mechanical key-lock. such locks are often battery operated, risking the possibility that the lock might stop working when a battery dies, leaving the user locked-out. this may be avoided where the battery is either charged or completely replaced by a wireless power transmission implementation as described herein. here, the term light switch (or other electrical switch) is meant to indicate any switch (e.g. on a wall of a room) in one part of the room that turns on/off a device (e.g. light fixture at the center of the ceiling) in another part of the room. to install such a switch by direct connection, one would have to run a wire all the way from the device to the switch. once such a switch is installed at a particular spot, it may be very difficult to move. alternately, one can envision a ‘wireless switch’, where “wireless” means the switching (on/off) commands are communicated wirelessly, but such a switch has traditionally required a battery for operation. in general, having too many battery operated switches around a house may be impractical, because those many batteries will need to be replaced periodically. so, a wirelessly communicating switch may be more convenient, provided it is also wirelessly powered. for example, there already exist communications wireless door-bells that are battery powered, but where one still has to replace the battery in them periodically. the remote doorbell button may be made to be completely wireless, where there may be no need to ever replace the battery again. note that here, the term ‘cordless’ or ‘wireless’ or ‘communications wireless’ is used to indicate that there is a cordless or wireless communications facility between the device and another electrical component, such as the base station for a cordless phone, the computer for a wireless keyboard, and the like. one skilled in the art will recognize that any electrical or electronics device may include a wireless communications facility, and that the systems and methods described herein may be used to add wireless power transmission to the device. as described herein, power to the electrical or electronics device may be delivered from an external or internal source resonator, and to the device or portion of the device. wireless power transmission may significantly reduce the need to charge and/or replace batteries for devices that enter the near vicinity of the source resonator and thereby may reduce the downtime, cost and disposal issues often associated with batteries. the systems and methods described herein may provide power to lights without the need for either wired power or batteries. that is, the systems and methods described herein may provide power to lights without wired connection to any power source, and provide the energy to the light non-radiatively across mid-range distances, such as across a distance of a quarter of a meter, one meter, three meters, and the like. a ‘light’ as used herein may refer to the light source itself, such as an incandescent light bulb, florescent light bulb lamps, halogen lamps, gas discharge lamps, fluorescent lamps, neon lamps, high-intensity discharge lamps, sodium vapor lamps, mercury-vapor lamps, electroluminescent lamps, light emitting diodes (led) lamps, and the like; the light as part of a light fixture, such as a table lamp, a floor lamp, a ceiling lamp, track lighting, recessed light fixtures, and the like; light fixtures integrated with other functions, such as a light/ceiling fan fixture, and illuminated picture frame, and the like. as such, the systems and methods described herein may reduce the complexity for installing a light, such as by minimizing the installation of electrical wiring, and allowing the user to place or mount the light with minimal regard to sources of wired power. for instance, a light may be placed anywhere in the vicinity of a source resonator, where the source resonator may be mounted in a plurality of different places with respect to the location of the light, such as on the floor of the room above, (e.g. as in the case of a ceiling light and especially when the room above is the attic); on the wall of the next room, on the ceiling of the room below, (e.g. as in the case of a floor lamp); in a component within the room or in the infrastructure of the room as described herein; and the like. for example, a light/ceiling fan combination is often installed in a master bedroom, and the master bedroom often has the attic above it. in this instance a user may more easily install the light/ceiling fan combination in the master bedroom, such as by simply mounting the light/ceiling fan combination to the ceiling, and placing a source coil (plugged into the house wired ac power) in the attic above the mounted fixture. in another example, the light may be an external light, such as a flood light or security light, and the source resonator mounted inside the structure. this way of installing lighting may be particularly beneficial to users who rent their homes, because now they may be able to mount lights and such other electrical components without the need to install new electrical wiring. the control for the light may also be communicated by near-field communications as described herein, or by traditional wireless communications methods. the systems and methods described herein may provide power from a source resonator to a device resonator that is either embedded into the device component, or outside the device component, such that the device component may be a traditional electrical component or fixture. for instance, a ceiling lamp may be designed or retrofitted with a device resonator integrated into the fixture, or the ceiling lamp may be a traditional wired fixture, and plugged into a separate electrical facility equipped with the device resonator. in an example, the electrical facility may be a wireless junction box designed to have a device resonator for receiving wireless power, say from a source resonator placed on the floor of the room above (e.g. the attic), and which contains a number of traditional outlets that are powered from the device resonator. the wireless junction box, mounted on the ceiling, may now provide power to traditional wired electrical components on the ceiling (e.g. a ceiling light, track lighting, a ceiling fan). thus, the ceiling lamp may now be mounted to the ceiling without the need to run wires through the infrastructure of the building. this type of device resonator to traditional outlet junction box may be used in a plurality of applications, including being designed for the interior or exterior of a building, to be made portable, made for a vehicle, and the like. wireless power may be transferred through common building materials, such as wood, wall board, insulation, glass. brick, stone, concrete, and the like. the benefits of reduced installation cost, re-configurability, and increased application flexibility may provide the user significant benefits over traditional wired installations. the device resonator for a traditional outlet junction box may include a plurality of electrical components for facilitating the transfer of power from the device resonator to the traditional outlets, such as power source electronics which convert the specific frequencies needed to implement efficient power transfer to line voltage, power capture electronics which may convert high frequency ac to usable voltage and frequencies (ac and/or dc), controls which synchronize the capture device and the power output and which ensure consistent, safe, and maximally efficient power transfer, and the like. the systems and methods described herein may provide advantages to lights or electrical components that operate in environments that are wet, harsh, controlled, and the like, such has outside and exposed to the rain, in a pool/sauna/shower, in a maritime application, in hermetically sealed components, in an explosive-proof room, on outside signage, a harsh industrial environment in a volatile environment (e.g. from volatile vapors or airborne organics, such as in a grain silo or bakery), and the like. for example, a light mounted under the water level of a pool is normally difficult to wire up, and is required to be water-sealed despite the need for external wires. but a pool light using the principles disclosed herein may more easily be made water sealed, as there may be no external wires needed. in another example, an explosion proof room, such as containing volatile vapors, may not only need to be hermetically sealed, but may need to have all electrical contacts (that could create a spark) sealed. again, the principles disclosed herein may provide a convenient way to supply sealed electrical components for such applications. the systems and methods disclosed herein may provide power to game controller applications, such as to a remote handheld game controller. these game controllers may have been traditionally powered solely by batteries, where the game controller's use and power profile caused frequent changing of the battery, battery pack, rechargeable batteries, and the like, that may not have been ideal for the consistent use to the game controller, such as during extended game play. a device resonator may be placed into the game controller, and a source resonator, connected to a power source, may be placed in the vicinity. further, the device resonator in the game controller may provide power directly to the game controller electronics without a battery; provide power to a battery, battery pack, rechargeable battery, and the like, which then provides power to the game controller electronics; and the like. the game controller may utilize multiple battery packs, where each battery pack is equipped with a device resonator, and thus may be constantly recharging while in the vicinity of the source resonator, whether plugged into the game controller or not. the source resonator may be resident in a main game controller facility for the game, where the main game controller facility and source resonator are supplied power from ac ‘house’ power; resident in an extension facility form ac power, such as in a source resonator integrated into an ‘extension cord’; resident in a game chair, which is at least one of plugged into the wall ac, plugged into the main game controller facility, powered by a battery pack in the game chair; and the like. the source resonator may be placed and implemented in any of the configurations described herein. the systems and methods disclosed herein may integrate device resonators into battery packs, such as battery packs that are interchangeable with other battery packs. for instance, some portable devices may use up electrical energy at a high rate such that a user may need to have multiple interchangeable battery packs on hand for use, or the user may operate the device out of range of a source resonator and need additional battery packs to continue operation, such as for power tools, portable lights, remote control vehicles, and the like. the use of the principles disclosed herein may not only provide a way for device resonator enabled battery packs to be recharged while in use and in range, but also for the recharging of battery packs not currently in use and placed in range of a source resonator. in this way, battery packs may always be ready to use when a user runs down the charge of a battery pack being used. for example, a user may be working with a wireless power tool, where the current requirements may be greater than can be realized through direct powering from a source resonator. in this case, despite the fact that the systems and methods described herein may be providing charging power to the in-use battery pack while in range, the battery pack may still run down, as the power usage may have exceeded the recharge rate. further, the user may simply be moving in and out of range, or be completely out of range while using the device. however, the user may have placed additional battery packs in the vicinity of the source resonator, which have been recharged while not in use, and are now charged sufficiently for use. in another example, the user may be working with the power tool away from the vicinity of the source resonator, but leave the supplemental battery packs to charge in the vicinity of the source resonator, such as in a room with a portable source resonator or extension cord source resonator, in the user's vehicle, in user's tool box, and the like. in this way, the user may not have to worry about taking the time to, and/or remembering to plug in their battery packs for future use. the user may only have to change out the used battery pack for the charged battery pack and place the used one in the vicinity of the source resonator for recharging. device resonators may be built into enclosures with known battery form factors and footprints and may replace traditional chemical batteries in known devices and applications. for example, device resonators may be built into enclosures with mechanical dimensions equivalent to aa batteries, aaa batteries, d batteries, 9v batteries, laptop batteries, cell phone batteries, and the like. the enclosures may include a smaller “button battery” in addition to the device resonator to store charge and provide extended operation, either in terms of time or distance. other energy storage devices in addition to or instead of button batteries may be integrated with the device resonators and any associated power conversion circuitry. these new energy packs may provide similar voltage and current levels as provided by traditional batteries, but may be composed of device resonators, power conversion electronics, a small battery, and the like. these new energy packs may last longer than traditional batteries because they may be more easily recharged and may be recharging constantly when they are located in a wireless power zone. in addition, such energy packs may be lighter than traditional batteries, may be safer to use and store, may operate over wider temperature and humidity ranges, may be less harmful to the environment when thrown away, and the like. as described herein, these energy packs may last beyond the life of the product when used in wireless power zones as described herein. the systems and methods described herein may be used to power visual displays, such as in the case of the laptop screen, but more generally to include the great variety and diversity of displays utilized in today's electrical and electronics components, such as in televisions, computer monitors, desktop monitors, laptop displays, digital photo frames, electronic books, mobile device displays (e.g. on phones, pdas, games, navigation devices, dvd players), and the like. displays that may be powered through one or more of the wireless power transmission systems described herein may also include embedded displays, such as embedded in electronic components (e.g. audio equipment, home appliances, automotive displays, entertainment devices, cash registers, remote controls), in furniture, in building infrastructure, in a vehicle, on the surface of an object (e.g. on the surface of a vehicle, building, clothing, signs, transportation), and the like. displays may be very small with tiny resonant devices, such as in a smart card as described herein, or very large, such as in an advertisement sign. displays powered using the principles disclosed herein may also be any one of a plurality of imaging technologies, such as liquid crystal display (lcd), thin film transistor lcd, passive lcd, cathode ray tube (crt), plasma display, projector display (e.g. lcd, dlp, lcos), surface-conduction electron-emitter display (sed), organic light-emitting diode (oled), and the like. source coil configurations may include attaching to a primary power source, such as building power, vehicle power, from a wireless extension cord as described herein, and the like; attached to component power, such as the base of an electrical component (e.g. the base of a computer, a cable box for a tv); an intermediate relay source coil; and the like. for example, hanging a digital display on the wall may be very appealing, such as in the case of a digital photo frame that receives its information signals wirelessly or through a portable memory device, but the need for an unsightly power cord may make it aesthetically unpleasant. however, with a device coil embedded in the digital photo frame, such as wrapped within the frame portion, may allow the digital photo frame to be hung with no wires at all. the source resonator may then be placed in the vicinity of the digital photo frame, such as in the next room on the other side of the wall, plugged directly into a traditional power outlet, from a wireless extension cord as described herein, from a central source resonator for the room, and the like. the systems and methods described herein may provide wireless power transmission between different portions of an electronics facility. continuing with the example of the laptop computer, and without limitation, the screen of the laptop computer may require power from the base of the laptop. in this instance, the electrical power has been traditionally routed via direct electrical connection from the base of the laptop to the screen over a hinged portion of the laptop between the screen and the base. when a wired connection is utilized, the wired connection may tend to wear out and break, the design functionality of the laptop computer may be limited by the required direct electrical connection, the design aesthetics of the laptop computer may be limited by the required direct electrical connection, and the like. however, a wireless connection may be made between the base and the screen. in this instance, the device resonator may be placed in the screen portion to power the display, and the base may be either powered by a second device resonator, by traditional wired connections, by a hybrid of resonator-battery-direct electrical connection, and the like. this may not only improve the reliability of the power connection due to the removal of the physical wired connection, but may also allow designers to improve the functional and/or aesthetic design of the hinge portion of the laptop in light of the absence of physical wires associated with the hinge. again, the laptop computer has been used here to illustrate how the principles disclosed herein may improve the design of an electric or electronic device, and should not be taken as limiting in any way. for instance, many other electrical devices with separated physical portions could benefit from the systems and methods described herein, such as a refrigerator with electrical functions on the door, including an ice maker, a sensor system, a light, and the like; a robot with movable portions, separated by joints; a car's power system and a component in the car's door; and the like. the ability to provide power to a device via a device resonator from an external source resonator, or to a portion of the device via a device resonator from either external or internal source resonators, will be recognized by someone skilled in the art to be widely applicable across the range of electric and electronic devices. the systems and methods disclosed herein may provide for a sharing of electrical power between devices, such as between charged devices and uncharged devices. for instance a charged up device or appliance may act like a source and send a predetermined amount of energy, dialed in amount of energy, requested and approved amount of energy, and the like, to a nearby device or appliance. for example, a user may have a cell phone and a digital camera that are both capable of transmitting and receiving power through embedded source and device resonators, and one of the devices, say the cell phone, is found to be low on charge. the user may then transfer charge from the digital camera to the cell phone. the source and device resonators in these devices may utilize the same physical resonator for both transmission and reception, utilize separate source and device resonators, one device may be designed to receive and transmit while the other is designed to receive only, one device may be designed to transmit only and the other to receive only, and the like. to prevent complete draining the battery of a device it may have a setting allowing a user to specify how much of the power resource the receiving device is entitled to. it may be useful, for example, to put a limit on the amount of power available to external devices and to have the ability to shut down power transmission when battery power falls below a threshold. the systems and methods described herein may provide wireless power transfer to a nearby electrical or electronics component in association with an electrical facility, where the source resonator is in the electrical facility and the device resonator is in the electronics component. the source resonator may also be connected to, plugged into, attached to the electrical facility, such as through a universal interface (e.g. a usb interface, pc card interface), supplemental electrical outlet, universal attachment point, and the like, of the electrical facility. for example, the source resonator may be inside the structure of a computer on a desk, or be integrated into some object, pad, and the like, that is connected to the computer, such as into one of the computer's usb interfaces. in the example of the source resonator embedded in the object, pad, and the like, and powered through a usb interface, the source resonator may then be easily added to a user's desktop without the need for being integrated into any other electronics device, thus conveniently providing a wireless energy zone around which a plurality of electric and/or electronics devices may be powered. the electrical facility may be a computer, a light fixture, a dedicated source resonator electrical facility, and the like, and the nearby components may be computer peripherals, surrounding electronics components, infrastructure devices, and the like, such as computer keyboards, computer mouse, fax machine, printer, speaker system, cell phone, audio device, intercom, music player, pda, lights, electric pencil sharpener, fan, digital picture frame, calculator, electronic games, and the like. for example, a computer system may be the electrical facility with an integrated source resonator that utilizes a ‘wireless keyboard’ and ‘wireless mouse’, where the use of the term wireless here is meant to indicate that there is wireless communication facility between each device and the computer, and where each device must still contain a separate battery power source. as a result, batteries would need to be replaced periodically, and in a large company, may result in a substantial burden for support personnel for replacement of batteries, cost of batteries, and proper disposal of batteries. alternatively, the systems and methods described herein may provide wireless power transmission from the main body of the computer to each of these peripheral devices, including not only power to the keyboard and mouse, but to other peripheral components such as a fax, printer, speaker system, and the like, as described herein. a source resonator integrated into the electrical facility may provide wireless power transmission to a plurality of peripheral devices, user devices, and the like, such that there is a significant reduction in the need to charge and/or replace batteries for devices in the near vicinity of the source resonator integrated electrical facility. the electrical facility may also provide tuning or auto-tuning software, algorithms, facilities, and the like, for adjusting the power transfer parameters between the electrical facility and the wirelessly powered device. for example, the electrical facility may be a computer on a user's desktop, and the source resonator may be either integrated into the computer or plugged into the computer (e.g. through a usb connection), where the computer provides a facility for providing the tuning algorithm (e.g. through a software program running on the computer). the systems and methods disclosed herein may provide wireless power transfer to a nearby electrical or electronics component in association with a facility infrastructure component, where the source resonator is in, or mounted on, the facility infrastructure component and the device resonator is in the electronics component. for instance, the facility infrastructure component may be a piece of furniture, a fixed wall, a movable wall or partition, the ceiling, the floor, and the source resonator attached or integrated into a table or desk (e.g. just below/above the surface, on the side, integrated into a table top or table leg), a mat placed on the floor (e.g. below a desk, placed on a desk), a mat on the garage floor (e.g. to charge the car and/or devices in the car), in a parking lot/garage (e.g. on a post near where the car is parked), a television (e.g. for charging a remote control), a computer monitor (e.g. to power/charge a wireless keyboard, wireless mouse, cell phone), a chair (e.g. for powering electric blankets, medical devices, personal health monitors), a painting, office furniture, common household appliances, and the like. for example, the facility infrastructure component may be a lighting fixture in an office cubical, where the source resonator and light within the lighting fixture are both directly connected to the facility's wired electrical power. however, with the source resonator now provided in the lighting fixture, there would be no need to have any additional wired connections for those nearby electrical or electronics components that are connected to, or integrated with, a device resonator. in addition, there may be a reduced need for the replacement of batteries for devices with device resonators, as described herein. the use of the systems and methods described herein to supply power to electrical and electronic devices from a central location, such as from a source resonator in an electrical facility, from a facility infrastructure component and the like, may minimize the electrical wiring infrastructure of the surrounding work area. for example, in an enterprise office space there are typically a great number of electrical and electronic devices that need to be powered by wired connections. with utilization of the systems and methods described herein, much of this wiring may be eliminated, saving the enterprise the cost of installation, decreasing the physical limitations associated with office walls having electrical wiring, minimizing the need for power outlets and power strips, and the like. the systems and methods described herein may save money for the enterprise through a reduction in electrical infrastructure associated with installation, re-installation (e.g., reconfiguring office space), maintenance, and the like. in another example, the principles disclosed herein may allow the wireless placement of an electrical outlet in the middle of a room. here, the source could be placed on the ceiling of a basement below the location on the floor above where one desires to put an outlet. the device resonator could be placed on the floor of the room right above it. installing a new lighting fixture (or any other electric device for that matter, e.g. camera, sensor, etc., in the center of the ceiling may now be substantially easier for the same reason). in another example, the systems and methods described herein may provide power “through” walls. for instance, suppose one has an electric outlet in one room (e.g. on a wall), but one would like to have an outlet in the next room, but without the need to call an electrician, or drill through a wall, or drag a wire around the wall, or the like. then one might put a source resonator on the wall in one room, and a device resonator outlet/pickup on the other side of the wall. this may power a flat-screen tv or stereo system or the like (e.g. one may not want to have an ugly wire climbing up the wall in the living room, but doesn't mind having a similar wire going up the wall in the next room, e.g. storage room or closet, or a room with furniture that blocks view of wires running along the wall). the systems and methods described herein may be used to transfer power from an indoor source to various electric devices outside of homes or buildings without requiring holes to be drilled through, or conduits installed in, these outside walls. in this case, devices could be wirelessly powered outside the building without the aesthetic or structural damage or risks associated with drilling holes through walls and siding. in addition, the systems and methods described herein may provide for a placement sensor to assist in placing an interior source resonator for an exterior device resonator equipped electrical component. for example, a home owner may place a security light on the outside of their home which includes a wireless device resonator, and now needs to adequately or optimally position the source resonator inside the home. a placement sensor acting between the source and device resonators may better enable that placement by indicating when placement is good, or to a degree of good, such as in a visual indication, an audio indication, a display indication, and the like. in another example, and in a similar way, the systems and methods described herein may provide for the installation of equipment on the roof of a home or building, such as radio transmitters and receivers, solar panels and the like. in the case of the solar panel, the source resonator may be associated with the panel, and power may be wirelessly transferred to a distribution panel inside the building without the need for drilling through the roof. the systems and methods described herein may allow for the mounting of electric or electrical components across the walls of vehicles (such as through the roof) without the need to drill holes, such as for automobiles, water craft, planes, trains, and the like. in this way, the vehicle's walls may be left intact without holes being drilled, thus maintaining the value of the vehicle, maintaining watertightness, eliminating the need to route wires, and the like. for example, mounting a siren or light to the roof of a police car decreases the future resale of the car, but with the systems and methods described herein, any light, horn, siren, and the like, may be attached to the roof without the need to drill a hole. the systems and methods described herein may be used for wireless transfer of power from solar photovoltaic (pv) panels. pv panels with wireless power transfer capability may have several benefits including simpler installation, more flexible, reliable, and weatherproof design. wireless power transfer may be used to transfer power from the pv panels to a device, house, vehicle, and the like. solar pv panels may have a wireless source resonator allowing the pv panel to directly power a device that is enabled to receive the wireless power. for example, a solar pv panel may be mounted directly onto the roof of a vehicle, building, and the like. the energy captured by the pv panel may be wirelessly transferred directly to devices inside the vehicle or under the roof of a building. devices that have resonators can wirelessly receive power from the pv panel. wireless power transfer from pv panels may be used to transfer energy to a resonator that is coupled to the wired electrical system of a house, vehicle, and the like allowing traditional power distribution and powering of conventional devices without requiring any direct contact between the exterior pv panels and the internal electrical system. with wireless power transfer significantly simpler installation of rooftop pv panels is possible because power may be transmitted wirelessly from the panel to a capture resonator in the house, eliminating all outside wiring, connectors, and conduits, and any holes through the roof or walls of the structure. wireless power transfer used with solar cells may have a benefit in that it can reduced roof danger since it eliminates the need for electricians to work on the roof to interconnect panels, strings, and junction boxes. installation of solar panels integrated with wireless power transfer may require less skilled labor since fewer electrical contacts need to be made. less site specific design may be required with wireless power transfer since the technology gives the installer the ability to individually optimize and position each solar pv panel, significantly reducing the need for expensive engineering and panel layout services. there may not be need to carefully balance the solar load on every panel and no need for specialized dc wiring layout and interconnections. for rooftop or on-wall installations of pv panels, the capture resonator may be mounted on the underside of the roof, inside the wall, or in any other easily accessible inside space within a foot or two of the solar pv panel. a diagram showing a possible general rooftop pv panel installation is shown in fig. 51 . various pv solar collectors may be mounted in top of a roof with wireless power capture coils mounted inside the building under the roof. the resonator coils in the pv panels can transfer their energy wirelessly through the roof to the wireless capture coils. the captured energy from the pv cells may be collected and coupled to the electrical system of the house to power electric and electronic devices or coupled to the power grid when more power than needed is generated. energy is captured from the pv cells without requiring holes or wires that penetrate the roof or the walls of the building. each pv panel may have a resonator that is coupled to a corresponding resonator on the interior of the vehicle or building. multiple panels may utilize wireless power transfer between each other to transfer or collect power to one or a couple of designated panels that are coupled to resonators on the interior of the vehicle of house. panels may have wireless power resonators on their sides or in their perimeter that can couple to resonators located in other like panels allowing transfer of power from panel to panel. an additional bus or connection structure may be provided that wirelessly couples the power from multiple panels on the exterior of a building or vehicle and transfers power to one or a more resonators on the interior of building or vehicle. for example, as shown in fig. 51 , a source resonator 5102 may be coupled to a pv cell 5100 mounted on top of roof 5104 of a building. a corresponding capture resonator 5106 is placed inside the building. the solar energy captured by the pv cells can then be transferred between the source resonators 5102 outside to the device resonators 5106 inside the building without having direct holes and connections through the building. each solar pv panel with wireless power transfer may have its own inverter, significantly improving the economics of these solar systems by individually optimizing the power production efficiency of each panel, supporting a mix of panel sizes and types in a single installation, including single panel “pay-as-you-grow” system expansions. reduction of installation costs may make a single panel economical for installation. eliminating the need for panel string designs and careful positioning and orienting of multiple panels, and eliminating a single point of failure for the system. wireless power transfer in pv solar panels may enable more solar deployment scenarios because the weather-sealed solar pv panels eliminate the need to drill holes for wiring through sealed surfaces such as car roofs and ship decks, and eliminate the requirement that the panels be installed in fixed locations. with wireless power transfer, pv panels may be deployed temporarily, and then moved or removed, without leaving behind permanent alterations to the surrounding structures. they may be placed out in a yard on sunny days, and moved around to follow the sun, or brought inside for cleaning or storage, for example. for backyard or mobile solar pv applications, an extension cord with a wireless energy capture device may be thrown on the ground or placed near the solar unit. the capture extension cord can be completely sealed from the elements and electrically isolated, so that it may be used in any indoor or outdoor environment. with wireless power transfer no wires or external connections may be necessary and the pv solar panels can be completely weather sealed. significantly improved reliability and lifetime of electrical components in the solar pv power generation and transmission circuitry can be expected since the weather-sealed enclosures can protect components from uv radiation, humidity, weather, and the like. with wireless power transfer and weather-sealed enclosures it may be possible to use less expensive components since they will no longer be directly exposed to external factors and weather elements and it may reduce the cost of pv panels. power transfer between the pv panels and the capture resonators inside a building or a vehicle may be bidirectional. energy may be transmitted from the house grid to the pv panels to provide power when the panels do not have enough energy to perform certain tasks such. reverse power flow can be used to melt snow from the panels, or power motors that will position the panels in a more favorable positions with respect to the sun energy. once the snow is melted or the panels are repositioned and the pv panels can generate their own energy the direction of power transfer can be returned to normal delivering power from the pv panels to buildings, vehicles, or devices. pv panels with wireless power transfer may include auto-tuning on installation to ensure maximum and efficient power transfer to the wireless collector. variations in roofing materials or variations in distances between the pv panels and the wireless power collector in different installations may affect the performance or perturb the properties of the resonators of the wireless power transfer. to reduce the installation complexity the wireless power transfer components may include a tuning capability to automatically adjust their operating point to compensate for any effects due to materials or distance. frequency, impedance, capacitance, inductance, duty cycle, voltage levels and the like may be adjusted to ensure efficient and safe power transfer the systems and methods described herein may be used to provide a wireless power zone on a temporary basis or in extension of traditional electrical outlets to wireless power zones, such as through the use of a wireless power extension cord. for example, a wireless power extension cord may be configured as a plug for connecting into a traditional power outlet, a long wire such as in a traditional power extension cord, and a resonant source coil on the other end (e.g. in place of, or in addition to, the traditional socket end of the extension the wireless extension cord may also be configured where there are source resonators at a plurality of locations along the wireless extension cord. this configuration may then replace any traditional extension cord where there are wireless power configured devices, such as providing wireless power to a location where there is no convenient power outlet (e.g. a location in the living room where there's no outlet), for temporary wireless power where there is no wired power infrastructure (e.g. a construction site), out into the yard where there are no outlets (e.g. for parties or for yard grooming equipment that is wirelessly powered to decrease the chances of cutting the traditional electrical cord), and the like. the wireless extension cord may also be used as a drop within a wall or structure to provide wireless power zones within the vicinity of the drop. for example, a wireless extension cord could be run within a wall of a new or renovated room to provide wireless power zones without the need for the installation of traditional electrical wiring and outlets. the systems and methods described herein may be utilized to provide power between moving parts or rotating assemblies of a vehicle, a robot, a mechanical device, a wind turbine, or any other type of rotating device or structure with moving parts such as robot arms, construction vehicles, movable platforms and the like. traditionally, power in such systems may have been provided by slip rings or by rotary joints for example. using wireless power transfer as described herein, the design simplicity, reliability and longevity of these devices may be significantly improved because power can be transferred over a range of distances without any physical connections or contact points that may wear down or out with time. in particular, the preferred coaxial and parallel alignment of the source and device coils may provide wireless power transmission that is not severely modulated by the relative rotational motion of the two coils. the systems and methods described herein may be utilized to extend power needs beyond the reach of a single source resonator by providing a series of source-device-source-device resonators. for instance, suppose an existing detached garage has no electrical power and the owner now wants to install a new power service. however, the owner may not want to run wires all over the garage, or have to break into the walls to wire electrical outlets throughout the structure. in this instance, the owner may elect to connect a source resonator to the new power service, enabling wireless power to be supplied to device resonator outlets throughout the back of the garage. the owner may then install a device-source ‘relay’ to supply wireless power to device resonator outlets in the front of the garage. that is, the power relay may now receive wireless power from the primary source resonator, and then supply available power to a second source resonator to supply power to a second set of device resonators in the front of the garage. this configuration may be repeated again and again to extend the effective range of the supplied wireless power. multiple resonators may be used to extend power needs around an energy blocking material. for instance, it may be desirable to integrate a source resonator into a computer or computer monitor such that the resonator may power devices placed around and especially in front of the monitor or computer such as keyboards, computer mice, telephones, and the like. due to aesthetics, space constraints, and the like an energy source that may be used for the source resonator may only be located or connected to in the back of the monitor or computer. in many designs of computer or monitors metal components and metal containing circuits are used in the design and packaging which may limit and prevent power transfer from source resonator in the back of the monitor or computer to the front of the monitor or computer. an additional repeater resonator may be integrated into the base or pedestal of the monitor or computer that couples to the source resonator in the back of the monitor or computer and allows power transfer to the space in front of the monitor or computer. the intermediate resonator integrated into the base or pedestal of the monitor or computer does not require an additional power source, it captures power from the source resonator and transfers power to the front around the blocking or power shielding metal components of the monitor or computer. the systems and methods described herein may be built-into, placed on, hung from, embedded into, integrated into, and the like, the structural portions of a space, such as a vehicle, office, home, room, building, outdoor structure, road infrastructure, and the like. for instance, one or more sources may be built into, placed on, hung from, embedded or integrated into a wall, a ceiling or ceiling panel, a floor, a divider, a doorway, a stairwell, a compartment, a road surface, a sidewalk, a ramp, a fence, an exterior structure, and the like. one or more sources may be built into an entity within or around a structure, for instance a bed, a desk, a chair, a rug, a mirror, a clock, a display, a television, an electronic device, a counter, a table, a piece of furniture, a piece of artwork, an enclosure, a compartment, a ceiling panel, a floor or door panel, a dashboard, a trunk, a wheel well, a post, a beam, a support or any like entity. for example, a source resonator may be integrated into the dashboard of a user's car so that any device that is equipped with or connected to a device resonator may be supplied with power from the dashboard source resonator. in this way, devices brought into or integrated into the car may be constantly charged or powered while in the car. the systems and methods described herein may provide power through the walls of vehicles, such as boats, cars, trucks, busses, trains, planes, satellites and the like. for instance, a user may not want to drill through the wall of the vehicle in order to provide power to an electric device on the outside of the vehicle. a source resonator may be placed inside the vehicle and a device resonator may be placed outside the vehicle (e.g. on the opposite side of a window, wall or structure). in this way the user may achieve greater flexibility in optimizing the placement, positioning and attachment of the external device to the vehicle, (such as without regard to supplying or routing electrical connections to the device). in addition, with the electrical power supplied wirelessly, the external device may be sealed such that it is water tight, making it safe if the electric device is exposed to weather (e.g. rain), or even submerged under water. similar techniques may be employed in a variety of applications, such as in charging or powering hybrid vehicles, navigation and communications equipment, construction equipment, remote controlled or robotic equipment and the like, where electrical risks exist because of exposed conductors. the systems and methods described herein may provide power through the walls of vacuum chambers or other enclosed spaces such as those used in semiconductor growth and processing, material coating systems, aquariums, hazardous materials handling systems and the like. power may be provided to translation stages, robotic arms, rotating stages, manipulation and collection devices, cleaning devices and the like. the systems and methods described herein may provide wireless power to a kitchen environment, such as to counter-top appliances, including mixers, coffee makers, toasters, toaster ovens, grills, griddles, electric skillets, electric pots, electric woks, waffle makers, blenders, food processors, crock pots, warming trays, induction cooktops, lights, computers, displays, and the like. this technology may improve the mobility and/or positioning flexibility of devices, reduce the number of power cords stored on and strewn across the counter-top, improve the washability of the devices, and the like. for example, an electric skillet may traditionally have separate portions, such as one that is submersible for washing and one that is not submersible because it includes an external electrical connection (e.g. a cord or a socket for a removable cord). however, with a device resonator integrated into the unit, all electrical connections may be sealed, and so the entire device may now be submersed for cleaning. in addition, the absence of an external cord may eliminate the need for an available electrical wall outlet, and there is no longer a need for a power cord to be placed across the counter or for the location of the electric griddle to be limited to the location of an available electrical wall outlet. the systems and methods described herein may provide continuous power/charging to devices equipped with a device resonator because the device doesn't leave the proximity of a source resonator, such as fixed electrical devices, personal computers, intercom systems, security systems, household robots, lighting, remote control units, televisions, cordless phones, and the like. for example, a household robot (e.g. roomba) could be powered/charged via wireless power, and thus work arbitrarily long without recharging. in this way, the power supply design for the household robot may be changed to take advantage of this continuous source of wireless power, such as to design the robot to only use power from the source resonator without the need for batteries, use power from the source resonator to recharge the robot's batteries, use the power from the source resonator to trickle charge the robot's batteries, use the power from the source resonator to charge a capacitive energy storage unit, and the like. similar optimizations of the power supplies and power circuits may be enabled, designed, and realized, for any and all of the devices disclosed herein. the systems and methods described herein may be able to provide wireless power to electrically heated blankets, heating pads/patches, and the like. these electrically heated devices may find a variety of indoor and outdoor uses. for example, hand and foot warmers supplied to outdoor workers such as guards, policemen, construction workers and the like might be remotely powered from a source resonator associated with or built into a nearby vehicle, building, utility pole, traffic light, portable power unit, and the like. the systems and methods described herein may be used to power a portable information device that contains a device resonator and that may be powered up when the information device is near an information source containing a source resonator. for instance, the information device may be a card (e.g. credit card, smart card, electronic card, and the like) carried in a user's pocket, wallet, purse, vehicle, bike, and the like. the portable information device may be powered up when it is in the vicinity of an information source that then transmits information to the portable information device that may contain electronic logic, electronic processors, memory, a display, an lcd display, leds, rfid tags, and the like. for example, the portable information device may be a credit card with a display that “turns on” when it is near an information source, and provide the user with some information such as, “you just received a coupon for 50% off your next coca cola purchase”. the information device may store information such as coupon or discount information that could be used on subsequent purchases. the portable information device may be programmed by the user to contain tasks, calendar appointments, to-do lists, alarms and reminders, and the like. the information device may receive up-to-date price information and inform the user of the location and price of previously selected or identified items. the systems and methods described herein may provide wireless power transmission to directly power or recharge the batteries in sensors, such as environmental sensors, security sensors, agriculture sensors, appliance sensors, food spoilage sensors, power sensors, and the like, which may be mounted internal to a structure, external to a structure, buried underground, installed in walls, and the like. for example, this capability may replace the need to dig out old sensors to physically replace the battery, or to bury a new sensor because the old sensor is out of power and no longer operational. these sensors may be charged up periodically through the use of a portable sensor source resonator charging unit. for instance, a truck carrying a source resonator equipped power source, say providing ˜kw of power, may provide enough power to a ˜mw sensor in a few minutes to extend the duration of operation of the sensor for more than a year. sensors may also be directly powered, such as powering sensors that are in places where it is difficult to connect to them with a wire but they are still within the vicinity of a source resonator, such as devices outside of a house (security camera), on the other side of a wall, on an electric lock on a door, and the like. in another example, sensors that may need to be otherwise supplied with a wired power connection may be powered through the systems and methods described herein. for example, a ground fault interrupter breaker combines residual current and over-current protection in one device for installation into a service panel. however, the sensor traditionally has to be independently wired for power, and this may complicate the installation. however, with the systems and methods described herein the sensor may be powered with a device resonator, where a single source resonator is provided within the service panel, thus simplifying the installation and wiring configuration within the service panel. in addition, the single source resonator may power device resonators mounted on either side of the source resonator mounted within the service panel, throughout the service panel, to additional nearby service panels, and the like. the systems and methods described herein may be employed to provide wireless power to any electrical component associated with electrical panels, electrical rooms, power distribution and the like, such as in electric switchboards, distribution boards, circuit breakers, transformers, backup batteries, fire alarm control panels, and the like. through the use of the systems and methods described herein, it may be easier to install, maintain, and modify electrical distribution and protection components and system installations. in another example, sensors that are powered by batteries may run continuously, without the need to change the batteries, because wireless power may be supplied to periodically or continuously recharge or trickle charge the battery. in such applications, even low levels of power may adequately recharge or maintain the charge in batteries, significantly extending their lifetime and usefulness. in some cases, the battery life may be extended to be longer than the lifetime of the device it is powering, making it essentially a battery that “lasts forever”. the systems and methods described herein may be used for charging implanted medical device batteries, such as in an artificial heart, pacemaker, heart pump, insulin pump, implanted coils for nerve or acupressure/acupuncture point stimulation, and the like. for instance, it may not be convenient or safe to have wires sticking out of a patient because the wires may be a constant source of possible infection and may generally be very unpleasant for the patient. the systems and methods described herein may also be used to charge or power medical devices in or on a patient from an external source, such as from a bed or a hospital wall or ceiling with a source resonator. such medical devices may be easier to attach, read, use and monitor the patient. the systems and methods described herein may ease the need for attaching wires to the patient and the patient's bed or bedside, making it more convenient for the patient to move around and get up out of bed without the risk of inadvertently disconnecting a medical device. this may, for example, be usefully employed with patients that have multiple sensors monitoring them, such as for measuring pulse, blood pressure, glucose, and the like. for medical and monitoring devices that utilize batteries, the batteries may need to be replaced quite often, perhaps multiple times a week. this may present risks associated with people forgetting to replace batteries, not noticing that the devices or monitors are not working because the batteries have died, infection associated with improper cleaning of the battery covers and compartments, and the like. the systems and methods described herein may reduce the risk and complexity of medical device implantation procedures. today many implantable medical devices such as ventricular assist devices, pacemakers, defibrillators and the like, require surgical implantation due to their device form factor, which is heavily influenced by the volume and shape of the long-life battery that is integrated in the device. in one aspect, there is described herein a non-invasive method of recharging the batteries so that the battery size may be dramatically reduced, and the entire device may be implanted, such as via a catheter. a catheter implantable device may include an integrated capture or device coil. a catheter implantable capture or device coil may be designed so that it may be wired internally, such as after implantation. the capture or device coil may be deployed via a catheter as a rolled up flexible coil (e.g. rolled up like two scrolls, easily unrolled internally with a simple spreader mechanism). the power source coil may be worn in a vest or article of clothing that is tailored to fit in such a way that places the source in proper position, may be placed in a chair cushion or bed cushion, may be integrated into a bed or piece of furniture, and the like. the systems and methods described herein may enable patients to have a ‘sensor vest’, sensor patch, and the like, that may include at least one of a plurality of medical sensors and a device resonator that may be powered or charged when it is in the vicinity of a source resonator. traditionally, this type of medical monitoring facility may have required batteries, thus making the vest, patch, and the like, heavy, and potentially impractical. but using the principles disclosed herein, no batteries (or a lighter rechargeable battery) may be required, thus making such a device more convenient and practical, especially in the case where such a medical device could be held in place without straps, such as by adhesive, in the absence of batteries or with substantially lighter batteries. a medical facility may be able to read the sensor data remotely with the aim of anticipating (e.g. a few minutes ahead of) a stroke, a heart-attack, or the like. when the vest is used by a person in a location remote from the medical facility, such as in their home, the vest may then be integrated with a cell-phone or communications device to call an ambulance in case of an accident or a medical event. the systems and methods described herein may be of particular value in the instance when the vest is to be used by an elderly person, where traditional non-wireless recharging practices (e.g. replacing batteries, plugging in at night, and the like) may not be followed as required. the systems and methods described herein may also be used for charging devices that are used by or that aid handicapped or disabled people who may have difficulty replacing or recharging batteries, or reliably supplying power to devices they enjoy or rely on. the systems and methods described herein may be used for the charging and powering of artificial limbs. artificial limbs have become very capable in terms of replacing the functionality of original limbs, such as arms, legs, hands and feet. however, an electrically powered artificial limb may require substantial power, (such as 10-20 w) which may translate into a substantial battery. in that case, the amputee may be left with a choice between a light battery that doesn't last very long, and a heavy battery that lasts much longer, but is more difficult to ‘carry’ around. the systems and methods described herein may enable the artificial limb to be powered with a device resonator, where the source resonator is either carried by the user and attached to a part of the body that may more easily support the weight (such as on a belt around the waist, for example) or located in an external location where the user will spend an adequate amount of time to keep the device charged or powered, such as at their desk, in their car, in their bed, and the like. the systems and methods described herein may be used for charging and powering of electrically powered exo-skeletons, such as those used in industrial and military applications, and for elderly/weak/sick people. an electrically powered exo-skeleton may provide up to a 10-to-20 times increase in “strength” to a person, enabling the person to perform physically strenuous tasks repeatedly without much fatigue. however, exo-skeletons may require more than 100 w of power under certain use scenarios, so battery powered operation may be limited to 30 minutes or less. the delivery of wireless power as described herein may provide a user of an exo-skeleton with a continuous supply of power both for powering the structural movements of the exo-skeleton and for powering various monitors and sensors distributed throughout the structure. for instance, an exo-skeleton with an embedded device resonator(s) may be supplied with power from a local source resonator. for an industrial exo-skeleton, the source resonator may be placed in the walls of the facility. for a military exo-skeleton, the source resonator may be carried by an armored vehicle. for an exo-skeleton employed to assist a caretaker of the elderly, the source resonator(s) may be installed or placed in or the room(s) of a person's home. the systems and methods described herein may be used for the powering/charging of portable medical equipment, such as oxygen systems, ventilators, defibrillators, medication pumps, monitors, and equipment in ambulances or mobile medical units, and the like. being able to transport a patient from an accident scene to the hospital, or to move patients in their beds to other rooms or areas, and bring all the equipment that is attached with them and have it powered the whole time offers great benefits to the patients' health and eventual well-being. certainly one can understand the risks and problems caused by medical devices that stop working because their battery dies or because they must be unplugged while a patient is transported or moved in any way. for example, an emergency medical team on the scene of an automotive accident might need to utilize portable medical equipment in the emergency care of patients in the field. such portable medical equipment must be properly maintained so that there is sufficient battery life to power the equipment for the duration of the emergency. however, it is too often the case that the equipment is not properly maintained so that batteries are not fully charged and in some cases, necessary equipment is not available to the first responders. the systems and methods described herein may provide for wireless power to portable medical equipment (and associated sensor inputs on the patient) in such a way that the charging and maintaining of batteries and power packs is provided automatically and without human intervention. such a system also benefits from the improved mobility of a patient unencumbered by a variety of power cords attached to the many medical monitors and devices used in their treatment. the systems and methods described herein may be used to for the powering/charging of personal hearing aids. personal hearing aids need to be small and light to fit into or around the ear of a person. the size and weight restrictions limit the size of batteries that can be used. likewise, the size and weight restrictions of the device make battery replacement difficult due to the delicacy of the components. the dimensions of the devices and hygiene concerns make it difficult to integrate additional charging ports to allow recharging of the batteries. the systems and methods described herein may be integrated into the hearing aid and may reduce the size of the necessary batteries which may allow even smaller hearing aids. using the principles disclosed herein, the batteries of the hearing aid may be recharged without requiring external connections or charging ports. charging and device circuitry and a small rechargeable battery may be integrated into a form factor of a conventional hearing aid battery allowing retrofit into existing hearing aids. the hearing aid may be recharged while it is used and worn by a person. the energy source may be integrated into a pad or a cup allowing recharging when the hearing is placed on such a structure. the charging source may be integrated into a hearing aid dryer box allowing wireless recharging while the hearing aid is drying or being sterilized. the source and device resonator may be used to also heat the device reducing or eliminating the need for an additional heating element. portable charging cases powered by batteries or ac adaptors may be used as storage and charging stations. the source resonator for the medical systems described above may be in the main body of some or all of the medical equipment, with device resonators on the patient's sensors and devices; the source resonator may be in the ambulance with device resonators on the patient's sensors and the main body of some or all of the equipment; a primary source resonator may be in the ambulance for transferring wireless power to a device resonator on the medical equipment while the medical equipment is in the ambulance and a second source resonator is in the main body of the medical equipment and a second device resonator on the patient sensors when the equipment is away from the ambulance; and the like. the systems and methods described herein may significantly improve the ease with which medical personnel are able to transport patients from one location to another, where power wires and the need to replace or manually charge associated batteries may now be reduced. the systems and methods described herein may be used for the charging of devices inside a military vehicle or facility, such as a tank, armored carrier, mobile shelter, and the like. for instance, when soldiers come back into a vehicle after “action” or a mission, they may typically start charging their electronic devices. if their electronic devices were equipped with device resonators, and there was a source resonator inside the vehicle, (e.g. integrated in the seats or on the ceiling of the vehicle), their devices would start charging immediately. in fact, the same vehicle could provide power to soldiers/robots (e.g. packbot from irobot) standing outside or walking beside the vehicle. this capability may be useful in minimizing accidental battery-swapping with someone else (this may be a significant issue, as soldiers tend to trust only their own batteries); in enabling quicker exits from a vehicle under attack; in powering or charging laptops or other electronic devices inside a tank, as too many wires inside the tank may present a hazard in terms of reduced ability to move around fast in case of “trouble” and/or decreased visibility; and the like. the systems and methods described herein may provide a significant improvement in association with powering portable power equipment in a military environment. the systems and methods described herein may provide wireless powering or charging capabilities to mobile vehicles such as golf carts or other types of carts, all-terrain vehicles, electric bikes, scooters, cars, mowers, bobcats and other vehicles typically used for construction and landscaping and the like. the systems and methods described herein may provide wireless powering or charging capabilities to miniature mobile vehicles, such as mini-helicopters, airborne drones, remote control planes, remote control boats, remote controlled or robotic rovers, remote controlled or robotic lawn mowers or equipment, bomb detection robots, and the like. for instance, mini-helicopter flying above a military vehicle to increase its field of view can fly for a few minutes on standard batteries. if these mini-helicopters were fitted with a device resonator, and the control vehicle had a source resonator, the mini-helicopter might be able to fly indefinitely. the systems and methods described herein may provide an effective alternative to recharging or replacing the batteries for use in miniature mobile vehicles. in addition, the systems and methods described herein may provide power/charging to even smaller devices, such as microelectromechanical systems (mems), nano-robots, nano devices, and the like. in addition, the systems and methods described herein may be implemented by installing a source device in a mobile vehicle or flying device to enable it to serve as an in-field or in-flight re-charger, that may position itself autonomously in proximity to a mobile vehicle that is equipped with a device resonator. the systems and methods described herein may be used to provide power networks for temporary facilities, such as military camps, oil drilling setups, remote filming locations, and the like, where electrical power is required, such as for power generators, and where power cables are typically run around the temporary facility. there are many instances when it is necessary to set up temporary facilities that require power. the systems and methods described herein may enable a more efficient way to rapidly set up and tear down these facilities, and may reduce the number of wires that must be run throughout the faculties to supply power. for instance, when special forces move into an area, they may erect tents and drag many wires around the camp to provide the required electricity. instead, the systems and methods described herein may enable an army vehicle, outfitted with a power supply and a source resonator, to park in the center of the camp, and provide all the power to nearby tents where the device resonator may be integrated into the tents, or some other piece of equipment associated with each tent or area. a series of source-device-source-device resonators may be used to extend the power to tents that are farther away. that is, the tents closest to the vehicle could then provide power to tents behind them. the systems and methods described herein may provide a significant improvement to the efficiency with which temporary installations may be set up and torn down, thus improving the mobility of the associated facility. the systems and methods described herein may be used in vehicles, such as for replacing wires, installing new equipment, powering devices brought into the vehicle, charging the battery of a vehicle (e.g. for a traditional gas powered engine, for a hybrid car, for an electric car, and the like), powering devices mounted to the interior or exterior of the vehicle, powering devices in the vicinity of the vehicle, and the like. for example, the systems and methods described herein may be used to replace wires such as those are used to power lights, fans and sensors distributed throughout a vehicle. as an example, a typical car may have 50 kg of wires associated with it, and the use of the systems and methods described herein may enable the elimination of a substantial amount of this wiring. the performance of larger and more weight sensitive vehicles such as airplanes or satellites could benefit greatly from having the number of cables that must be run throughout the vehicle reduced. the systems and methods described herein may allow the accommodation of removable or supplemental portions of a vehicle with electric and electrical devices without the need for electrical harnessing. for example, a motorcycle may have removable side boxes that act as a temporary trunk space for when the cyclist is going on a long trip. these side boxes may have exterior lights, interior lights, sensors, auto equipment, and the like, and if not for being equipped with the systems and methods described herein might require electrical connections and harnessing. an in-vehicle wireless power transmission system may charge or power one or more mobile devices used in a car: mobile phone handset, bluetooth headset, blue tooth hands free speaker phone, gps, mp3 player, wireless audio transceiver for streaming mp3 audio through car stereo via fm, bluetooth, and the like. the in vehicle wireless power source may utilize source resonators that are arranged in any of several possible configurations including charging pad on dash, charging pad otherwise mounted on floor, or between seat and center console, charging “cup” or receptacle that fits in cup holder or on dash, and the like. the wireless power transmission source may utilize a rechargeable battery system such that said supply battery gets charged whenever the vehicle power is on such that when the vehicle is turned off the wireless supply can draw power from the supply battery and can continue to wirelessly charge or power mobile devices that are still in the car. the plug-in electric cars, hybrid cars, and the like, of the future need to be charged, and the user may need to plug in to an electrical supply when they get home or to a charging station. based on a single over-night recharging, the user may be able to drive up to 50 miles the next day. therefore, in the instance of a hybrid car, if a person drives less than 50 miles on most days, they will be driving mostly on electricity. however, it would be beneficial if they didn't have to remember to plug in the car at night. that is, it would be nice to simply drive into a garage, and have the car take care of its own charging. to this end, a source resonator may be built into the garage floor and/or garage side-wall, and the device resonator may be built into the bottom (or side) of the car. even a few kw transfer may be sufficient to recharge the car over-night. the in-vehicle device resonator may measure magnetic field properties to provide feedback to assist in vehicle (or any similar device) alignment to a stationary resonating source. the vehicle may use this positional feedback to automatically position itself to achieve optimum alignment, thus optimum power transmission efficiency. another method may be to use the positional feedback to help the human operator to properly position the vehicle or device, such as by making led's light up, providing noises, and the like when it is well positioned. in such cases where the amount of power being transmitted could present a safety hazard to a person or animal that intrudes into the active field volume, the source or receiver device may be equipped with an active light curtain or some other external device capable of sensing intrusion into the active field volume, and capable of shutting off the source device and alert a human operator. in addition, the source device may be equipped with self-sensing capability such that it may detect that its expected power transmission rate has been interrupted by an intruding element, and in such case shut off the source device and alert a human operator. physical or mechanical structures such as hinged doors or inflatable bladder shields may be incorporated as a physical barrier to prevent unwanted intrusions. sensors such as optical, magnetic, capacitive, inductive, and the like may also be used to detect foreign structures or interference between the source and device resonators. the shape of the source resonator may be shaped such to prevent water or debris accumulation. the source resonator may be placed in a cone shaped enclosure or may have an enclosure with an angled top to allow water and debris to roll off. the source of the system may use battery power of the vehicle or its own battery power to transmit its presence to the source to initiate power transmission. the source resonator may be mounted on an embedded or hanging post, on a wall, on a stand, and the like for coupling to a device resonator mounted on the bumper, hood, body panel, and the like, of an electric vehicle. the source resonator may be enclosed or embedded into a flexible enclosure such as a pillow, a pad, a bellows, a spring loaded enclosure and the like so that the electric vehicle may make contact with the structure containing the source coil without damaging the car in any way. the structure containing the source may prevent objects from getting between the source and device resonators. because the wireless power transfer may be relatively insensitive to misalignments between the source and device coils, a variety of flexible source structures and parking procedures may be appropriate for this application. the systems and methods described herein may be used to trickle charge batteries of electric, hybrid or combustion engine vehicles. vehicles may require small amounts of power to maintain or replenish battery power. the power may be transferred wirelessly from a source to a device resonator that may be incorporated into the front grill, roof, bottom, or other parts of the vehicle. the device resonator may be designed to fit into a shape of a logo on the front of a vehicle or around the grill as not to obstruct air flow through the radiator. the device or source resonator may have additional modes of operation that allow the resonator to be used as a heating element which can be used to melt of snow or ice from the vehicle. an electric vehicle or hybrid vehicle may require multiple device resonators, such as to increase the ease with which the vehicle may come in proximity with a source resonator for charging (i.e. the greater the number and varied position of device resonators are, the greater the chances that the vehicle can pull in and interface with a diversity of charging stations), to increase the amount of power that can be delivered in a period of time (e.g. additional device resonators may be required to keep the local heating due to charging currents to acceptable levels), to aid in automatic parking/docking the vehicle with the charging station, and the like. for example, the vehicle may have multiple resonators (or a single resonator) with a feedback system that provides guidance to either the driver or an automated parking/docking facility in the parking of the vehicle for optimized charging conditions (i.e., the optimum positioning of the vehicle's device resonator to the charging station's source resonator may provide greater power transfer efficiency). an automated parking/docking facility may allow for the automatic parking of the vehicle based on how well the vehicle is coupled. the power transmission system may be used to power devices and peripherals of a vehicle. power to peripherals may be provided while a vehicle is charging, or while not charging, or power may be delivered to conventional vehicles that do not need charging. for example, power may be transferred wirelessly to conventional non-electric cars to power air conditioning, refrigeration units, heaters, lights, and the like while parked to avoid running the engine which may be important to avoid exhaust build up in garage parking lots or loading docks. power may for example be wirelessly transferred to a bus while it is parked to allow powering of lights, peripherals, passenger devices, and the like avoiding the use of onboard engines or power sources. power may be wirelessly transferred to an airplane while parked on the tarmac or in a hanger to power instrumentation, climate control, de-icing equipment, and the like without having to use onboard engines or power sources. wireless power transmission on vehicles may be used to enable the concept of vehicle to grid (v2g). vehicle to grid is based on utilizing electric vehicles and plug-in hybrid electric vehicles (phev) as distributed energy storage devices, charged at night when the electric grid is underutilized, and available to discharge back into the grid during episodes of peak demand that occur during the day. the wireless power transmission system on a vehicle and the respective infrastructure may be implemented in such a way as to enable bidirectional energy flow—so that energy can flow back into the grid from the vehicle—without requiring a plug in connection. vast fleets of vehicles, parked at factories, offices, parking lots, can be viewed as “peaking power capacity” by the smart grid. wireless power transmission on vehicles can make such a v2g vision a reality. by simplifying the process of connecting a vehicle to the grid, (i.e. by simply parking it in a wireless charging enabled parking spot), it becomes much more likely that a certain number of vehicles will be “dispatchable” when the grid needs to tap their power. without wireless charging, electric and phev owners will likely charge their vehicles at home, and park them at work in conventional parking spots. who will want to plug their vehicle in at work, if they do not need charging? with wireless charging systems capable of handling 3 kw, 100,000 vehicles can provide 300 megawatts back to the grid—using energy generated the night before by cost effective base load generating capacity. it is the streamlined ergonomics of the cordless self charging phev and electric vehicles that make it a viable v2g energy source. the systems and methods described herein may be used to power sensors on the vehicle, such as sensors in tires to measure air-pressure, or to run peripheral devices in the vehicle, such as cell phones, gps devices, navigation devices, game players, audio or video players, dvd players, wireless routers, communications equipment, anti-theft devices, radar devices, and the like. for example, source resonators described herein may be built into the main compartment of the car in order to supply power to a variety of devices located both inside and outside of the main compartment of the car. where the vehicle is a motorcycle or the like, devices described herein may be integrated into the body of the motorcycle, such as under the seat, and device resonators may be provided in a user's helmet, such as for communications, entertainment, signaling, and the like, or device resonators may be provided in the user's jacket, such as for displaying signals to other drivers for safety, and the like. the systems and methods described herein may be used in conjunction with transportation infrastructure, such as roads, trains, planes, shipping, and the like. for example, source resonators may be built into roads, parking lots, rail-lines, and the like. source resonators may be built into traffic lights, signs, and the like. for example, with source resonators embedded into a road, and device resonators built into vehicles, the vehicles may be provided power as they drive along the road or as they are parked in lots or on the side of the road. the systems and methods described herein may provide an effective way for electrical systems in vehicles to be powered and/or charged while the vehicle traverses a road network, or a portion of a road network. in this way, the systems and methods described herein may contribute to the powering/charging of autonomous vehicles, automatic guided vehicles, and the like. the systems and methods described herein may provide power to vehicles in places where they typically idle or stop, such as in the vicinity of traffic lights or signs, on highway ramps, or in parking lots. the systems and methods described herein may be used in an industrial environment, such as inside a factory for powering machinery, powering/charging robots, powering and/or charging wireless sensors on robot arms, powering/charging tools and the like. for example, using the systems and methods described herein to supply power to devices on the arms of robots may help eliminate direct wire connections across the joints of the robot arm. in this way, the wearing out of such direct wire connections may be reduced, and the reliability of the robot increased. in this case, the device resonator may be out on the arm of the robot, and the source resonator may be at the base of the robot, in a central location near the robot, integrated into the industrial facility in which the robot is providing service, and the like. the use of the systems and methods described herein may help eliminate wiring otherwise associated with power distribution within the industrial facility, and thus benefit the overall reliability of the facility. the systems and methods described herein may be used for underground applications, such as drilling, mining, digging, and the like. for example, electrical components and sensors associated with drilling or excavation may utilize the systems and methods described herein to eliminate cabling associated with a digging mechanism, a drilling bit, and the like, thus eliminating or minimizing cabling near the excavation point. in another example, the systems and methods described herein may be used to provide power to excavation equipment in a mining application where the power requirements for the equipment may be high and the distances large, but where there are no people to be subjected to the associated required fields. for instance, the excavation area may have device resonator powered digging equipment that has high power requirements and may be digging relatively far from the source resonator. as a result the source resonator may need to provide high field intensities to satisfy these requirements, but personnel are far enough away to be outside these high intensity fields. this high power, no personnel, scenario may be applicable to a plurality of industrial applications. the systems and methods described herein may also use the near-field non-radiative resonant scheme for information transfer rather than, or in addition to, power transfer. for instance, information being transferred by near-field non-radiative resonance techniques may not be susceptible to eavesdropping and so may provide an increased level of security compared to traditional wireless communication schemes. in addition, information being transferred by near-field non-radiative resonance techniques may not interfere with the em radiative spectrum and so may not be a source of em interference, thereby allowing communications in an extended frequency range and well within the limits set by any regulatory bodies. communication services may be provided between remote, inaccessible or hard-to-reach places such as between remote sensors, between sections of a device or vehicle, in tunnels, caves and wells (e.g. oil wells, other drill sites) and between underwater or underground devices, and the like. communications services may be provided in places where magnetic fields experience less loss than electric fields. the systems and methods described herein may enable the simultaneous transmission of power and communication signals between sources and devices in wireless power transmission systems, or it may enable the transmission of power and communication signals during different time periods or at different frequencies. the performance characteristics of the resonator may be controllably varied to preferentially support or limit the efficiency or range of either energy or information transfer. the performance characteristics of the resonators may be controlled to improve the security by reducing the range of information transfer, for example. the performance characteristics of the resonators may be varied continuously, periodically, or according to a predetermined, computed or automatically adjusted algorithm. for example, the power and information transfer enabled by the systems and methods described herein may be provided in a time multiplexed or frequency multiplexed manner. a source and device may signal each other by tuning, changing, varying, dithering, and the like, the resonator impedance which may affect the reflected impedance of other resonators that can be detected. the information transferred as described herein may include information regarding device identification, device power requirements, handshaking protocols, and the like. the source and device may sense, transmit, process and utilize position and location information on any other sources and/or devices in a power network. the source and device may capture or use information such as elevation, tilt, latitude and longitude, and the like from a variety of sensors and sources that may be built into the source and device or may be part of a component the source or device connect. the positioning and orientation information may include sources such as global positioning sensors (gps), compasses, accelerometers, pressure sensors, atmospheric barometric sensors, positioning systems which use wi-fi or cellular network signals, and the like. the source and device may use the position and location information to find nearby wireless power transmission sources. a source may broadcast or communicate with a central station or database identifying its location. a device may obtain the source location information from the central station or database or from the local broadcast and guide a user or an operator to the source with the aid of visual, vibrational, or auditory signals. sources and devices may be nodes in a power network, in a communications network, in a sensor network, in a navigational network, and the like or in kind of combined functionality network. the position and location information may also be used to optimize or coordinate power delivery. additional information about the relative position of a source and a device may be used to optimize magnetic field direction and resonator alignment. the orientation of a device and a source which may be obtained from accelerometers and magnetic sensors, and the like, for example, may be used to identify the orientation of resonators and the most favorable direction of a magnetic field such that the magnetic flux is not blocked by the device circuitry. with such information a source with the most favorable orientation, or a combination of sources, may be used. likewise, position and orientation information may be used to move or provide feedback to a user or operator of a device to place a device in a favorable orientation or location to maximize power transmission efficiency, minimize losses, and the like. the source and device may include power metering and measuring circuitry and capability. the power metering may be used to track how much power was delivered to a device or how much power was transferred by a source. the power metering and power usage information may be used in fee based power delivery arrangements for billing purposes. power metering may be also be used to enable power delivery policies to ensure power is distributed to multiple devices according to specific criteria. for example, the power metering may be used to categorize devices based on the amount of power they received and priority in power delivery may be given to those having received the least power. power metering may be used to provide tiered delivery services such as “guaranteed power” and “best effort power” which may be billed at separate rates. power metering may be used to institute and enforce hierarchical power delivery structures and may enable priority devices to demand and receive-more power under certain circumstances or use scenarios. power metering may be used to optimize power delivery efficiency and minimize absorption and radiation losses. information related to the power received by devices may be used by a source in conjunction with information about the power output of the source to identify unfavorable operating environments or frequencies. for example, a source may compare the amount of power which was received by the devices and the amount of power which it transmitted to determine if the transmission losses may be unusually or unacceptably large. large transmission losses may be due to an unauthorized device receiving power from the source and the source and other devices may initiate frequency hopping of the resonance frequency or other defensive measures to prevent or deter unauthorized use. large transmission losses may be due to absorption losses for example, and the device and source may tune to alternate resonance frequencies to minimize such losses. large transmission losses may also indicate the presence of unwanted or unknown objects or materials and the source may turn down or off its power level until the unwanted or unknown object is removed or identified, at which point the source may resume powering remote devices. the source and device may include authentication capability. authentication may be used to ensure that only compatible sources and devices are able to transmit and receive power. authentication may be used to ensure that only authentic devices that are of a specific manufacturer and not clones or devices and sources from other manufacturers, or only devices that are part of a specific subscription or plan, are able to receive power from a source. authentication may be based on cryptographic request and respond protocols or it may be based on the unique signatures of perturbations of specific devices allowing them to be used and authenticated based on properties similar to physically unclonable functions. authentication may be performed locally between each source and device with local communication or it may be used with third person authentication methods where the source and device authenticate with communications to a central authority. authentication protocols may use position information to alert a local source or sources of a genuine device. the source and device may use frequency hopping techniques to prevent unauthorized use of a wireless power source. the source may continuously adjust or change the resonant frequency of power delivery. the changes in frequency may be performed in a pseudorandom or predetermined manner that is known, reproducible, or communicated to authorized device but difficult to predict. the rate of frequency hopping and the number of various frequencies used may be large and frequent enough to ensure that unauthorized use is difficult or impractical. frequency hopping may be implemented by tuning the impedance network, tuning any of the driving circuits, using a plurality of resonators tuned or tunable to multiple resonant frequencies, and the like. the source may have a user notification capability to show the status of the source as to whether it is coupled to a device resonator and transmitting power, if it is in standby mode, or if the source resonator is detuned or perturbed by an external object. the notification capability may include visual, auditory, and vibrational methods. the notification may be as simple as three color lights, one for each state, and optionally a speaker to provide notification in case of an error in operation. alternatively, the notification capability may involve an interactive display that shows the status of the source and optionally provides instructions on how to fix or solve any errors or problems identified. as another example, wireless power transfer may be used to improve the safety of electronic explosive detonators. explosive devices are detonated with an electronic detonator, electric detonator, or shock tube detonator. the electronic detonator utilizes stored electrical energy (usually in a capacitor) to activate the igniter charge, with a low energy trigger signal transmitted conductively or by radio. the electric detonator utilizes a high energy conductive trigger signal to provide both the signal and the energy required to activate the igniter charge. a shock tube sends a controlled explosion through a hollow tube coated with explosive from the generator to the igniter charge. there are safety issues associated with the electric and electronic detonators, as there are cases of stray electromagnetic energy causing unintended activation. wireless power transfer via sharply resonant magnetic coupling can improve the safety of such systems. using the wireless power transfer methods disclosed herein, one can build an electronic detonation system that has no locally stored energy, thus reducing the risk of unintended activation. a wireless power source can be placed in proximity (within a few meters) of the detonator. the detonator can be equipped with a resonant capture coil. the activation energy can be transferred when the wireless power source has been triggered. the triggering of the wireless power source can be initiated by any number of mechanisms: radio, magnetic near field radio, conductive signaling, ultrasonics, laser light. wireless power transfer based on resonant magnetic coupling also has the benefit of being able to transfer power through materials such as rock, soil, concrete, water, and other dense materials. the use of very high q coils as receivers and sources, having very narrow band response and sharply tuned to proprietary frequencies, further ensure that the detonator circuits cannot capture stray emi and activate unintentionally. the resonator of a wirelessly powered device may be external, or outside of the device, and wired to the battery of the device. the battery of the device may be modified to include appropriate rectification and control circuitry to receive the alternating currents of the device resonator. this can enable configurations with larger external coils, such as might be built into a battery door of a keyboard or mouse, or digital still camera, or even larger coils that are attached to the device but wired back to the battery/converter with ribbon cable. the battery door can be modified to provide interconnection from the external coil to the battery/converter (which will need an exposed contact that can touch the battery door contacts. while the invention has been described in connection with certain preferred embodiments, other embodiments will be understood by one of ordinary skill in the art and are intended to fall within the scope of this disclosure, which is to be interpreted in the broadest sense allowable by law. all documents referenced herein are hereby incorporated by reference.
|
033-720-925-990-302
|
IT
|
[
"WO",
"EP",
"US",
"AU",
"IT",
"JP"
] |
A61K39/00,A61K38/00,A61P9/00,A61P35/00,C07K14/47,C07K14/78
| 2001-02-27T00:00:00 |
2001
|
[
"A61",
"C07"
] |
antiangiogenic peptides
|
peptides with antiangiogenic activity with a sequence corresponding to that of fragments of human endostatin.
|
claims 1. peptides comprising 20 to 50 amino acids with sequences corresponding to the 6-179 sequence of endostatin, the salts and the non toxic derivatives thereof. 2. peptides as claimed in claim 1 with sequence ranging from the amino acids 6 to 92 of the human sequence. 3. peptides as claimed in claim 2 with sequence ranging from the amino acids 6 to 64. 4. peptides as claimed in any one of the above claims selected from those with sequence 6-49, 11-64, 50-92, 93-133 or 134-179 of the sequence of human endostatin. 5. peptide as claimed in claim 4 having the sequence 6-49 of human endostatin. 6. pharmaceutical compositions containing the peptides of claims 1-5 in admixture with a suitable carrier. 7. use of the peptides of claims 1-5 for the preparation of medicaments with antiangiogenic activity.
|
"antiangiogenic peptides" the present invention relates to peptides with antiangiogemc activity having a sequence corresponding to fragments of human endostatin. background of the invention angiogenesis is the process of outgrowth of new capillaries from pre- existing blood vessels. this phenomenon occurs in various physiological and pathological conditions and is particularly involved in tumor growth and in formation and maintenance of metastasis. angiogenesis is a complex multistep process that includes proliferation, migration and differentiation of endothelial cells, with parallel degradation events of the extra-cellular matrix, formation of tubules and "sprouting" of new capillaries. endostatin is a c-terminal fragment of xciii collagen with molecular weight of 20 kda, that specifically inhibits endothelial cells proliferation in vitro and angiogenesis and tumor growth in vivo. in particular, systemic administration of recombinant endostatin causes regression of tumors in mice. however, administration - and consequently production - of large amounts of endostatin are necessary to observe these effects. moreover, the protein is unstable and, when recombinantly produced in e. coli, solubility problems arise. availability of molecules endowed with biological activity comparable to endostatin, but having smaller dimensions and higher stability and solubility, may be extremely useful. peptides with a sequence corresponding to murine endostatin described by folkman in wo 97/15666, have been disclosed in wo 99/29855, wo 99/48924 and wo 00/63249. in particular, wo 99/29855 (beth israel deaconess medical center) discloses mutants and peptides of murine endostatin (deletion of 9 amino acids 176-184 in the c-terminal region) and characterized by the sequence syivlcie (168-175) in the c-terminal region. wo 99/48924 (children's medical center, ben-sasson) discloses peptides having from about 10 to about 28 amino acids deriving from the ahr sequence (angiogenic homology region), corresponding to the 36-70 region of human endostatin. hybrid peptides containing 10-11 amino acids corresponding to the endostatin ahr sequence and other 10-11 amino acids corresponding to the ahr sequence of other proteins (tsp-1, tsp-4; tsp = thrombospondin) are therein described in detail. finally, wo 00/63249, in the applicant's name, discloses the fragments corresponding to the sequences 1-39, 40-89, 90-134, 135-184 of murine endostatin. some of said fragments are more active than the whole endostatin molecule. the murine sequence has about 86% homology with the human sequence. disclosure of the invention it has now been found that some peptides having from 20 to 50 amino acids with sequences corresponding to the sequence 6-179 of human endostatin show antiangiogemc activity markedly higher than endostatin itself and than the above cited known peptides. therefore the invention relates to said peptides, pharmaceutical compositions containing them and the use thereof for the preparation of medicaments with antiangiogenic activity. description of the figures figure 1 shows the human endostatin sequences in comparison with the murine; figure 2 shows the percentage inhibition curves of cellular migration obtained with peptide 6-49 in comparison with human endostatin; figures 3a and 3b show the graphic representation of the percent inhibition of dna synthesis in endothelial human cells eahy926 by peptide 6-49 and by human endostatin respectively; figure 4 shows the percent inhibition of tubules formation by peptide 6-49 in the in vivo matrigel assay; figure 5 shows the results obtained in the in vitro matrigel assay, by measuring the hemoglobin amount in the gelatinized pellet implanted in c57/bl6 mice treated with peptide 6-49. detailed disclosure of the invention the peptides of the invention have a sequence from 20 to 50. preferably from 30 to 45, neighboring amino acids of any region of the sequence 6-179 of human endostatin. the invention also comprises the derivatives of said peptides obtained by substitution of natural amino acids with the corresponding amino acids of the d series and/or by derivatization of hydroxy, thio or amino functional groups of serine, threonine, cysteine, tyrosine, lysine, arginine residues and/or by functionalization of the terminal nh 2 (for example, by acylation with acetyl groups) and/or by retro-inversion of one or more peptide bonds, according to known techniques which allow to stabilize peptides against hydrolytic enzymes, therefore improving the pharmacokinetic characteristics. examples of peptides of the invention are, with reference to the human endostatin sequence reported in figure 1, those defined by the sequences 6- 40. 6-49, 7-42, 8-52, 10-44, 10-47, 11-64, 12-43,13-50. 15-55, 17-47, 25-65, 33-77, 41-80. 49-88, 50-92, 70-117, 88-110. 90-127, 93- 133, 111-150. 124- 161, 130-170. 133-179, etc. particularly preferred peptides are those defined by the sequence ranging from the amino acids 6-49, 11-64,-50-92, 93-133 and 134-179 of the human endostatin sequence. peptides with sequence ranging from the amino acids 6 to 92 of the human sequence are particularly preferred, more preferably those with sequence ranging from the amino acids 6 to 64. peptide 6-49 is most preferred. the peptides object of the present invention can be prepared with methods and reactions conventionally used in the peptide synthesis. the protection of the amino groups in the amino acids can be carried out by use of 9-fluorenylmethoxycarbonyl (fmoc), tert-butoxycarbonyl (boc), benzyloxycarbonyl (z), trityl (trt) moieties and others commonly used in the peptide chemistry. the carboxylic group can be protected by means of the tert-butyl ester, benzyl ester, p-methoxybenzyl ester and others conventionally used for said purposes. these protective groups can be removed according to processes known in literature, such as by treatment with trifluoroacetic acid, anhydrous hydrofluoric acid, piperidine and the like. the amino acids can be condensed by using active esters such as pentafluorophenyl ester (opfp), 3-hydroxy-4-oxo-3,4-dihydro- 1,2,3- benzotriazine ester (odhbt), or carboxy-activators such as benzotriazol-1- yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate (pybop), 2-(lh- benzotriazol- 1 -yl- 1 , 1 ,3 ,3-tetramethyl)-uronium tetrafluoroborate (tbtu) and the other activators conventionally used for this type of reactions. the purification of the polypeptides described in the present invention can also be carried out according to known techniques of protem chemistry, such as reverse phase hplc, gel filtration, ion exchange chromatography and preparative electrophoresis. more particularly, the peptides can be prepared using the solid phase peptide synthesis and the automatic synthesizer biolynx plus, mod. 4170 by novabiochem (nottingham, great britain) (a. dryland and r. c. sheppard, j. chem. soc, perkin 1, 125, 1986). the protection of the α-amino groups in the amino acids can be carried out by use of 9-fluorenylmethoxycarbonyl (fmoc). the functional groups of the amino acids side chains are protected using the following protective groups: tert-butyl for aspartic acid, glutamic acid, serine, threonine and tyrosine; tert-butoxycarbonyl for lysine and trypthophan; trityl for histidine; 2,2,4,6, 7-pentamethyl-dihydro-benzofuran-5-sulfonyl for arginine; tert-butyl and trityl for cysteine. the synthesis is gradually carried out starting from the c-terminal fmoc-amino acid, attached by an ester bond to a resin consisting of polyethylene oxide grafted to a polystyrene matrix and functionalized by a 4-hydroxymethyl-phenoxyacetic acid residue (e. bayer, angew. chem., 103, 117, 1991). fmoc is removed by using a solution of piperidine in dimethylformamide (dmf). pentafluorophenyl esters of fmoc-amino acids are generally used for the condensation reactions. in the case of serine and threonine, the use of odhbt esters was preferred, whereas in the case of arginine and histidine the carboxylic group was activated by pybop in the presence of diisopropylethylamine, with three hour reaction times. to maximize the reaction yields, a five equivalent excess of fmoc-amino acid is used. the times of deprotection and condensation reactions are automatically determined by the synthesizer; the technician will select the acylation times only in the case of activation with pybop. the peptide is cleaved from the solid carrier, at the same time removing all the protective groups, by acidolysis with a mixture having the following composition: 80% tfa, 5% h 2 0, 2.5% ethanedithiol, 2.5% phenol and 5% thioanisole. the resulting crude polypeptides are purified by reverse phase semipreparative hplc, using a column "jupiter" (250 x 10 mm) c 18 , 10 μ (phenomenex, u.s.a.) and an aktabasic apparatus 100 mod. 18-1405 (amersham pharmacia biotech, freiburg). solvent a: 90% of 0.1% trifluoroacetic acid and 10% of acetonitrile; solvent b: 90% of acetonitrile and 10%) of 0.1% trifluoroacetic acid. gradient: from solvent a to solvent b in 65 minutes. flow rate: 5 ml / minute. detection at λ = 226 nm. 20-25 mg of product are loaded for each run. the main fractions are collected and freeze-dried. the purified polypeptides are characterized by amino acid analysis and electrospray mass spectrometry with a finnigan mat apparatus mod. lcq. the peptides of the invention were found to be particularly active as angiogenesis inhibitors, as evidenced in cell migration, chemotaxis and proliferation tests using eahy 926 human endothelial cells as well as in assays based on the use of matrigel in vitro and in vivo. for the envisaged therapeutical uses, the peptides of the invention or the salts or non toxic derivatives thereof will be suitably formulated in pharmaceutical compositions in admixture with a suitable diluent or carrier. the peptide compositions will be usually administered parenterally, albeit other administration routes, such as the oral, rectal, sublingual or transdermal, are not excluded. dosages will depend on a number of factors and they will be easily determined by those skilled in the art, according to the case. anyway a dosage range from about 0.01 to about 1 mg/kg/day may be contemplated. the following examples will illustrate the invention in greater detail. example 1 phe-gln-pro-val-leu-his(trt)-leu-val-ala-leu-asn-ser(tbu)-pro- leu-ser(tbu)-gly-gly-met-arg(pbf)-gly-ile-arg(pbf)-gly-ala-asp(otbu)- phe-gln-cys(acm)-phe-gln-gln-ala-arg(pbf)-ala-val-gly-leu-ala-gly- thr(tbu)-phe-arg(pbf)-ala-phe-resin. 666 mg (0.1 ml) of fmoc-phe-resin were suspended in 25 ml of dmf and after 2 hours they were loaded into the reaction column. the fmoc-amino acid-resin was then subjected to the following treatments: a) washings with dmf; b) removal of fmoc by treatment with a 20% piperidine solution in dmf; c) washings with dmf; d) condensation with the suitable fmoc-amino acid active ester (5 equivalents) in the presence of n-hydroxy-benzotriazole (5 equivalents) as catalyst, with the addition of an anionic dye (novachrome, calbiochem-novabiochem ag, laufelfingen, switzerland) for automatically monitoring the reaction time. the carboxyl was activated by using pybop, without addition of dye, only in the case of fmoc-arg(pbf) and fmoc-his(trt). this cycle of operations was repeated with the suitable fmoc-amino acid to finally obtain the protected resin-tetratetracontapeptide. the product was then placed in a sintered glass funnel and washed in succession with dmf, tert-amyl alcohol, acetic acid, tert-amyl alcohol, methylene chloride and ethyl ether. 1211 mg of the protected resin-tetratetracontapeptide were obtained. example 2 phe-gln-pro-val-leu-his-leu-val- ala-leu- asn-ser-pro-leu-ser-gly- gly-met-arg-gly-ile-arg-gly-ala-asp-phe-gln-cys(acm)-phe-gln-gln- ala-arg-ala-val-gly-leu-ala-gly-thr-phe-arg-ala-phe. 1211 mg of protected resin-tetratetracontapeptide were suspended in 200 ml of a mixture having the following composition: 80% tfa, 5% h 2 0, 2.5% ethanedithiol, 2.5% phenol and 5% thioanisole; the mixture was reacted for 2 hours with occasional stirring. after filtration under vacuum, the resin was washed with tfa (2 x 50 ml). the filtrate was slowly added with dry ethyl ether to precipitate the polypeptide. the product was filtered, repeatedly washed with dry ethyl ether and finally dried under vacuum over koh. the crude compound was purified by semipreparative hplc as described above, to obtain 97 mg of pure tetratetracontapeptide. [α] 20 d -74.5° (c = 0.1 water). mass spectrum: molecular peak (m + 1) = 4778 da. amino acid analysis: asp = 2.10 (2); thr = 0.98 (1); ser = 1.99 (2); glu = 4.11 (4); pro = 1.82 (2); gly - 6.21 (6); ala = 5.96 (6); cys = 0.96 (1); val = 2.98 (3); met = 0.95 (1); he = 1.1 (1); leu = 4.93 (5); phe = 4.89 (5); his = 0.89 (1); arg = 3.96 (4). example 3 leu-ser(tbu)-ser(tbu)-arg(pbf)-leu-gln-asρ(otbu)-leu-tyr(tbu)- ser(tbu)-ile-val-arg(pbf)-arg(pbf)-ala-asp(otbu)-arg(pbf)-ala-ala-val- pro-ile-val-asn-leu-lys(boc)-asp(otbu)-glu(otbu)-leu-leu-phe-pro- ser-(tbu)-trp(boc)-glu(otbu)-ala-leu-phe-ser(tbu)-gly-ser(tbu)- glu(otbu)-gly-resin. 454 mg (0.1 mmoles) of fmoc-gly-resin were suspended in 25 ml of dmf and after two hours placed in the reaction column. the operations described in example 1 were then repeated using the suitable fmoc-amino acid in each run. in this synthesis also, the fmoc-arg(pbf) and fmoc-his(trt) carboxylic groups were activated with pybop, those of fmoc-ser(tbu) and fmoc-thr(tbu) with dhbt ester, whereas for all the other fmoc-amino acids the pfp ester was used. after assembling all of the amino acids, the product was washed as described in example 1, and dried under vacuum. 1190 mg of protected resin-tritetracontapeptide were obtained. example 4 leu-ser-ser-arg-leu-gln-asp-leu-tyr-ser-ile-val-arg-arg-ala-asp- arg-ala-ala-val-pro-ile-val-asn-leu-lys-asp-glu-leu-leu-phe-pro-ser- trp-glu-ala-leu-phe-ser-gly-ser-glu-gly. 1190 mg of protected resin-tritetracontapeptide were treated with 200 ml of a mixture of the following composition: 80%> tfa; 5% h 2 0; 2.5% ethanedithiol; 2.5% phenol and 5% thioanisole and the procedure described in example 2 was followed. the crude polypeptide was purified by semipreparative hplc as described above, to obtain 81 mg of pure tritetracontapeptide. [α] 20 d - 71.2° (c = 0.1 water). mass spectrum: molecular peak (m + 1) = 4821 da. analysis of the amino acids: asp = 3.89 (4); ser = 5.82 (6); glu = 4.05 (4); pro = 1.96 (2); gly = 2.09 (2); ala = 3.95 (4); val = 3.03 (3); lie = 1.96 (2); leu = 6.87 (7); tyr = 0.98 (1); phe = 2.07 (2); lys = 1.05 (1); arg = 3.87 (4); trp = 1.11 (1). example 5 pro-leu-lys(boc)-pro-gly-ala-arg(pbf)-ile-phe-ser(tbu)-phe- asp(otbu)-gly-lys(boc)-asp(otbu)-val-leu-arg(pbf)-his(trt)-pro- thr(tbu)-trp(boc)-pro-gln-lys(boc)-ser(tbu)-val-trp(boc)-his(trt)-gly- ser(tbu)-asρ(otbu)-pro-asn-gly-arg(pbf)-arg(pbf)-leu-thr(tbu)- glu(otbu)-ser(tbu)-resin. 526 mg (0.1 mmoles) of fmoc-ser(tbu)-resin were suspended in 25 ml of dmf and after 2 hours they were loaded into the reaction column. then the cycle of operations described in example 1 was repeated, using the suitable fmoc-amino acid in each run, in the order indicated in the sequence reported above. 1081 mg of protected resin-monotetracontapeptide were obtained. example 6 pro-leu-lys-pro-gly-ala-arg-ile-phe-ser-phe-asp-gly-lys-asp-val- leu-arg-his-pro-thr-trp-pro-gln-lys-ser-val-trp-his-gly-ser-asp-pro- asn-gly-arg-arg-leu-thr-glu-ser. 1081 mg of protected resin-monotetracontapeptide were suspended in 200 ml of a mixture having the following composition: 80% tfa, 5% h 2 0, 2.5%> ethanedithiol, 2.5% phenol and 5% thioanisole. the mixture was reacted for three hours with occasional stirring. the crude product was purified by semipreparative hplc as described above, to obtain 101 mg of pure monotetracontapeptide. [α] 20 d - 77.0° (c = 0.1 water). mass spectrum: molecular peak (m + 1) = 4672 da. analysis of the amino acids: asp = 3.88 (4); thr = 2.03 (2); ser = 3.95 (4); glu = 2.01 (2); pro = 4.87 (5); gly = 4.12 (4); ala = 0.99 (1); val = 2.10 (2); he = 1.02 (1); leu = 3.07 (3); phe = 1.97 (2); lys = 3.07 (3); arg = 3.88 (4); trp = 2.12 (2). example 7 tyr(tbu)-cys(trt)-glu(otbu)-thr(tbu)-trp(boc)-arg(pbf)-thr(tbu)- glu(otbu)-ala-pro-ser(tbu)-ala-thr(tbu)-gly-gln-ala-ser(tbu)-ser(tbu)- leu-leu-gly-gly-arg(pbf)-leu-leu-gly-gln-ser(tbu)-ala-ala-ser(tbu)- cys(trt)-his(trt)-his(trt)-ala-tyr(tbu)-ile-val-leu-cys(tbu)-ile- glu(otbu)-asn-ser(tbu)-phe-met-resin. 500 mg (0.1 ml) of fmoc-met-resin were suspended in 25 ml of dmf and after 2 hours loaded into the reaction column, then the operative cycle reported in example 1 was repeated, using the suitably activated fmoc- amino acid for each cycle, in the order indicated in the sequence reported above. 960 mg of protected resin-hexatetracontapeptide were obtained. example 8 tyr-cys(trt)-glu-thr-trp-arg-thr-glu-ala-pro-ser-ala-thr-gly- gln-ala-ser-ser-leu-leu-gly-gly-arg-leu-leu-gly-gln-ser-ala-ala-ser- cys(trt)-his-his-ala-tyr-ile-val-leu-cys(tbu)-ile-glu-asn-ser-phe-met. 960 mg of protected resin-hexatetracontapeptide were treated with 200 ml of a mixture having the following composition: tfa 80%; 5% h 2 0; 2.5%o ethanedithiol; 2.5% phenol and 5% thioanisole. the mixture was reacted for 3 hours with occasional stirring, then the procedure of example 2 was followed. the crude product was purified by semipreparative hplc as described above, to obtain 98 mg of pure, non oxidized hexatetracontapeptide. [ ] 20 d - 48.9° (c = 0.1 water). mass spectrum: molecular peak (m + 1) = 5455 da. amino acid analysis: asp = 0.96 (1); thr = 2.97 (3); ser = 5.87 (6); glu = 5.03 (5); pro = 0.93 (1); gly = 4.12 (4); ala = 5.88 (6); cys = 2.84 (3); val = 1.05 (1); met = 0.91 (1); he = 2.11 (2); leu = 4.82 (5); tyr = 1.94 (2); phe = 1.20 (1); his = 1.91 (2); arg = 2.03; trp = 0.95 (1). example 9 tyr-cys-glu-thr-trp-arg-thr-glu-ala-pro-ser-ala-thr-gly-gln-ala- ser-ser-leu-leu-gly-gly-arg-leu-leu-gly-gln-ser-ala-ala-ser-cys-his- his-ala-tyr-ile-val-leu-cys-(tbu)-ile-glu-asn-ser-phe-met. 98 g (17.96 mmoles) of non oxidized hexatetracontapeptide were dissolved in 200 ml of 75% methanol and then added drop by drop and under stirring with a solution of 10 mg of iodine in 30 ml of 75% methanol. after reacting the mixture for 3 hours at room temperature, a 10% ascorbic acid aqueous solution was added until complete decolourization of iodine. methanol was thoroughly evaporated off under vacuum and the remaining aqueous solution was freeze-dried. the resulting crude peptide was finally purified by semipreparative hplc, in the conditions described above. 11 mg of pure oxidized hexatetracontapeptide were obtained. [α] 20 d - 24° (c = 0.05 water), mass spectrum: molecular peak (m + 1) = 4968 da. amino acid analysis: asp = 1.03 (1); thr = 2.87 (3); ser = 5.91 (6); glu = 4.99 (5); pro = 0.95 (1); gly = 3.87 (4); ala = 5.91 (6); cys = 2.79 (3); val = 0.97 (1); met = 0.93 (1); he = 2.21 (2); leu = 4.92 (5); tyr = 1.89 (2); phe = 1.09 (1); his = 1.89 (2): arg = 1.99 (2); trp = 0.87 (1). example 10 d-phe-gln-pro-val-leu-his(trt)-leu-val-ala-leu-asn-ser(tbu)-pro- leu-ser(tbu)-gly-gly-met-d-arg(pbf)-gly-ile-d-arg(pbf)-gly-ala- asp(otbu)-d-phe-gln-cys(acm)-d-phe-gln-gln-ala-d-arg(pbf)-aia-val- gly-leu-ala-gly-thr(fbu)-phe-d-arg(pbf)-ala-phe-resin. analogously to example 1, using fmoc -d-arg(pbf) instead of fmoc- arg(pbf), 1187 mg of protected resin-tetratetracontapeptide were obtained starting from 500 mg of fmoc-phe-resin suspended in 25 ml of dmf. example 11 d-phe-gln-pro-val-leu-his-leu-val- ala-leu- asn-ser-pro-leu-ser- gly-gly-met-d-arg-gly-ile-d-arg-gly-ala-asp-d-phe-gln-cys(acm)-d- phe-gln-gln-ala-d-arg-ala-val-gly-leu-ala-gly-thr-phe-d-arg-ala- phe. analogously to example 2, from 1 187 mg of product of example 10. 83 mg of pure peptide were obtained having the following characteristics: mass spectrum: molecular peak (m+l):4778 da. [α] 20 d : -55.8° (c = 0.5 water). example 12 his(trt)-leu-val-ala-leu-asn-ser(tbu)-pro-leu-ser(tbu)-gly-gly- met-arg(pbf)-gly-ile-arg(pbf)-gly-ala-asp(otbu)-phe-gln-cys(acm)- phe-gln-gln-ala-arg(pbf)-ala-val-gly-leu-ala-gly-thr(tbu)-phe- arg(pbf)-ala-phe-leu-ser(tbu)-ser(tbu)-arg(pbf)-leu-gln-asp(otbu)- leu-tyr(tbu)-ser(tbu)-ile-val-arg(pbf)-arg(pbf)-ala-resin. analogously to example 1, starting from the suitable fmoc-amino acids, 1285 mg of protected resin-tetrapentacontapeptide were obtained from 500 mg of fmoc- ala-resin in 25 ml of dmf. example 13 his-leu-val-ala-leu-asn-ser-pro-leu-ser-gly-gly-met-arg-gly-ile- arg-gly-ala-asp-phe-gln-cys-phe-gln-gln-ala-arg-ala-val-gly-leu- ala-gly-thr-phe-arg-ala-phe-leu-ser-ser-arg-leu-gln-asp-leu-tyr-ser- ile-val-arg-arg-ala. analogously to example 2, from 1285 mg of the compound of example 12, 125 mg of pure peptide were obtained, having the following characteristics: mass spectrum: molecular peak (m+l):5953 da. [α] 20 d : -62.6° (c = 0.45 water). example 14 endothelial human cells ea.hy.926 were grown in dmem supplemented with 10% fetal bovine serum (fbs) and with the appropriate concentrations of glutamine and antibiotics. before the experiments, the cells had been deprived of serum for 24 hours in 0.1% fbs. ea.hy.926 cells migration has been evaluated by chemotaxis test in a 48 well boy den chamber using polycarbonate filters of 12 μm porosity pre- treated with a 10 μg/ml type i collagen solution. the cells were added to the wells of the superior chamber at the density of 15.000 cells/well in the presence or in the absence of the endostatin fragment 6-49 or of human endostatin. the chemotactic stimulus, represented by a conditioned medium obtained by a culture of glioma cells, was added to the lower chamber. after 4 hours of incubation at 37°c, non migrated cells were removed by a scraper and the filter was colored with diff quick. migrated cells were then counted at a 400 x magnification in 6 different fields. the results, reported in figure 2, are expressed as a percentage of the maximal migration induced by the conditioned medium in the presence of the peptide or of endostatin. peptide 6-49 causes maximal inhibition of cell migration of about 60% starting from the concentration of 10 "9 m, with an id 50 of 3 x 10 "13 , while endostatin determines a maximal inhibition of 70% at 10 "9 m, with an id 's™o of 5 x 10 '12 m. example 15 ea.hy.926 cells were inoculated in 96 well-plates and, after being deprived of serum for 24 hours, were stimulated with 10% fbs in the presence or in the absence of different concentrations of the peptide 6-49 or of endostatin for further 24 hours. tritiated tymidine (1 μci/well) was added during the last 6 hours of incubation. the cells were then extracted in 10%) tca and the radioactivity incorporated in the tca-insoluble fraction was determined after solubilization in 0.5 m naoh. the results, reported in figures 3a and 3b, are expressed as the percentage of the maximal stimulation induced by 10% serum in the absence of the drug. peptide 6-49 induces maximal inhibition of dna synthesis of about 80%) starting from the concentration of 10 '12 m, with an id 50 of 5 x 10 "15 m. human endostatin induces maximal inhibition of dna synthesis of about 55% starting from the concentration of 10 "13 m, with an id 50 of 10 "m . example 16 the formation of tubular structures, similar to capillaries, was evaluated by seeding the endothelial cells on a matrigel carrier, a reconstructed basal membrane, with the characteristic of being liquid at 4°c and of undergoing polymerization at 37°c forming a tri-dimensional gel. proangiogenic factors, such as fibroblast growth factor (fgf) or vascular endothelial growth factor (vegf), were added to the medium in the presence of the peptide 9-49 and the plates were incubated at 37°c under 5% c0 2 atmosphere. tubules formation was monitored observing the cells with an inverted microscope and, after recording the image by means of photography, a quantification was performed by evaluating the area occupied by the cells and by the capillaries network. upon observation under the microscope, it is evident that the peptide of invention is able to inhibit the capacity of endothelial cells to form tubular structures similar to capillaries, which on the contrary are clearly evident in the untreated control cells (figure 4a). in figure 4b, a quantitative analysis of the effect, carried out by a proper software (nih image), is reported. treatment with the fragment 6-49 reduces tubules formation to 23% compared with controls, considered as 100%>. example 17 500 ml of matrigel containing fgf 2 ng/ml and heparin 36 u/ml were inoculated s.c. in the abdominal region of male mice c57/bl6, of age from 6 to 10 weeks. where indicated, fragment 6-49 was added to the solution of matrigel at concentrations of 1 and 10 μg/mouse. six animals were used in each experiment. after 4 days, the gelatinized matrigel pellet was recovered and the amount of hemoglobin therein was measured by means of a commercial kit based on drabkin's method (sigma aldrich). as it can be observed in figure 5, which shows the data obtained in three independent experiments, the fragment 6-49, already at the dose of 1 mg/mouse, is capable of reducing hemoglobin levels in the matrigel pellets, which indicates a decreased formation of vessels in animals treated with the fragment compared with controls.
|
035-303-436-649-07X
|
JP
|
[
"US",
"JP"
] |
A61M1/14,A61M1/16,A61M1/36,A61M60/113,A61M60/216,A61M60/38,A61M60/422,A61M60/523,A61M60/818
| 1991-11-19T00:00:00 |
1991
|
[
"A61"
] |
integrated heart-lung machine
|
an integrated heart-lung machine, which includes a blood pump having a casing of a cup-like shape interiorly defining a pump chamber at an intermediate portion thereof for pumping in and out blood from a blood inlet to a guide flange formed at opposite ends of the casing; a rotor having a rotary member securely fixed to the fore end thereof within the pump chamber and journalled in the guide flange; an artificial lung of a doughnut-like or cylindrical shape connected contiguously to a blood flow passage in the guide flange and concentrically with the rotor; a stator detachably fitted in an intermediate portion between the rotor and the artificial lung; and a pedestal base located at one side of the artificial lung and provided with a blood outlet in communication with the artificial lung. accordingly, influent blood to the pump chamber is sent into the artificial lung through the blood passage by the pumping action of the rotor, and is refreshed by contact with air or oxygen in the lung, which is maintained in a heated state by the stator, and returned to the patient's body through the blood outlet. this arrangement permits minimizing of the length of the blood circulating passages to and through the machine and permits shortening and minimizing of the blood passages interconnecting the blood pump, artificial lung and blood filter, while preventing blood contamination and leaks as well as blood cell destruction. easy installation and handling is also permitted in a sanitary region on a bed or on an operating table.
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1. an integrated heart-lung machine, comprising: a blood pump having a casing of a substantially cup-like shape, the casing having a blood inlet and a guide flange, the casing interiorly defining a pump chamber at an intermediate portion thereof for pumping in and out blood from said blood inlet to said guide flange, said guide flange having a blood flow passage formed therein; a rotor having a rotational shaft with rotor blades securely fixed to the fore end thereof within said pump chamber and the rotational shaft being journalled in said guide flange; an artificial lung having one of a substantially doughnut-like and cylindrical shape connected contiguously to said blood flow passage in said guide flange and positioned concentrically with said rotor; a stator detachably fitted in an intermediate portion between said rotor and said artificial lung; and a pedestal base located at one side of said artificial lung and provided with a blood outlet in communication with said artificial lung wherein said blood flow passage is of a helical shape and wherein said guide flange includes a blood chamber located between said rotor blades and said rotor which is communicated with said artificial lung substantially along an entire inner peripheral portion thereof and which is communicated with said blood flow passage. 2. an integrated heart-lung machine as defined in claim 1, wherein said pedestal base is provided with a filter at said blood outlet in communication with said artificial lung. 3. an integrated heart-lung machine as defined in claim 1, wherein said stator and said artificial lung include an outer sleeve and an inner sleeve of thermally conductive material, respectively, and which comprise a holder for holding said outer and inner sleeves together. 4. an integrated heart-lung machine as defined in claim 1, wherein said blood outlet is located on the same side of the machine as said blood inlet. 5. an integrated heart-lung machine as defined in claim 1, which comprises a flow sensor which is removably located in said blood outlet. 6. an integrated heart-lung machine as defined in claim 1, which comprises a filter located in said blood outlet of said pedestal base and in communication with said artificial lung.
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background of the invention 1. field of the invention this invention relates to a heart-lung machine for pumping blood out of a patient's body for blood treatment and returning the treated blood to the patient's body. 2. description of prior art extracorporeal circulation type heart-lung machines have been known, for example, from japanese patent publication h2-12108 disclosing a heart-lung machine which is composed of a series of separably connected operating units including an artificial lung unit for refreshing blood through oxidation, and a heat exchanger unit in which heated water is circulated to maintain the blood at a predetermined temperature, and also from japanese laid-open patent application h2-41172 disclosing a heart-lung machine which has a blood treating section (i.e. an artificial lung) and a blood feed mechanism integrally incorporated into outer and inner portions of a cylindrical casing, respectively, such that blood, inflowing through an apex portion of a blood guide member of a substantially conical shape, is discharged through a blood discharge port by rotation of a rotary member for introduction into the blood treating section and then being allowed to flow out through a blood outlet on the downstream side, the blood treating section being interiorly provided with a heat exchanger for circulation of a heat exchanging medium therethrough. in the former case where the blood pump, artificial lung and heat exchanger are connected in series as separable operating units, however, the machine involves a lengthy flow passage for the blood to be treated and necessitates providing a support stand exclusively for fixedly retaining the position of the machine body. in this connection, since it is difficult to install the machine in a sanitary region in the vicinity of a patient and since the heat exchanger unit needs a separate heat source, difficulties are often encountered in reducing the volume of the blood in the feed system or the blood pumped to a marked degree, coupled with the inconvenient and troublesome job of connecting inflow and outflow tubes for the heat exchanging medium to and from the heat exchanger unit. further, in the latter case, blood strikes against guide blades under the influence of the centrifugal force of the pump, and, as the blood is introduced into the artificial lung at a high velocity under the guidance of the guide blades, it vigorously strikes the casing of the artificial lung at the blood inlet thereof and also against hollow yarns of the lung. it follows that the blood is susceptible to destruction of blood cells (hemolysis) due to physical stresses. summary of the invention it is a primary object of the present invention to provide an integrated heart-lung machine which is easy to handle and avoids the destruction of blood cells. it is another object of the present invention to provide an integrated heart-lung machine which can be installed at a position close to a patient or an operating table. in accordance with the present invention, the abovestated objectives are achieved by the provision of an integrated heart-lung machine, essentially including: a blood pump having a casing of a cup-like shape interiorly defining a pump chamber in an intermediate portion thereof for pumping in and out blood from a blood inlet to a guide flange formed at opposite ends of the casing; a rotor having a rotary member securely fixed to the fore end thereof within the pump chamber and journalled in the guide flange; an artificial lung of a doughnut-like or cylindrical shape connected contiguously to a blood flow passage in the guide flange and concentrically with the rotor; a stator detachably fitted in an intermediate portion between the rotor and the artificial lung; and a pedestal base located at one side of the artificial lung and provided with a blood outlet in communication with the artificial lung. the above and other objects, features and advantages of the invention will become apparent from the following description and the appended claims, taken in conjunction with the accompanying drawings which show by way of example preferred embodiments of the invention. brief description of the drawings in the accompanying drawings: fig. 1 is a sectional view of a first embodiment of the invention; fig. 2 is a sectional view of the heart-lung machine of the first embodiment, with the stator in a detached state; fig. 3 is a sectional view taken along line iii--iii of fig. 1; fig. 4 is a sectional view taken along line iv--iv of fig. 1; and fig. 5 is a sectional view of a second embodiment of the invention. description of preferred embodiments hereafter, the invention is described more particularly, firstly by way of the first embodiment shown in figs. 1-4. in these figures, indicated at 1 is a casing of a cup-like shape having a blood inlet 1a projected from one end and a guide flange 2 fitted in the other end thereof. the guide flange 2 is provided with an aperture 2a axially in a center portion thereof and formed with a blood flow passage 2b and a blood chamber 2c in peripheral edge portions. in this instance, for the purpose of securing smooth blood flow, the blood flow passage 2b is formed so as to extend helically as far as a point on the inner side of the artificial lung 5 which will be described hereinafter. the blood chamber 2c is formed coextensively around the inner periphery of an artificial lung 5. denoted at 3 is a rotor which is constituted by a rotational shaft 3a and a magnet 3b. the rotational shaft 3a is supported in bearings 3c and shielded by a mechanical seal 3d from a pump chamber 4 which is defined by the casing 1 and the guide flange 2. blades 3e are fixed on the rotational shaft 3a. designated at 5 is the artificial lung which is provided with bundles of a multitude of porous hollow yarns 5c of polypropyrene or like material between an outer sleeve 5a, of an outer diameter substantially the same as that of the casing 1, and an inner sleeve 5b,and communicated with the blood chamber 2c. air or oxygen inlet 5d and outlet 5e are provided at the lower and upper ends of the outer sleeve 5a, respectively. the inner sleeve 5b is formed of a thermally conductive material such as stainless steel sus304 or the like. indicated at 6 is a motor stator which is constituted by an iron core 6a and winding 6b. the iron core 6a is fixedly laminated in an outer case 6c which is securely connected to a grip member 6d by means of screws and slidable in inward and outward directions in contact with the inner surface of the inner sleeve 5b of the artificial lung 5. the outer case 6c is also formed of a thermally conductive material, for example, stainless steel sus304 or the like. non-magnetic material is used for a cap-like outer wall 3f of the rotor 3 as well as for an inner wall 6e of the stator 6. the cap-like outer wall 3f is tightly fixed to the inner sleeve 5b to prevent the intrusion of bacteria from outside. indicated at 7 is a pedestal base of a trapezoidal shape, which is provided with a rectangular recess 7a on the top side to accommodate sponge 7b and filter 7c therein. this pedestal base 7 is further provided with blood inlet 7d and outlet 7e on its upper and lower sides, respectively. the aforementioned inlet 1a of the pump casing is located on the same side as the blood outlet 7e to facilitate the connection of tubes when the heart-lung machine is to be set on a patient. denoted at 8 is a lead wire and at 9 is a flow sensor which is, for example, an electromagnetic flowmeter or an ultrasonic doppler flowmeter, and is detachably located in a tubular portion of the blood outlet 7e. the heart-lung machine of the above-described embodiment operates in the manner described below. firstly, the stator 6, which has been sterilized in its entirety, is fitted between the inner sleeve 5b and the outer wall 3f of the rotor 3 as indicated by an arrow in fig. 2, and is slid into the position shown in fig. 1. thereafter, electric current is supplied to the lead wire 8 to produce a rotating magnetic field in the stator 6, which rotationally drives the rotor 3. as a result, the blades 3e are rotated in a predetermined direction. the influent blood from the inlet 1a is sent into the artificial lung 5 after decreasing its velocity to a sufficiently low level through the blood passage 2b and blood chamber 2c. in this regard, since the blood passage 2b is helically shaped, the blood which is discharged from the pump chamber 4 by rotation of the blades 3e is allowed to flow smoothly through the blood passage 2b without blood cell destruction or hemolysis. as the energy of flow velocity is converted into a pressure in the blood chamber 2c to a sufficient degree, the blood is urged to flow into the artificial lung 5 smoothly from the entire inner periphery thereof in such a manner as to prevent localized blood flows in the bundles of hollow yarns 5c. on the other hand, heat is generated by the stator 6 due to copper and iron losses and reactive power, which can be controlled through the power supply, allows for heating the outer case 6c of the stator 6 and the inner sleeve of the artificial lung 5 to a suitable temperature level, the outer case 6 and inner sleeve 5b maintaining the blood in the artificial lung 5 at a desired temperature through heat exchange with influent blood to the lung 5. further, the influent blood in the artificial lung 5 is brought into contact with oxygen or air, which has been introduced into the artificial lung 5 through the walls of a multitude of hollow yarns 5c, and refreshed with dissolved oxygen. the refreshed blood is discharged to the inlet 7d of the pedestal base 7b and, after removal of bubbles and thrombus at the sponge 7b and filter 7c, is returned through the blood outlet 7e. fig. 5 illustrates a second embodiment of the present invention, which is provided with a magnet 9 at the fore end of the rotational shaft 3a of the rotor 3 to form a magnetic coupling in cooperation with a magnet 10 which is fixed at the inner end of the blade shaft for the pump blades 3e. this arrangement completely prevents blood leakage. obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. it is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
|
038-385-702-407-905
|
US
|
[
"CN",
"EP",
"US"
] |
G08B3/10,G08B29/00,G10K9/122,G08B29/10,H04R1/00,H03F3/217,H04R17/00,H04R25/00,H04R29/00
| 2013-08-26T00:00:00 |
2013
|
[
"G08",
"G10",
"H04",
"H03"
] |
apparatus and method of silent monitoring alarm sounders
|
disclosed are an apparatus and method of silent monitoring alarm sounders. an alarm sounder, which incorporates a piezo-electric output transducer, can be silently monitored using a variable frequency square wave. an initial frequency, close to the upper limit of human hearing, is coupled to the sounder. the transducer draws very little current at this initial frequency. the frequency of the square wave is systematically reduced, and the current draw is continually monitored. a high current indicates a low impedance type of fault. a low current throughout the frequency range indicates a potential high frequency type of fault.
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an alarm sounder comprising: a housing (20); a class-d amplifier (32) coupled to a piezo-electric transducer (34), wherein the class-d amplifier and the piezo-electric transducer are carried in the housing; and control circuits (24) coupled to the class-d amplifier wherein the control circuits are configured to couple a monitoring waveform to the class-d amplifier at an initial high frequency with a low frequency signal envelope, wherein the initial high frequency is substantially inaudible to human hearing, wherein the control circuits are configured to subsequently apply a plurality of descending frequencies to the class-d amplifier while measuring a current for the piezo-electric transducer at each of the plurality of descending frequencies, and wherein at least one of the plurality of descending frequencies is a frequency in a human hearing frequency range. the alarm sounder as in claim 1 further comprising interface circuits (12a) configured to communicate with a displaced regional monitoring control unit. the alarm sounder as in claim 1 wherein the control circuits (24) are configured to carry out an initial calibration process to establish a reference value. the alarm sounder as in claim 1 wherein the control circuits are configured to cease application of the plurality of descending frequencies when a predetermined current value for the current of the piezo-electric transducer is detected, and wherein a local capacitor is configured to provide a current flow to drive the class-d amplifier (32). the alarm sounder as in claim 4 wherein the control circuits (24) are configured to monitor a capacitor voltage of the local capacitor over a period of time and to establish the current flow therefrom. the alarm sounder as in claim 1 wherein the control circuits (24) include volume control circuits coupled to a storage capacitor (28). the alarm sounder as in claim 6 wherein the control circuits (24) are configured to measure a decay time parameter of the storage capacitor (28). the alarm sounder as in claim 7 wherein the control circuits (24) are configured to increase a duty cycle of a test signal rhat drives the piezo-electric transducer (34). the alarm sounder as in claim 8 wherein the control circuits are configured to increase a volume parameter of the test signal. the alarm sounder of claim 1 wherein the class-d amplifier (32) is configured to drive the piezoelectric transducer (34) with a variable background monitoring waveform that is initially set at a first frequency that substantially exceeds an end of a predetermined audio band of approximately 20 khz. the alarm sounder as in claim 10 wherein the variable background monitoring waveform comprises a square wave. the alarm sounder as in claim 11 further comprising a capacitor (28), wherein a voltage decay on the capacitor is indicative of a sounder monitoring current. the alarm sounder as in claim 12 wherein the control circuits monitor the voltage decay to measure a sounder audio producing current. the alarm sounder as in claim 13 wherein the sounder is configured to intermittently reduce a frequency of the variable background monitoring waveform while the control circuits continue to monitor the sounder audio producing current. a method of monitoring operation of a piezo-electric transducer comprising: generating a variable frequency square wave starting at a frequency close to an upper limit of hearing at approximately 20 khz and at steps below 20khz; driving the piezo-electric transducer(34) with the variable frequency square wave; monitoring a transducer current as the frequency of the variable frequency square wave is being varied; and determining if the transducer current indicates expected operation of the piezo-electric transducer with no shorts or open circuits.
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field the application pertains to audible alarm indicating output devices, or sounders. more particularly, the application pertains to substantially silent monitoring of alarm sounders. background modern analogue addressable fire alarm systems use many loop powered alarm sounders controlled by microcontrollers, to alert people in protected areas to the presence of a fire alarm condition. many alarm sounders use piezo-electric transducers (a piezo) to reduce the current consumption of the sounders in the alarm condition. typically these analogue addressable systems can continuously monitor all outstation types on each addressable loop for faults, to ensure the system can be relied on to detect fires and alert people. in the case of alarm sounders, the actual sounder output can normally only be switched on and verified during regular tests with the system in the alarm state. while it would be an enormous benefit to continuously verify that the alarm sounder can actually provide its correct output, background monitoring has always proved difficult to successfully implement especially with sounders using a piezo element. in known systems, complex monitoring waveforms need to be generated, so that background monitoring is normally only available on speech variants. however, as a relatively large acoustic output during the background monitoring has always proved to be unavoidable, its use in bedrooms for example, is clearly unacceptable. one way to guarantee reliable fault detection of the sounder would be to require that the monitoring frequency be fixed at a relatively low in-band frequency. this configuration would produce a monitoring current high enough to provide reliable discrimination. this however would prevent the monitoring from being silent, and it would limit its general use. united states patent application publication no. us2002/0126001a1 describes a buffered voltage doubling circuit for using a piezoelectric transducer and a frequency swept signal generator to produce audible sounds. it includes a schmitt trigger, and has the advantage of producing more sound for less power compared with standard inductive circuits. summary of the invention the present invention provides a sounder as defined in claim 1. the sounder may include the features of any one or more of dependent claims 2 to 14. the present invention also provides a method as defined in claim 15. brief description of the drawings fig. 1 is a block diagram of an embodiment hereof; fig. 2 is a flow diagram of aspects of operation of the embodiment of fig. 1 ; and fig. 3 is a flow diagram of additional aspects of the method of fig. 2 . detailed description while disclosed embodiments can take many different forms, specific embodiments hereof are shown in the drawings and will be described herein in detail with the understanding that the present disclosure is to be considered as an exemplification of the principles hereof, as well as the best mode of practicing same, and is not intended to limit the claims hereof to the specific embodiment illustrated. silent monitoring, in accordance herewith can be provided for a fire alarm piezo-electric sounder that uses a class-d drive amplifier which normally produces attention tones between 500hz and 1 khz. significant higher harmonics are also normally produced through-out the audio band, and optionally, the sounder may be used to produce speech messages. the class-d amplifier uses the audio output providing piezo-electric transducer as a filtering capacitor. the volume is normally controlled by adjusting the supply voltage feed to a storage capacitor connected to the amplifier. silent monitoring can be implemented by periodically producing a high frequency square wave, starting at a frequency close to the upper limit of hearing of approximately 20 khz. the amplifier is set to the maximum volume, and then the supply rail to the amplifier is turned off, allowing the amplifier to be energized by a local storage capacitor coupled to the supply rails. normally the amplifier will draw a small current due to the piezo being driven at a frequency far outside the speech band and higher than the upper corner frequency of the amplifier. this also causes the amplifier to attenuate the monitoring frequency so it becomes inaudible. the drop in voltage on the storage capacitor over a fixed period is directly proportional to the current used and is monitored by local control circuits, which could include a microcontroller, in the alarm sounder. if the piezo element or, the amplifier draws a very high current, then this is clearly a low impedance type of fault and can easily be detected by the local control circuits as such. if the current is lower than expected, then this could be a high impedance type of fault; however it could also be due to the very high efficiency of the amplifier, the variation in its impedance at this high frequency or due to the component variation of the particular piezo element and storage capacitor used. while all the variations could be initially calibrated out during manufacturing, it is know that component values will change with the effects of temperature and age. in one aspect hereof, the alarm sounder generates a square wave monitoring frequency at descending frequency steps below 20 khz, with the transition between steps carefully controlled to minimise the audio content. if an adequate, but not excessive monitoring current can be detected at any step, then this process will stop and the test will have been passed, if however the current is always too small then the test will only stop and fail at a drive frequency well into the audio band. the overall effect of this optimising technique is to produce a preferred monitoring frequency that will reliably monitor the sounder and give the lowest possible audio output and therefore annoyance. if an open circuit type of fault is discovered, the sounder will actually be tested at its maximum volume and at a drive frequency which is consistent with the sounder's normal operation during an alarm. in this case it is a certainty that a real fault must exists, however even this will be a silent test. fig. 1 illustrates a block diagram of an alarm/monitoring apparatus 10 which incorporates silent testing of one or more alarm sounders in accordance herewith. fig. 2 and fig. 3 illustrate aspects of methods 100, 200 respectively of testing such sounders. apparatus 10 includes an alarm/monitoring control unit, or panel 12 of a type generally known to those of skill in the art. the unit 12 is in bidirectional communication with a plurality 14 of substantially identical alarm sounders 14a, 14b...14i...14n via a medium 16. the medium 16 could be implemented, for example as an electric cable. the unit 12 can communicate information and commands to and receive information from members of the plurality 14 along with smoke, fire, or intrusion detectors, without limitation as would be used in monitoring a region r and providing alarm related information to individuals in that region. sounder 14i is representative of members of the plurality 14. a description thereof will suffice for the other members of the plurality 14 as well. sounder 14i is carried by a housing 20 which could be mounted on a surface in the region r to provide audible alarm indicating outputs. sounder 14i receives commands, and other information along with electrical energy from unit 12 via medium 16. sounder 14i can also communicate status or test results to the unit 12 via medium 16 and interface circuits 12a. if desired, sounder 14i could be in wireless communication with unit 12 and receive its electrical energy from a local source, without limitation. housing 20 of sounder 14i carries a programmable control unit, or microcontroller, 22a along with pre-stored control software 22b. housing 20 also carries volume control circuits 24, storage capacitor 28, monitoring circuitry 30, a class-d amplifier 32 a piezoelectric audible output transducer 34 and an a/c load 36. in operation as discussed below, microcontroller 22a periodically background tests the alarm sounder 14i using a test signal when the alarm sounder is not active to determine if it is capable of giving an audio alarm when required. this test signal starts at an inaudible high initial frequency close to 20 khz. first, the quiescent current taken by the class-d amplifier 32, the monitor circuitry 30 and the hold-up time of the storage capacitor 28 is measured in a calibration test 200 discussed further relative to fig.3 . the microcontroller 22a sets the volume to 0%, as at 202, using a pwm control line 40, which drives the volume control circuit 24. the volume control circuit 24 supplies a voltage supply level on line 26 to a class-d amplifier 32 and hence controls its volume. microcontroller 22a then sets a pwm drive frequency, line 40a, to a very low duty cycle of just less than 0.5%, as at 206, at the initial start frequency of 20 khz, as at 204. the audio envelope generated in this step change is masked by the fact that the volume is set to 0%. the volume is then ramped up to its maximum 100% level, as at 208, using the pwm control line 40 over a number of seconds, so that the frequency content of the envelope appearing on the output of class-d amplifier 32 is too low to be audible. storage capacitor 28 is now charged up to its maximum voltage, which is equal to the regulated input voltage 42 obtainable from the medium 16. microcontroller 22a now turns off the volume control circuit 24, as at 210, by setting the pwm control line 40 to 0%. storage capacitor 28 now slowly discharges at a rate dependent on the actual value of the capacitor 28, the static circuit loading and the dynamic loading caused by the finite switching losses of the class-d amplifier 32. the piezoelectric transducer 34 causes almost no loading because of the very small duty cycle of the class-d amplifier 326. after about a one second discharge period, as at 212, microcontroller 22a measures the monitor circuitry 30 using an analogue to digital converter connected to adc port line 44, as at 214. this calibration reading is termed adc1 and could be the result of a number of samples averaged together to filter noise. it should also be understood that this adc1 value could also be checked to see if it is in an expected range, so that many other hardware faults could be determined. with respect to fig. 2 , following on from the calibration test, of fig. 3 , the duty cycle of the initial test frequency is slowly increased to 50%, as at 102, to produce a square wave drive waveform and the volume is also slowly increased to a maximum 100%, as at 104, by the microcontroller 22a. in both cases the rate of change is limited so that the frequency content from the class-d amplifier 32 remains inaudible. the output of the class-d amplifier 32 is now at the maximum drive power for the piezoelectric transducer 34, for this particular frequency. microcontroller 22a now turns off the volume control circuit 24, as at 106, so that storage capacitor 28 will discharge at a higher rate determined mainly by the loading from the piezoelectric transducer 34. after about one second, as at 108, the microcontroller 22a measures the monitor circuitry 30 using an analogue to digital converter connected to the adc port line 44. this reading is termed adc2, as at 110, and may be the result of a number of samples averaged together. a small a/c load 36 may be placed asymmetrically on the piezoelectric transducer 34 to increase its high frequency loading and the class-d amplifier 32 may be driven only on the opposite side of the piezoelectric transducer 34, with a single ended output 38. the a/c load 36 could be just a capacitor, with a value that is small compared to the capacitance of the piezoelectric transducer. microcontroller 22a now removes the calibration value adc1 from the first test measurement adc2, giving a delta measurement to determine the load impedance of the alarm sounder. if the delta measurement is too high, as at 112, it indicates an excessively high current caused by a low impedance fault, either due to the piezoelectric transducer 34 or class-d amplifier 32 being faulty. microcontroller 22a then reports back to the control panel 12 that a short-circuit fault exists on the alarm sounder 14i, as at 114. if however the delta measurement is too low, it does not necessarily mean that an open circuit fault has occurred, it could be that the loading caused by the class-d amplifier 32 driving the piezoelectric transducer 34 at such a high frequency is just too small to measure reliably, as the test frequency is far outside the normal operational range of an alarm sounder, such as 14i. if the delta measurement is too low, as at 116, then the microcontroller 22a goes through a process of reducing the test frequency by a small amount (say by 1 khz) and repeating the above test measurement (as at 104-110) to obtain a new value of adc2. as the test frequency moves closer to the normal operational frequency of the alarm sounder, then the load current taken by the class-d amplifier 32 due to the piezoelectric transducer 34 must increase if the alarm sounder is really fault free. the microcontroller 22a will then finish the silent monitoring when it detects that an open circuit does not exist. this will be at a frequency that exactly minimizes the audio output noise and maximizes the robustness of the measurement. if however the delta measurement is too low on each new test frequency and the test frequency has reached the normal operational frequency range of the alarm sounder, say for example as low as 3khz, then at this minimum frequency it is certain that a real open circuit fault must exists and the microcontroller 22a will stop the test and report an open circuit fault to the control panel. note that in this condition the monitoring has also remained silent even while the test frequency is well into the audio band and at its maximum volume. assuming a successful test of the alarm sounder resulted in no faults being found, then the square wave test frequency remains on for about ten seconds, as at 120, so that the storage capacitor 28 is fully discharged i.e. the class-d amplifier 32 falls to 0% volume, as at 122, before microcontroller 22a ramps the test frequency off to end the test. this process again ensures that the frequency content of the audio envelope is masked.
|
038-828-747-088-311
|
US
|
[
"TW",
"KR",
"US",
"WO",
"JP",
"CN"
] |
C23C16/455,C23C16/08,C23C16/18,H01L39/12,H01L43/10,C23C16/06,G11B5/62,C23C16/46,H01L21/285
| 2018-06-27T00:00:00 |
2018
|
[
"C23",
"H01",
"G11"
] |
cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material
|
a method of depositing a metal-containing material is disclosed. the method can include use of cyclic deposition techniques, such as cyclic chemical vapor deposition and atomic layer deposition. the metal-containing material can include intermetallic compounds. a structure including the metal-containing material and a system for forming the material are also disclosed.
|
1. a cyclic deposition process for depositing an intermetallic compound, the cyclic deposition method comprising the steps of: providing a first gas-phase reactant comprising a first metal from a first gas-phase reactant source vessel to a reaction chamber to react with a surface of a substrate to form a first metal species; and providing a second gas-phase reactant comprising a second metal to the reaction chamber to react with the first metal species to thereby form the intermetallic compound, wherein the first gas-phase reactant comprises a transition metal and bidentate nitrogen containing adduct forming ligand, and wherein the second gas-phase reactant comprises a metal-containing organic compound. 2. the cyclic deposition process of claim 1 , wherein the transition metal comprises a group 8-11 metal. 3. the cyclic deposition process of claim 1 , wherein the second gas-phase reactant is selected from the group consisting of compounds having formula of r-m-h wherein r is an organic group and m is a metal. 4. the cyclic deposition process of claim 3 , wherein the group consisting of compounds having formula of r-m-h have formula of r (x-n) -m x -h n , wherein x is the formal oxidation state of the metal and n is 1 to 5. 5. the cyclic deposition process of claim 3 , wherein r is independently selected from the group consisting of c1-c5 alkyl groups. 6. the cyclic deposition process of claim 3 , wherein r is cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionalities. 7. the cyclic deposition process of claim 1 , wherein the second metal is selected from the group consisting of sn, in, al, ga, ge, as, sb, pb and bi. 8. the cyclic deposition process of claim 1 , wherein the second gas-phase reactant comprises a metallic reducing agent. 9. the cyclic deposition process of claim 1 , wherein the first gas-phase reactant comprises a diamine adduct of a corresponding metal chloride. 10. the cyclic deposition process of claim 1 , wherein the first gas-phase reactant comprises a metal halide compound comprising the bidentate nitrogen containing adduct ligand. 11. the cyclic deposition process of claim 1 , wherein the first gas-phase reactant comprises at least one of cobalt chloride (tmeda) and nickel chloride (tmpda). 12. the cyclic deposition process of claim 1 , wherein the second gas-phase reactant comprises tbth. 13. a cyclic deposition process for forming a metal-containing material, the cyclic deposition process comprising: providing a first gas-phase precursor comprising a first metal to a reaction chamber from a first gas-phase reactant source vessel to form a first metal species; and providing a second gas-phase reactant comprising a compound having a general formula of r-m-h, wherein r is an organic group and m is a metal to react with the first metal species to thereby form the metal-containing material, wherein a temperature within the reaction chamber is greater than 0° c. and less than 600° c., wherein the first gas-phase precursor comprises a metal halide compound comprising a bidentate nitrogen containing adduct ligand, and wherein the first metal comprises a transition metal. 14. the cyclic deposition process of claim 13 , wherein the metal-containing material comprises elemental metal. 15. the cyclic deposition process of claim 13 , wherein the second metal is selected from the group consisting of sn, in, ga, al, ge, as, sb, pb and bi. 16. the cyclic deposition process of claim 13 , wherein the compound having a general formula of r-m-h has formula of r (x-n) -m x -h n , wherein x is the formal oxidation state of the metal and n is 1 to 5. 17. the cyclic deposition process of claim 13 , wherein the first gas-phase reactant comprises a diamine adduct of a corresponding metal chloride. 18. the cyclic deposition process of claim 13 , wherein the first gas-phase reactant comprises at least one of cobalt chloride (tmeda) and nickel chloride (tmpda). 19. the cyclic deposition process of claim 13 , wherein the second gas-phase reactant comprises tbth.
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cross-reference to related applications this application is a national stage entry of international patent application no. pct/ib2019/000817, filed jun. 21, 2019, entitled “cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material,” which claims priority to u.s. provisional patent application no. 62/690,478, filed on jun. 27, 2018 entitled “cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material,” the disclosures of which are hereby incorporated by reference in their entirety. parties of joint research agreement the invention claimed herein was made by, or on behalf of, and/or in connection with a joint research agreement between the university of helsinki and asm microchemistry oy. the agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement. field of invention the present disclosure relates generally to methods for depositing a metal-containing material on a surface of a substrate, films and structures including the metal-containing material, and reactors and systems for depositing the metal-containing material. background of the disclosure deposition of metal-containing material can be used in the manufacture of a variety of devices, such as semiconductor devices, flat panel display devices, photovoltaic devices, microelectromechanical systems (mems), magnetoresistance devices, superconductive devices, energy (e.g., hydrogen) storage devices, lithium or sodium ion batteries and the like and/or to form catalytic material. for many applications, it is often desirable to deposit the metal-containing material over a surface, which may include three-dimensional features, such as trenches and/or protrusions, which can have relatively high aspect ratios, in a uniform and/or conformal manner. recently, because of their relatively unique physical and chemical properties, interest has grown in possibly using intermetallic compounds in the formation of various devices. intermetallic compounds generally have a specific, ordered crystalline structure, which can be distinct from alloys formed of the same metals; the specific structure can lead to material properties that are superior to non-intermetallic compounds. such properties include, for example, magnetoresistance, superconductivity, catalytic activity, and hydrogen storage capability. by way of examples, intermetallic compounds containing co or ni and sn with varying stoichiometry have been studied as anode materials for li- and na-ion batteries, as ferromagnetic materials for magnetic devices, and for catalytic purposes. metal-containing material, such as co—sn and ni—sn with varying stoichiometry, including the intermetallic co 3 sn 2 and ni 3 sn 2 phases of the material, have generally been prepared by, for example, ball milling, arc melting, different solution-based techniques, solvo- and hydrothermal routes, electrodeposition, sputtering, and electron beam evaporation. chemical vapor deposition (cvd) from two single-source reactants, me 3 snco(co) 4 and ph 3 snco(co) 4 , has been employed to deposit an alloy of co and sn with 1:1 stoichiometry and only a minor constituent of co 3 sn 2 . ni 3 sn, ni 3 sn 2 , and ni 3 sn 4 have also been deposited by cvd using snme 4 and ni substrates followed by hydrogen treatment at high temperatures: although such techniques can be used to form intermetallic compounds, such techniques are generally not well suited for forming uniform, conformal films of intermetallic material on a surface of a substrate. cyclic deposition techniques, such as atomic layer deposition, can be used to deposit material in a relatively uniform (e.g., uniform crystalline structure, uniform composition, and/or uniform thickness) and conformal manner over complex, three-dimensional structures on a substrate surface in a controlled and reproducible manner. however, such techniques have generally not been employed to deposit several metal-containing materials, including intermetallic compounds. rather, the intermetallic compounds in particular are typically formed using other techniques and/or require additional, often high-temperature processes. accordingly, improved methods for forming metal-containing material, such as intermetallic compounds, are desired. additionally, improved techniques for forming uniform and/or conformal films of metal-containing material are desired. any discussion of problems provided in this section has been included in this disclosure solely for the purpose of providing a context for the present invention, and should not be taken as an admission that any or all of the discussion was known at the time the invention was made. summary of the disclosure this summary is provided to introduce a selection of concepts in a simplified form. these concepts are described in further detail in the detailed description of example embodiments of the disclosure below. this summary is not intended to necessarily identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. in accordance with at least one embodiment of the disclosure, a method for depositing an intermetallic compound is disclosed. in accordance with various aspects, the method is a cyclic deposition process that includes providing a first gas-phase reactant (also referred to herein as a precursor) comprising a first metal to a reaction chamber to react with a surface of a substrate to form a first metal species; and providing a second gas-phase reactant comprising a second metal to a reaction chamber to react with the first metal species to thereby form the intermetallic compound. additional reactants can similarly be used to form intermetallic compounds including more than two metals. as set forth in more detail below, a film of the intermetallic compound can be formed on a substrate surface without additional high temperature and/or reducing steps. the cyclic deposition process can include, for example, atomic layer deposition. in accordance with at least one other embodiment of the disclosure, a method for forming a metal-containing material is disclosed. the metal-containing material can include one, two, or three or more metals as described herein. the method can be a cyclic deposition process, such as an atomic layer deposition or cyclic chemical vapor deposition process. the cyclic deposition process can include providing a first gas-phase reactant comprising a first metal to a reaction chamber to form a first metal species and providing a second gas-phase reactant comprising a compound having a general formula of r-m-h (e.g., r (x-n) -m x -h n ), wherein r is an organic group and m is a metal to react with the first metal species to thereby form the metal-containing material. in accordance with various examples, x is the formal oxidation state of m and n can range from 1 to 5. in accordance with various aspects, the metal-containing material comprises one or more of metal mixture, an alloy, and an intermetallic compound. a film comprising the metal-containing material can be metallic, conductive, non-conductive, or semiconductive. exemplary films can be superconductive, magnetoresistive, ferromagnetic, or a catalyst. in accordance with at least one additional embodiment of the disclosure, a method for supplying a first gas-phase reactant comprising a first metal and a second gas-phase reactant comprising a second metal (e.g., comprising a compound having a general formula of r-m-h (e.g., r (x-n) -m x -h n , wherein r is an organic group, x is the formal oxidation state of the metal, n is 1 to 5 and m is a metal) is provided. the method may comprise: providing a second gas-phase reactant source vessel configured for containing the second gas-phase reactant (e.g., any of the second gas-phase reactants described herein), fluidly connecting the second gas-phase reactant source vessel to the reaction chamber; heating second gas-phase reactant contained in the second gas-phase reactant source vessel to a temperature of about 0° c. to about 400° c., about 20° c. to about 200° c., or about 20° c. to about 100° c.; generating a vapor pressure of the second gas-phase reactant of at least 0.001 mbar; and supplying the second gas-phase reactant to the reaction chamber. in some embodiments of the disclosure, a reactor system utilizing reactive volatile chemicals is provided. the reactor system can include a reaction chamber, a first gas-phase reactant source vessel in fluid communication with the reaction chamber, and a second gas-phase reactant source vessel in fluid communication with the reaction chamber. the second gas-phase reactant can include, for example, a compound having a general formula of r-m-h—e.g., r (x-n) -m x -h n , wherein r is an organic group, x is the formal oxidation state of the metal, n is 1 to 5, and m is a metal. for purposes of summarizing the disclosure and the advantages achieved over the prior art, certain objects and advantages may have been described herein above. of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the disclosure. thus, for example, those skilled in the art will recognize that the embodiments of the disclosure may be carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein. brief description of the drawing figures the subject matter of the present disclosure is particularly pointed out and distinctly claimed in the concluding portion of the specification. a more complete understanding of the present disclosure, however, may best be obtained by referring to the detailed description and claims when considered in connection with the drawing figures, wherein like numerals denote like elements and wherein: fig. 1 illustrates a process flow of an exemplary cyclical deposition method according to at least one embodiment of the disclosure; fig. 2 illustrates another process flow of an exemplary cyclical deposition method according to at least one embodiment of the disclosure; fig. 3 illustrates a schematic diagram of an exemplary device structure including a metal-containing film deposited according to at least one embodiment of the disclosure; fig. 4 illustrates an example of a metal halide compound utilized in a cyclical deposition process according to at least one embodiment of the disclosure; fig. 5 illustrates a schematic diagram of an exemplary reactor system according to at least one embodiment of the disclosure; and fig. 6 illustrates an exemplary second gas-phase reactant according to at least one embodiment of the disclosure. it will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. for example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of illustrated embodiments of the present invention. detailed description of exemplary embodiments the description of exemplary embodiments of the present disclosure provided below is merely exemplary and is intended for purposes of illustration only; the following description is not intended to limit the scope of the invention. moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. as set forth in more detail below, exemplary embodiments of the disclosure relate to methods and apparatus for depositing metal-containing material, such as intermetallic compounds, and to films and structures that include the metal-containing material. while the ways in which the present disclosure addresses various drawbacks of prior systems and methods are described in more detail below, in general, various systems and methods described herein employ improved reactants (sometimes generally referred to as precursors) and/or improved deposition techniques to deposit metal-containing material with desired properties. as used herein, the terms “precursor” and/or “reactant” may refer to one or more gases/vapors that take part in a chemical reaction or from which a gas-phase substance that takes part in a reaction is derived. the chemical reaction can take place in the gas phase and/or between a gas phase and a surface of a substrate and/or a species on a surface of a substrate. as used herein, the term “cyclic deposition” may refer to the sequential introduction of reactants into a reaction chamber to deposit a film over a substrate and includes deposition techniques such as atomic layer deposition and cyclical chemical vapor deposition. as used herein, the term “cyclical chemical vapor deposition” may refer to any process wherein a substrate is sequentially exposed to two or more volatile reactants, which react and/or decompose on a substrate to produce a desired material. as used herein, the term “atomic layer deposition” (ald) may refer to a vapor deposition process in which deposition cycles, e.g., a plurality of consecutive deposition cycles, are conducted in a reaction chamber. typically, during each cycle, a first reactant is chemisorbed to a surface of a substrate, forming a monolayer or sub-monolayer that does not readily react with additional first reactant (i.e., a self-limiting reaction). thereafter, another, second reactant or a reaction gas may subsequently be introduced into the process chamber for use in converting the chemisorbed substance to the desired material. further, purging steps may also be utilized during each deposition cycle to remove excess first reactant from the reaction chamber and/or remove excess second reactant, reaction gas, and/or reaction byproducts from the reaction chamber after conversion of the chemisorbed first and/or second reactant. further, the term “atomic layer deposition,” as used herein, is also meant to include processes designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ale), molecular beam epitaxy (mbe), gas source mbe, organometallic mbe, and chemical beam epitaxy, when performed with alternating pulses of reactants, reactive gas, and/or purge (e.g., inert carrier) gas. as used herein, the term “substrate” may refer to any material having a surface onto which a material can be deposited. a substrate can include a bulk material such as silicon (e.g., single crystal silicon), and may include one or more layers overlying the bulk material, including, for example, a chemisorbed species. further, the substrate can include various features, such as trenches, vias, lines, and the like formed within or on at least a portion of the substrate. the features can have an aspect ratio, defined as a feature's height divided by the feature's width, of, for example, greater than or equal to 5, greater than or equal to 10, greater than or equal to 15, or greater than or equal to 20. as used herein, the term “film,” “thin film,” “layer,” and “thin layer” may refer to any continuous or non-continuous material deposited—e.g., by methods disclosed herein. for example, “film,” “thin film,” “layer,” and “thin layer” can include 2d materials, nanorods, nanotubes, or nanoparticles or even partial or full molecular layers or partial or full atomic layers or clusters of atoms and/or molecules. “film,” “thin film,” “layer,” and “thin layer” may comprise material or a layer with pinholes, but still be at least partially continuous. as used herein, the term “metal-containing film” and “metal-containing material” may refer to a film or material that contains at least one metal species. as used herein, the term “metal” can include a semimetal or metalloid. as used herein, an “intermetallic” or an “intermetallic compound” may refer to a compound that includes two or more metal elements with a defined stoichiometry and an ordered crystal structure. intermetallic compounds differ from metal alloys by their crystal structure; the crystalline structures of intermetallic compounds are arranged in a specific structure, whereas alloys typically exhibit the crystal structure of one of the participating metal components. an intermetallic compound is formed when the bonds between the unlike atoms are stronger than the bonds between the atoms of the same element. a number of example materials are given throughout the current disclosure; it should be noted that the chemical formulas given for each of the example materials should not be construed as limiting, and that the non-limiting example materials given should not be limited by a given example stoichiometry. the present disclosure includes methods for depositing metal-containing material—e.g., films of the metal-containing material-onto a substrate. the methods can be carried out using a cyclical deposition process to deposit the metal-containing material to, for example, form a metal-containing film on the substrate. exemplary methods can deposit metal-containing films, such as films comprised, consisting essentially of, or consisting of an intermetallic compound at relatively low temperatures. additionally or alternatively, the methods can deposit metal-containing material with large-area thickness, crystallinity, and/or composition uniformity of film comprising, consisting essentially of, or consisting of the metal-containing material. turning now to the figures, fig. 1 illustrates a cyclic deposition method 100 in accordance with at least one embodiment of the disclosure. method 100 can be used to form an intermetallic compound, such as a film of the intermetallic compound on a substrate surface. method 100 begins with a step 110 which comprises providing at least one substrate into a reaction chamber and heating the substrate to a deposition temperature. the deposition temperature may depend on, for example, one or more reactants used to form the intermetallic compound. by way of examples, the reaction chamber can be heated to greater than 0° c. and less than 600° c., less than 500° c., less than 400° c., less than 300° c. or less than 250° c., or between about 20° c. to about 700° c., about 50° c. to about 500° c., or about 50° c. to about 400° c., about 75° c. to about 300° c. or about 100° c. to about 250° c. by way of particular examples, the intermetallic compound can include co 3 sn 2 , and, in this case, the temperature can range from about 170° c. to about 200° c.; similarly, when the intermetallic compound includes ni 3 sn 2 , the temperature can range from about 125° c. to about 175° c., or about 140° c. to about 160° c. a pressure within the reaction chamber may be controlled to provide a desired pressure in the reaction chamber for a deposition process. for example, the pressure within the reaction chamber during the cyclical deposition process may be less than 1000 mbar, or less than 100 mbar, or less than 10 mbar, or less than 5 mbar, or even, in some instances, less than 1 mbar, or from about 10 −8 mbar to about 1000 mbar, from about 10 −3 mbar to about 100 mbar, from about 10 −2 mbar to about 50 mbar, or from about 0.1 mbar to about 10 mbar. method 100 may continue with a step 120 , which includes providing a first gas-phase reactant comprising a first metal to the reaction chamber to react with a surface of a substrate to form a first metal species. this step may be at the same pressure and temperature noted above in connection with step 110 . a pulse time or a time that the first gas-phase reactant is provided to the reaction chamber can range from, for example, between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. during step 120 , a flowrate of the first gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm. after the step of providing a first gas-phase reactant, any excess first gas-phase reactant and any reaction byproducts may be removed from the reaction chamber by a purge/pump process (step 125 ). a duration of step 125 can be, for example, between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. a flow of a purge gas during step 125 may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm. although separately illustrated, step 125 can be considered part of step 120 . method 100 may continue with step 130 of providing a second gas-phase reactant comprising a second metal to the reaction chamber to react with the first metal species to thereby form the intermetallic compound. this step may be at the same or different pressure and/or temperature noted above in connection with step 110 . a pulse time or a time that the second gas-phase reactant is provided to the reaction chamber can range from between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. during step 130 , the flowrate of the second gas-phase reactant may be the same or similar as the flowrates noted above during step 120 . as illustrated in fig. 1 , as the second gas-phase reactant reacts with species on the substrate surface, an intermetallic compound—e.g., a film comprising, consisting essentially of, or consisting of an intermetallic compound is formed (step 140 ). after step 140 , any excess second gas-phase reactant and any reaction byproducts may be removed from the reaction chamber by a purge/pump process (step 145 ). a flow and/or duration of a purge gas in this step can be the same or similar to those noted above in step 125 . further, although separately illustrated, step 145 can be considered part of step 130 . steps 120 and 130 (and optionally purge steps 125 and/or 145 ) may constitute one deposition cycle. in some embodiments of the disclosure, method 100 may comprise repeating the deposition cycle one or more times. for example, method 100 may continue with a decision gate 150 , which determines if the cyclical deposition method 100 continues or exits via step 160 . decision gate 150 can be determined based on the thickness of or an amount of the deposited intermetallic compound. for example, if the thickness of the intermetallic compound is insufficient for the desired device structure, then the method 100 may return to step 120 , and steps 120 - 145 may be repeated. once the intermetallic compound has been deposited to a desired thickness or amount, the method may end at step 160 , and the substrate may be subjected to additional processes to form one or more devices or device structures. in accordance with various aspects of method 100 , the intermetallic compound forms upon reacting the second gas-phase reactant with a first metal species that forms on a surface during step 120 . thus, the intermetallic compound or layer or film comprising, consisting essentially of, or consisting of the intermetallic compound can be formed without an additional reduction step and/or heating step. further, as set forth above, the intermetallic compound can be formed at relatively low temperatures. the first gas-phase reactant can include any first metal that is different from the second metal. by way of examples, the first metal can be or include a transition metal (e.g., a group 3-12 metal), a group 3-6 metal, a group 7-12 metal, a lanthanide metal, a group 8-11 metal, and/or a group 9-10 metal. in accordance with alternative embodiments, such as those described below in connection with fig. 2 , the first gas-phase reactant can include a first metal that is the same as the second metal. when the first metal and the second metal are the same, an elemental metallic film can be formed. as noted above, such elemental metallic films can include semimetals or metalloids. the first gas-phase reactant can be or include a metal halide compound, wherein the metal is or includes the first metal. the metal halide compound may comprise a metal chloride, a metal iodide, a metal fluoride, or a metal bromide. in some embodiments of the disclosure, the metal halide compound may comprise a metal species, including, but not limited to, at least one of cobalt, nickel, or copper. in some embodiments of the disclosure, the metal halide compound may comprise at least one of a cobalt chloride, a nickel chloride, and a copper chloride. in some embodiments, the metal halide compound may comprise a bidentate nitrogen containing adduct forming ligand. in some embodiments, the metal halide compound may comprise an adduct forming ligand including two nitrogen atoms, wherein each of the nitrogen atoms are bonded to at least one carbon atom. in some embodiments of the disclosure, the metal halide compound comprises one or more nitrogen atoms bonded to a central metal atom thereby forming a metal complex. an example of such a compound is illustrated in fig. 4 . additional first gas-phase reactants can include adduct forming ligands that include phosphorous, oxygen, and/or sulfur. in some embodiments, the first gas-phase reactant may comprise a transition metal compound with an adduct forming ligand. in some embodiments, the first gas-phase phase reactant may comprise a transition metal compound. in some embodiments, the first gas-phase reactant may comprise a transition metal halide compound. in some embodiments, the first gas-phase reactant may comprise a transition metal compound with an adduct forming ligand, such as monodentate, bidentate, or multidentate adduct forming ligand. in some embodiments, the first gas-phase reactant may comprise a transition metal halide compound with adduct forming ligand, such as monodentate, bidentate, or multidentate adduct forming ligand. in some embodiments, the first gas-phase reactant may comprise a transition metal compound with adduct forming ligand comprising nitrogen, such as monodentate, bidentate, or multidentate adduct forming ligand comprising nitrogen. in some embodiments, the first gas-phase reactant may comprise a transition metal compound with adduct forming ligand comprising phosphorous, oxygen, or sulfur, such as monodentate, bidentate, or multidentate adduct forming ligand comprising phosphorous, oxygen or sulfur. for example, in some embodiments, the transition metal halide compound may comprise a transition metal chloride, a transition metal iodide, a transition metal fluoride, or a transition metal bromide. in some embodiments of the disclosure, the transition metal halide compound may comprise a transition metal species, including, but not limited to, at least one of cobalt, nickel, or copper. in some embodiments of the disclosure, the transition metal halide compound may comprise at least one of a cobalt chloride, a nickel chloride, or a copper chloride. in some embodiments, the transition metal halide compound may comprise a bidentate nitrogen containing adduct forming ligand. in some embodiment, the transition metal halide compound may comprise an adduct forming ligand including two nitrogen atoms, wherein each of the nitrogen atoms are bonded to at least one carbon atom. in some embodiments of the disclosure, the transition metal halide compound comprises one or more nitrogen atoms bonded to a central transition metal atom thereby forming a metal complex. in some embodiments of the disclosure, the first gas-phase reactant may comprise a transition metal compound having the formula: (adduct) n -m-xa wherein each of the “adducts” is an adduct forming ligand and can be independently selected to be a mono-, a bi-, or a multidentate adduct forming ligand or mixtures thereof: n is from 1 to 4 in case of monodentate forming ligand, n is from 1 to 2 in case of bi- or multidentate adduct forming ligand; m is a transition metal, such as, for example, cobalt (co), copper (cu), or nickel (ni); wherein each of xa is another ligand, and can be independently selected to be a halide or other ligand; wherein a is from 1 to 4, and some instances a is 2. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound, such as a transition metal halide compound, may comprise a monodentate, bidentate, or multidentate adduct forming ligand which coordinates to the transition metal atom, of the transition metal compound, through at least one of a nitrogen atom, a phosphorous atom, an oxygen atom, or a sulfur atom. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise a cyclic adduct ligand. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise mono, di-, or polyamines. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise mono-, di-, or polyethers. in some embodiments, the adduct forming ligand in the transition metal compound may comprise mono-, di-, or polyphosphines. in some embodiments, the adduct forming ligand in the transition metal compound may comprise carbon and/or in addition to the nitrogen, oxygen, phosphorous, or sulfur in the adduct forming ligand. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise one monodentate adduct forming ligand. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise two monodentate adduct forming ligands. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise three monodentate adduct forming ligands. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise four monodentate adduct forming ligands. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise one bidentate adduct forming ligand. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise two bidentate adduct forming ligands. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise one multidentate adduct forming ligand. in some embodiments of the disclosure, the adduct forming ligand in the transition metal compound may comprise two multidentate adduct forming ligands. in some embodiments of the disclosure, the adduct forming ligand comprises nitrogen, such as an amine, a diamine, or a polyamine adduct forming ligand. in such embodiments, the transition metal compound may comprise at least one of, triethylamine (tea), n,n,n′,n′-tetramethyl-1,2-ethylenediamine (cas: 110-18-9) (tmeda), n,n,n′,n′-tetramethylethylenediamine (cas: 150-77-6) (teeda), n,n′-diethyl-1,2-ethylenediamine (cas: 111-74-0) (deeda), n,n′-diisopropylethylenediamine (cas: 4013-94-9), n,n,n′,n′-tetramethyl-1,3-propanediamine (cas: 110-95-2) (tmpda), n,n,n′,n′-tetramethylmethanediamine (cas: 51-80-9) (tmmda), n,n,n′,n″,n″-pentamethyldiethylenetriamine (cas: 3030-47-5) (pmdeta), diethylenetriamine (cas: 111-40-0) (dien), triethylenetetramine (cas: 112-24-3) (trien), tris(2-aminoethyl)amine (cas: 4097-89-6) (tren, taea), 1,1,4,7,10,10-hexamethyltriethylenetetramine (cas: 3083-10-1) (hmteta), 1,4,8,11-tetraazacyclotetradecane (cas: 295-37-4) (cyclam), 1,4,7-trimethyl-1,4,7-triazacyclononane (cas: 96556-05-7), or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (cas: 41203-22-9). in some embodiments of the disclosure, the adduct forming ligand comprises phosphorous, such as a phosphine, a diphosphine, or a polyphosphine adduct forming ligand. for example, the transition metal compound may comprise at least one of, triethylphosphine (cas: 554-70-1), trimethyl phosphite (cas: 121-45-), 1,2-bis(diethylphosphino)ethane (cas: 6411-21-8) (bdepe), or 1,3-bis(diethylphosphino)propane (cas: 29149-93-7). in some embodiments of the disclosure, the adduct forming ligand comprises oxygen, such as an ether, a diether, or a polyether adduct forming ligand. for example, the transition metal compound may comprise at least one of, 1,4-dioxane (cas: 123-91-1), 1,2-dimethoxyethane (cas: 110-71-4) (dme, monoglyme), diethylene glycol dimethyl ether (cas: 111-96-6) (diglyme), triethylene glycol dimethyl ether (cas: 112-49-2) (triglyme), or 1,4,7,10-tetraoxacyclododecane (cas: 294-93-9) (12-crown-4). in some embodiments of the disclosure, the adduct forming ligand may comprise a thiother, or mixed ether amine, such as, for example, at least one of 1,7-diaza-12-crown-4: 1,7-dioxa-4,10-diazacyclododecane (cas: 294-92-8), or 1,2-bis(methylthio)ethane (cas: 6628-18-8). in some embodiments, the transition metal halide compound may comprise cobalt chloride n,n,n′,n′-tetramethyl-1,2-ethylenediamine (cocl 2 (tmeda)). in some embodiments, the transition metal halide compound may comprise cobalt bromide tetramethylethylenediamine (cobr 2 (tmeda)). in some embodiments, the transition metal halide compound may comprise cobalt iodide tetramethylethylenediamine (coi 2 (tmeda)). in some embodiments, the transition metal halide compound may comprise cobalt chloride n,n,n′,n′-tetramethyl-1,3-propanediamine (cocl 2 (tmpda)). in some embodiments of the disclosure, the transition metal halide compound may comprise at least one of cobalt chloride n,n,n′,n′-tetramethyl-1,2-ethylenediamine (cocl 2 (tmeda)), nickel chloride tetramethyl-1,3-propanediamine (nicl 2 (tmpda)), or nickel iodide tetramethyl-1,3-propanediamine (nii 2 (tmpda)). other suitable first gas-phase reactants may be substantially free of halogen species. first gas-phase reactants that are substantially free of halogen species (non-halogen containing metal precursors) include m(dmap)×(dmap=dimethylamino-2-propoxide), wherein m is a metal, β-diketonate, amidinate, and other typical ald metal precursors. in some embodiments, the non-halogen containing metal precursor may comprise at least one of copper, cobalt and nickel. the non-halogen containing metal precursor may therefore comprise at least one of cu(dmap) 2 , ni(dmap) 2 or co(dmap) 2 . in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand in which the metal center atom is bonded through at least one oxygen and at least one nitrogen atom in the bidentate ligand. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand in which the metal center atom is bonded through at least one nitrogen atom in the bidentate ligand. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand and at least one other ligand, such as monodentate ligand. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand and at least two other ligands, such as monodentate ligands. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand and at least one other ligand, such as monodentate ligand, which is bonded through n or o to the metal center atom. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand in which the metal center atom is bonded through at least one nitrogen atom and bonded through at least one other atom than nitrogen in the bidentate ligand. in some embodiments the non-halogen containing metal precursor may therefore comprise at least one bidentate ligand in which the metal center atom is bonded through at least two nitrogen atoms in the bidentate ligand. in some embodiments the non-halogen containing metal precursor comprises at least two bidentante ligands. in some embodiments the non-halogen containing metal precursor includes two bidentante ligands. some examples of suitable non-halide containing betadiketiminato (e.g., ni(pda) 2 ), (pda=pentane-2,4,-diketiminato) compounds include at least one d-diketiminato ligand, and have the general formula: wherein m is a metal selected from nickel, cobalt, ruthenium, iridium, palladium, platinum, silver and gold. each of r 1-5 is an organic ligand independently selected from h; and a c 1 -c 4 linear or branched, alky group, alkylsilyl group, alkylamide group, alkoxide group, or alkylsilylamide group. each l is independently selected from: a hydrocarbon; an oxygen-containing hydrocarbon; an amine; a polyamine; a bipyridine; an oxygen containing heterocycle; a nitrogen containing heterocycle; and combinations thereof; and ri is an integer ranging from 0 to 4, inclusive. a particular example includes ni(pda) 2 . some examples of suitable non-halide containing amidinate compounds (e.g., ni(ipr-amd) 2 ) include compounds having a formula selected from the group consisting of m(i)amd, m(ii)amd and m(iii)amd 3 and oligomers thereof, where m is a metal and amd is an amidinate moiety, such as copper(i) amidinates, cobalt(ii) amidinates, or amidinates of nickel, iron, ruthenium, manganese, chromium, vanadium, niobium, tantalum, titanium and/or lanthanum. in one or more embodiments, precursors for monovalent metals include volatile metal(i) amidinates, [m(i)(amd)]x, where x=2, 3. some of these compounds have a dimeric structure 1, in which r 1 , r 2 , r 3 , r 1 ′, r 2 ′ and r 3 ′ are groups made from one or more non-metal atoms. in some embodiments, r 1 , r 2 , r 3 , r 1 ′, r 2 ′ and r 3 ′ may be chosen independently from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl groups or other non-metal atoms or groups. in some embodiments, r 1 , r 2 , r 3 , r 1 , r 2 ′ and r 3 ′ are each independently alkyl or fluoroalkyl or silylalkyl groups containing 1 to 4 carbon atoms. suitable monovalent metals include copper(i), silver(i), gold(i), and iridium(i). in one or more embodiments, the metal amidinate is a copper amidinate, and the copper amidinate comprises copper(i) n,n′-diisopropylacetamidinate, corresponding to taking r 1 , r 2 , r 1 ′ and r 2 ′ as isopropyl groups, and r 3 and r 3 ′ as methyl groups in the general formula 1. in one or more embodiments, the metal(i) amidinate is a trimer having the general formula [m(i)(amd)] 3 . in one or more embodiments, divalent metal precursors include volatile metal(ii) bis-amidinates, [m(ii)(amd) 2 ] x , where x=1, 2. these compounds may have a monomeric structure 2, in which r 1 , r 2 , r 3 , r 1 ′, r 2 ′ and r 3 ′ are groups made from one or more non-metal atoms. in one or more embodiments, dimers of this structure, e.g., [m(ii)(amd) 2 ] 2 , may also be used. in some embodiments, r 1 , r 2 , r 3 , r 1 ′, r 2 ′ and r 2 ′ may be chosen independently from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl, or fluoroalkyl groups or other non-metal atoms or groups. in some embodiments, r 1 , r 2 , r 3 , r 1 ′, r 2 ′ and r 3 ′ are each independently alkyl or fluoroalkyl or silylalkyl groups containing 1 to 4 carbon atoms. suitable divalent metals include cobalt, iron, nickel, manganese, ruthenium, zinc, titanium, vanadium, chromium, europium, magnesium and calcium. in one or more embodiments, the metal(ii) amidinate is a cobalt amidinate, and the cobalt amidinate comprises cobalt(ii) bis(n,n′-diisopropylacetamidinate), corresponding to taking r 1 , r 2 , r 1 ′ and r 2 ′ as isopropyl groups, and r 3 and r 3 ′ as methyl groups in the general formula 2. in one or more embodiments, precursors for trivalent metals include volatile metal(iii) tris-amidinates, m(iii)(amd) 3 . typically, these compounds have a monomeric structure 3, in which r 1 , r 2 , r 3 , r 1 ′, r 2 ′, r 3 ′, r 1 ″, r 2 ″ and r 3 ″ are groups made from one or more non-metal atoms. in some embodiments, r 1 , r 2 , r 3 , r 1 ′, r 2 ′, r 3 ′, r 1 ″, r 2 ″ and r 3 ″ may be chosen independently from hydrogen, alkyl, aryl, alkenyl alkynyl, trialkylsilyl, halogen or partly fluorinated alkyl groups. in some embodiments, r 1 , r 2 , r 3 , r 1 ′, r 2 ′, r 3 ′, r 1 ″, r 2 ″ and r 3 ″ are each independently alkyl groups containing 1 to 4 carbon atoms. suitable trivalent metals include lanthanum, praseodymium and the other lanthanide metals, yttrium, scandium, titanium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, iridium, aluminum, gallium, indium, and bismuth. in one or more embodiments, the metal(iii) amidinate is a lanthanum amidinate, and the lanthanum amidinate comprises lanthanum(iii) tris(n,n′-di-tert-butylacetamidinate), corresponding to taking r 1 , r 2 , r 1 ′, r 2 ′, r 1 ″ and r 2 ′ as tert-butyl groups and r 3 , r 3 ′ and r 3 ″ as methyl groups in the general formula 3. as used herein, metal amidinates having the same ratio of metal to amidinate as the monomer, but varying in the total number of metallamidinate units in the compound are referred to as “oligomers” of the monomer compound. thus, oligomers of the monomer compound m(r)amd 2 include [m(ii)(amd) 2 ] x , where x is 2, 3, etc. similarly, oligomers of the monomer compound m(i)amd include [m(i)amd] x , where x is 2, 3, etc. particular examples include (n,n′-diisopropylacetamidinato)copper ([cu(ipr-amd)] 2 ), bis(n,n′-diisopropylacetamidinato)cobalt ([co(ipr-amd) 2 ]), cobalt bis(n,n′-di-tert-butylacetamidinate) ([co(tbu-amd) 2 ]), lanthanum tris(n,n′-diisopropylacetamidinate) ([la(ipr-amd) 3 ]), lanthanum tris(n,n′-diisopropyl-2-tert-butylamidinate) ([la(ipr-tbuamd) 3 ]. ½c 6 h 12 ), bis(n,n′-diisopropylacetamidinato)iron ([fe(ipr-amd) 2 ] 2 ), bis(n,n′-di-tert-butylacetamidinate) ([fe( t bu-amd) 2 ]), bis(n,n′-diisopropylacetarnidinato)nickel ([ni( i pr-amd) 2 ]), bis(n,n′-diisopropylacetamidinato)manganese ([mn( i pr-amd) 2 ] 2 ), manganese bis(n,n′-di-tert-butylacetamidinate) ([mn( t bu-amd) 2 ]), tris(n,n′-diisopropylacetamidinato)titanium ([ti( i pr-amd) 3 ]), tris(n,n′-diisopropylacetamidinato)vanadium ([v( i pr-amd) 3 ]), silver (n,n′-diisopropylacetamidinate) ([ag( i pr-amd)] x (x=2 and x=3), lithium n,n′-di-sec-butylacetamidinate, cobalt bis(n,n′-di-sec-butylacetamidinate) ([co(sec-bu-amd) 2 ]), copper(i) n,n′-di-sec-butylacetamidinate dimer ([cu(sec-bu-amd)] 2 ), bismuth tris(n,n′-di-tert-butylacetamidinate) dimer ([bi( t bu-amd) 3 ] 2 ), strontium bis(n,n′-di-tert-butylacetamidinate) ([sr( t bu-amd) 2 ]n), bismuth oxide, bi 2 o 3 , and tris(n,n′-diisopropylacetamidinato)ruthenium ([ru( i pr-amd) 3 ]). some examples of suitable non-halide containing iminoalkoxide compounds are described by the formula: wherein m is a metal selected from groups 2 to 12 of the periodic table; and r1, r2, r3, and r4 are each independently h or c1-c8 alkyl. in a refinement, r1, r2, r3, and r4 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. in another refinement, m is cu, cr, mn, fe, co, or ni. specific examples of compounds having this formula include, but are not limited to, bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)nickel(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)cobalt(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)iron(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)manganese(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)chromium(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)copper(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)nickel(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)cobalt(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)iron(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)copper(ii), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)manganese(ii), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)copper(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)nickel(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)cobalt(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)iron(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)manganese(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)chromium(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)copper(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)nickel(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)cobalt(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)iron(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)manganese(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)chrolium(ii), and bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)copper(ii). particular examples include bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)nickel(h), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)cobalt(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)iron(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)manganese(ii), bis(1-(tert-butylimino)-2,3,3-trimetylbutan-2-olate)chromoium(ii), bis(1-(tert-butylimino)-2,3,3-trimethylbutan-2-olate)copper(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)nickel(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)cobalt(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)iron(ii), bis(1-(tert-butylimino)-2,3-dimethylbutan-2-olate)copper(ii), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)manganese(ii), bis(3-((tert-butylimino)methyl)-2,2,4,4-tetramethylpentan-3-olate)copper(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)cobalt(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)iron(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)manganese(ii), bis(3-(isopropylimino)-2-methylbutan-2-olate)chromium(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)nickel(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)cobalt(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)iron(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)manganese(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)chrolium(ii), bis(3-(2,2-dimethylhydrazono)-2-methylbutan-2-olate)copper(ii). in some embodiments the non-halogen containing metal precursor does not comprise other metal atoms than the desired metal (e.g., co, ni, cu). in some embodiments the metal in the non-halogen containing metal precursor has oxidation state of 0. in some embodiments the metal in the non-halogen containing metal precursor has oxidation state of +i. in some embodiments the metal in the non-halogen containing metal precursor has oxidation state of +ii. in some embodiments the metal in the non-halogen containing metal precursor has oxidation state of +ii. in some embodiments the oxidation state is the oxidation state of the metal in the precursor at room temperature. the oxidation state may change in different conditions, such as in different pressures, temperatures and/or atmospheres as well as when contacted with different surface materials at the said different conditions. in some embodiments the non-halogen containing metal precursor does not comprise halides, such as f, cl, br or i. in some embodiments the non-halogen containing metal precursor comprises carbon, hydrogen and nitrogen and optionally oxygen. in some embodiments the non-halide containing copper precursor may comprise, for example, cu(dmap) 2 or copper(i) n,n′-diisopropylacetamidinate. in some embodiments, copper precursors can be selected from the group consisting of copper betadiketonate compounds, copper betadiketiminato compounds, copper aminoalkoxide compounds, such as cu(dmae) 2 , cu(deap) 2 or cu(dmamb) 2 , copper amidinate compounds, such as cu(sbu-amd)] 2 , copper cyclopentadienyl compounds, copper carbonyl compounds and combinations thereof. in some embodiments, x(acac)y or x(thd)y compounds are used, where x is copper, y is generally, but not necessarily 2 or 3 and thd is 2,2,6,6-tetramethyl-3,5-heptanedionato. in some embodiments the non-halide containing copper precursor is copper(ii)acetate, [cu(hmds)] 4 or cu(nhc)hmds (1,3-di-isopropyl-imidazolin-2-ylidene copper hexamethyl disilazide) or cu-betadiketiminates, such as cu(dki)vtms (dki=diketiminate). in some embodiments the non-halide containing nickel precursor may be, for example, bis(4-n-ethylamino-3-penten-2-n-ethyliminato)nickel (ii). in some embodiments, nickel precursors can be selected from the group consisting of nickel betadiketonate compounds, nickel betadiketiminato compounds, nickel aminoalkoxide compounds, nickel amidinate compounds, nickel cyclopentadienyl compounds, nickel carbonyl compounds and combinations thereof. in some embodiments, x(acac)y or x(thd)y compounds are used, where x is nickel, y is generally, but not necessarily 2 or 3 and thd is 2,2,6,6-tetramethyl-3,5-heptanedionato. in some embodiments the co precursor is a co beta-diketoiminato compound. in some embodiments the co precursor is a co ketoiminate compound. in some embodiments the co precursor is a co amidinate compound. in some embodiments the co precursor is a co beta-diketonate compound. in some embodiments the co precursor contains at least one ketoimine ligand or a derivative thereof. in some embodiments the co precursor contains at least one amidine ligand or a derivative thereof. in some embodiments the co precursor contains at least one ketonate ligand or a derivative thereof. in some embodiments the co precursor is co 2 (co) 8 , cctba, cocp 2 , co(cp-amd), co(cp(co) 2 ), tbu-allylco(co) 3 or co(hmds) 2 . alternatively, metal hydrides and/or alanes may be used as a first gas-phase reactant (e.g., for hydride-hydride type reactions). the second gas-phase reactant used in method 100 can include a metal-containing organic compound. for example, second gas-phase reactant can include a compound selected from the group consisting of compounds having formula of r-m-h (e.g., r (x-n) -m x -h n ), wherein r is an organic group and m is a metal to react with the first metal species to thereby form the metal-containing material. in accordance with various examples, x is the formal oxidation state of m and n can range from 1 to 5. by way of particular examples, m can be or include sn, in, ga, ge, as, sb, pb and bi. or, m could include al. for example, m can include sn, in, or ga. r can be or include an alkyl group or cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionalities. exemplary alkyl groups can be independently selected from the group of c1-c5 alkyl groups. in some cases, the second gas-phase reactant (e.g., the r-m-h compound) can be a metal reducing agent. fig. 6 illustrates the particular second gas-phase reactant example of tributyltin hydride (tbth). intermetallic films comprised, consisting essentially of, or consisting of the intermetallic compound, such as co 3 sn 2 or ni 3 sn 2 , as described herein can exhibit magnetic hysteresis with high coercivity values exceeding 500 oe. the resistivity values of such films (as well as film formed according to method 200 ) can range from about 10 to about 10 6 μωcm, from 20 to 10 4 μωcm, or from 50 to 1000 μωcm, for example, 80 to 180 μωcm, depending on film thickness and/or stoichiometry. also, ni 3 sn 2 thin films formed according to method 100 exhibit an intermetallic crystal structure and high purity. exemplary intermetallic compounds and films can be used in a variety of applications, including, for example, magnetoresistive devices, superconductive devices, as catalysts, as energy (e.g., hydrogen) storage, and the like. fig. 2 illustrates another cyclic deposition method 200 in accordance with at least one embodiment of the disclosure. method 200 can be used to deposit metal-containing material to, for example, form a film or layer comprising, consisting essentially of, or consisting of the metal-containing material. the metal-containing material can include any of the intermetallic compounds described above, as well as other metal-containing compounds described herein. when films (e.g., formed via either method 100 or 200 ) consist essentially of or consist of an intermetallic compound, the film may exhibit superior properties as described herein. method 200 begins with step 210 , which can be the same or similar to step 110 . for example, the temperature and pressures within the reaction chamber can be the same or similar to those set forth in step 110 . method 200 may continue with step 220 , which includes providing a first gas-phase, such as any of the first gas-phase reactants described above. this step may be at the same pressure and temperature noted above in connection with step 210 . a pulse time or a time that the first gas-phase reactant is provided to the reaction chamber can range from between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. during step 220 , a flowrate of the first gas-phase reactant may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 seem, or from about 10 to about 1000 sccm. after step 220 of providing a first gas-phase reactant, any excess first gas-phase reactant and any reaction byproducts may be removed from the reaction chamber by a purge/pump process (step 225 ). a flow of a purge gas during step 225 may be less than 2000 sccm, or less than 1000 sccm, or less than 500 seem, or less than 200 sccm, or even less than 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm. although separately illustrated, step 125 can be considered part of step 120 . method 200 may continue with step 230 , which includes providing a second gas-phase reactant comprising a compound having a general formula of r-m-h, wherein r is an organic group and m is a metal to react with the first metal species (e.g., on the substrate surface) to thereby form the metal-containing material. the compound having a general formula of r-m-h can be the same as described above. a pulse time or a time that the second gas-phase reactant is provided to the reaction chamber can range from between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. during step 230 , a flowrate of the second gas-phase reactant may be less than 2000 seem, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm, or may range from about 1 to about 5000 sccm, from about 5 to about 2000 sccm, or from about 10 to about 1000 sccm. although separately illustrated, step 225 can be considered part of step 220 . as illustrated in fig. 2 , as the second gas-phase reactant reacts with species on the substrate surface, a metal-containing material—e.g., a film comprising, consisting essentially of, or consisting of the metal-containing material is formed. after step 230 , any excess second gas-phase reactant and any reaction byproducts may be removed from the reaction chamber by a purge/pump process (step 245 ). a flowrate of a purge gas can be the same as noted above in step 225 . further, although separately illustrated, step 245 can be considered part of step 230 . steps 220 - 245 can be repeated as desired in the same or similar manner as steps 120 - 145 described above in connection with fig. 1 . for example, the steps can be repeated until a desired film thickness or amount of metal-containing material is deposited onto the substrate. first gas-phase reactant used in step 220 can be or include any of the first gas-phase reactants described herein. as noted above, the first gas-phase reactant and the second gas-phase reactant can include the same or different metals. for example, by combining a first gas-phase reactants, such as gecl3(dioxane) or some other ge precursor with r 3 geh, an elemental ge film can be formed. other elemental films (or multi-metal films) can similarly be formed. second gas-phase reactant comprising a compound having a general formula of r-m-h, wherein r is an organic group and m is a metal can be or include any of the r-m-h compounds described herein, such as those described above in connection with method 100 . in accordance with some embodiments of the disclosure, method 100 and/or method 200 can include atomic layer deposition (ald). ald is based on typically self-limiting reactions, whereby sequential and alternating pulses of reactants are used to deposit about one atomic (or molecular) monolayer of material per deposition cycle. the deposition conditions and reactants are typically selected to provide self-saturating reactions, such that an adsorbed layer of one reactant leaves a surface termination that is non-reactive with the gas phase reactants of the same reactant. the substrate is subsequently contacted with a different reactant that reacts with the previous termination to enable continued deposition. thus, each cycle of alternated pulses typically leaves no more than about one monolayer of the desired material. however, as mentioned above, in one or more ald cycles, more than one monolayer of material may be deposited, for example, if some gas phase reactions occur despite the alternating nature of the process. in some embodiments, the cyclical deposition processes are used to form metal-containing films on a substrate and the cyclical deposition process may be an ald-type process. in some embodiments, the cyclical deposition may be a hybrid ald/cvd or cyclical cvd process. for example, in some embodiments, the growth rate of the ald process may be low compared with a cvd process. one approach to increase the growth rate may be that of operating at a higher substrate temperature than that typically employed in an ald process, resulting in a chemical vapor deposition process, but still taking advantage of the sequential introduction of reactants. such a process may be referred to as cyclical cvd. the cyclical deposition processes described herein may be performed in an ald or cvd deposition system with a heated substrate. for example, in some embodiments, methods may comprise heating the substrate to a temperature of between approximately 80° c. and approximately 150° c., or even heating the substrate to a temperature of between approximately 80° c. and approximately 120° c. of course, the appropriate temperature window for any given cyclical deposition process, such as for an ald reaction, will depend upon the surface termination and reactant species involved. here, the temperature varies depending on the reactants being used and is generally at or below about 700° c. in some embodiments, the deposition temperature is generally at or above about 100° c. for vapor deposition processes, in some embodiments, the deposition temperature is between about 100° c. and about 300° c., and in some embodiments, the deposition temperature is between about 120° c. and about 200° c. in some embodiments, the deposition temperature is less than about 500° c., or less than below about 400° c., or less than about 350° c., or below about 300° c. in some instances, the deposition temperature can be below about 300° c., below about 200° c. or below about 100° c. in some instances, the deposition temperature can be above about 20° c., above about 50° c. and above about 75° c. in some embodiments of the disclosure, the deposition temperature, i.e., the temperature of the substrate during deposition, is the same or similar to the temperatures noted above in connection with methods 100 and 200 . as illustrated in figs. 1 and 2 , cyclic processes, including ald processes, may include purge steps, such as purge steps 125 , 145 , 225 , and 245 described above. purge gases used during such steps can include one or more inert gases, such as argon (ar) or nitrogen (n2), to prevent or mitigate gas-phase reactions between reactants, between process steps and to enable self-saturating surface reactions. in some embodiments, however, the substrate may additionally or alternatively be moved (e.g., to another reaction chamber) to separately contact a first gas-phase reactant and a second gas-phase reactant. thus, steps 120 / 130 and/or steps 220 / 230 need not be performed in the same reaction chamber. additionally or alternatively, a vacuum pump may be used to assist in the purging. it should be appreciated that in some embodiments of the disclosure, the order of providing a first gas-phase reactant and providing a second gas-phase reactant may be such that the substrate is first contacted with the second gas-phase reactant followed by the first gas-phase reactant. in other words, steps 120 , 130 and 220 , 230 can be reversed. in addition, in some embodiments, the cyclical deposition process may comprise contacting the substrate with first gas-phase reactant one or more times prior to contacting the substrate with second gas-phase reactant one or more times and similarly may alternatively comprise contacting the substrate with the second gas-phase reactant one or more times prior to contacting the substrate with the first gas-phase reactant one or more times. at least some embodiments of the disclosure (e.g., method 100 and/or method 200 ) may comprise non-plasma reactants, e.g., the first and second gas-phase reactants are substantially free of ionized reactive species. in some embodiments, the first and second gas-phase reactants are substantially free of ionized reactive species, excited species or radical species. for example, both the first gas-phase reactant and the second gas-phase reactant may comprise non-plasma reactants to prevent ionization damage to the underlying substrate and the associated defects thereby created. the use of non-plasma reactants may be especially useful when the underlying substrate contains fragile fabricated, or least partially fabricated, semiconductor device structures, as the high energy plasma species may damage and/or deteriorate device performance characteristics. although not illustrated in fig. 2 , in some embodiments of the disclosure, exemplary methods of the disclosure may comprise an additional process step comprising contacting the substrate with a third vapor phase reactant comprising a reducing agent. in some embodiments, the reducing agent may comprise at least one of hydrogen (h 2 ), a hydrogen (h 2 ) plasma, ammonia (nh 3 ), an ammonia (nh 3 ) plasma, hydrazine (n 2 h 4 ), silane (sih 4 ), disilane (si 2 h 6 ), trisilane (si 3 h 8 ), germane (geh 4 ), digermane (ge 2 h 6 ), borane (bh 3 ), diborane (b 2 h 6 ), tertiary butyl hydrazine (c 4 h 12 n 2 ), a selenium reactant, a boron reactant, a phosphorous reactant, a sulfur reactant, an organic reactant (e.g., alcohols, aldehydes, or carboxylic acids) or a hydrogen reactant. in some embodiments of the disclosure, exemplary cyclical deposition methods of the disclosure may comprise contacting the substrate with a second vapor phase reactant which is a reducing agent (without any additional precursor/reactant contacting steps). however, as noted above, in accordance with at least some examples, no reducing agent or reduction reaction is required to form the desired material, such as intermetallic material. if used, the third vapor phase reactant comprising a reducing agent may be introduced into the reaction chamber and contact the substrate at a number of process stages in an exemplary cyclical deposition method. in some embodiments of the disclosure, the reducing agent may be introduced into the reaction chamber and contact the substrate separately from the first gas-phase reactant and/or separately from the second gas-phase reactant. for example, the reducing agent may be introduced into the reaction chamber and contact the substrate prior to contacting the substrate with the first gas-phase reactant, after contacting the substrate with the first gas-phase reactant and prior to contacting the substrate with the second gas-phase reactant, and/or after contacting the substrate with the second gas-phase reactant. in some embodiments of the disclosure, the reducing agent may be introduced into the reaction chamber and contact the substrate simultaneously with the first gas-phase reactant and/or simultaneously with the second gas-phase reactant. for example, the reducing agent and the first gas-phase reactant may be co-flowed into the reaction chamber and simultaneously contact the substrate, and/or the reducing agent and the second gas-phase reactant may be co-flowed into the reaction chamber and simultaneously contact the substrate. in some embodiments, the growth rate of the metal-containing material and/or intermetallic compound is from about 0.005 å/cycle to about 5 å/cycle, from about 0.01 å/cycle to about 2.0 å/cycle. in some embodiments, the growth rate of metal-containing material and/or intermetallic compound is more than about 0.05 å/cycle, more than about 0.1 å/cycle, more than about 0.15 å/cycle, more than about 0.20 å/cycle, more than about 0.25 å/cycle, or more than about 0.3 å/cycle. in some embodiments, the growth rate of the metal-containing material and/or intermetallic compound is less than about 2.0 å/cycle, less than about 1.0 å/cycle, less than about 0.75 å/cycle, less than about 0.5 å/cycle, or less than about 0.2 å/cycle. in some embodiments of the disclosure, the growth rate of the metal-containing material and/or intermetallic compound may be approximately 0.4 å/cycle. by way of particular examples, in the case of co 3 sn 2 , the growth ranged from about 0.7 and 1.3 å/cycle at deposition temperatures of about 170-200° c., and in the case of ni 3 sn 2 , a growth rate of about 1.3 å/cycle at 160° c. was observed when nicl 2 (tmpda) was used as a first gas-phase reactant. fig. 3 illustrates a structure 300 that includes a substrate 302 and a layer or film 304 . structure 300 can be or include a partially-fabricated device structure. as noted above, substrate 302 can include bulk material, such as bulk semiconductor material, and layers formed thereon and/or therein. film 302 can include an intermetallic compound or a metal-containing material, such as intermetallic compound or metal-containing material deposited according to the embodiments described herein. in some embodiments, film 304 may be continuous at a thickness below approximately 100 nanometers, or below approximately 60 nanometers, or below approximately 50 nanometers, or below approximately 40 nanometers, or below approximately 30 nanometers, or below approximately 25 nanometers, or below approximately 20 nanometers, or below approximately 15 nanometers, or below approximately 10 nanometers, or below approximately 5 nanometers, or lower. the continuity referred to herein can be physical continuity or electrical continuity. in some embodiments, the thickness at which film 304 may be physically continuous may not be the same as the thickness at which a film is electrically continuous, and the thickness at which a film 304 may be electrically continuous may not be the same as the thickness at which a film is physically continuous. in some embodiments, the intermetallic and/or metal-containing film (e.g., film 304 ) deposited according to some of the embodiments described herein may have a thickness from about 20 nanometers to about 100 nanometers. in some embodiments, the intermetallic and/or metal-containing film deposited according to some of the embodiments described herein may have a thickness from about 20 nanometers to about 60 nanometers. in some embodiments, the intermetallic and/or metal-containing film deposited according to some of the embodiments described herein may have a thickness greater than about 20 nanometers, or greater than about 30 nanometers, or greater than about 40 nanometers, or greater than about 50 nanometers, or greater than about 60 nanometers, or greater than about 100 nanometers, or greater than about 250 nanometers, or greater than about 500 nanometers. in some embodiments, the intermetallic and/or metal-containing film deposited according to some of the embodiments described herein may have a thickness of less than about 50 nanometers, less than about 30 nanometers, less than about 20 nanometers, less than about 15 nanometers, less than about 10 nanometers, less than about 5 nanometers, less than about 3 nanometers, less than about 2 nanometers, or even less than about 1 nanometer. in some embodiments of the disclosure, the intermetallic and/or metal-containing film may be deposited on a three-dimensional structure, e.g., anon-planar substrate comprising high aspect ratio features. in some embodiments, the step coverage of the intermetallic and/or metal-containing film may be equal to or greater than about 50%, or greater than about 80%, or greater than about 90%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or greater in structures having aspect ratios (height/width) of more than about 2, more than about 5, more than about 10, more than about 25, more than about 50, or even more than about 100. the intermetallic compound and/or metal-containing material or corresponding films thereof comprises the first metal and the second metal as described herein. by way of particular examples, the first metal can include co, ni, pt, or any of the other first metals noted herein and the second metal can include sn, in, ga, ge, as, sb, pb and bi (e.g., sn, in, or fe) or any of the other second metals noted herein, including al. exemplary intermetallic and/or metal-containing compounds include (hexagonal) co 3 sn 2 or ni 3 sn 2 . intermetallic and/or metal-containing compounds could also have other stoichiometry or other crystal structure, which can be obtained by, for example, heat treatment or by tuning the deposition conditions. other exemplary intermetallic compounds and/or metal-containing materials comprise compounds of in—sb, pt—in, pt—sn, pt—ir, pd—pt, ru—pt, ru, co, co—w, ru—mn, cu—mn, and co—pt. other particular examples of intermetallic compounds and/or metal-containing materials include co, ni, cu, and/or pt and one or more of sn, in, ga, ge, as, sb, pb, al, and bi. in some cases, a film including the intermetallic compound and/or metal-containing material does not include al, ga, and/or in and a transition metal. in some embodiments of the disclosure, intermetallic compound and/or metal-containing material and/or films including same, as described herein, may comprise less than about 5 atomic % oxygen, less than about 2 atomic % oxygen, less than about 1 atomic % oxygen, or less than about 0.5 atomic % oxygen. in further embodiments, the compounds, materials, or films may comprise less than about 5 atomic % hydrogen, or less than about 2 atomic % hydrogen, or less than about 1 atomic % hydrogen, or even less than about 0.5 atomic % hydrogen. in yet further embodiments, the compounds, materials, or films may comprise less than about 5 atomic % carbon, or less than about 2 atomic % carbon, or less than about 1 atomic % carbon, or even less than about 0.5 atomic % carbon. in yet further embodiments, the compounds, materials, and films may comprise less than about 5 atomic % halide species, or less than about 2 atomic % halide species, or less than about 1 atomic % halide species, or even less than about 0.5 atomic % halide species. in some embodiments, the atomic % composition of the intermetallic compounds, metal-containing materials, and films including same may be determined utilizing time of flight elastic recoil detection analysis (tof-erda). reactors capable of being used to deposit metal-containing films can be used to form the intermetallic compounds, metal-containing materials, and films described herein. such reactors include ald reactors, as well as cvd reactors equipped with appropriate equipment and means for providing the reactants. according to some embodiments, a hot-walled, cross-flow reactor can be used. according to some embodiments, other cross-flow, batch, minibatch, or spatial ald reactors may be used. examples of suitable reactors that may be used include commercially available single substrate (or single wafer) deposition equipment such as pulsar® reactors (such as the pulsar® 2000 and the pulsar® 3000 and pulsar® xp ald), and emerald® xp and the emerald® reactors, available from asm america, inc. of phoenix, ariz. and asm europe b.v., almere, netherlands. other commercially available reactors include those from asm japan k.k. (tokyo, japan) under the tradename eagle® xp and xp8. in some embodiments, the reactor is a spatial ald reactor, in which the substrate moves or rotates during processing. in some embodiments of the disclosure, a batch reactor may be used. suitable batch reactors include, but are not limited to, advance® 400 series reactors commercially available from asm europe b.v. (almere, netherlands) under the trade names a400 and a412 plus. in some embodiments, the wafers rotate during processing. in other embodiments, the batch reactor comprises a minibatch reactor configured to accommodate 10 or fewer substrates (e.g., semiconductor wafers), 8 or fewer substrates, 6 or fewer substrates, 4 or fewer substrates, or 2 or fewer substrates. in some embodiments in which a batch reactor is used, wafer-to-wafer non-uniformity is less than 3% (1sigma), less than 2%, less than 1% or even less than 0.5%. the deposition processes described herein can optionally be carried out in a reactor or a reaction chamber connected to a cluster tool. in a cluster tool, because each reaction chamber is dedicated to one type of process, the temperature of the reaction chamber in each module can be kept constant, which improves the throughput compared to a reactor in which the substrate is heated up to the process temperature before each run. additionally, in a cluster tool it is possible to reduce the time to pump the reaction chamber to the desired process pressure levels between substrates. in some embodiments of the disclosure, the deposition process may be performed in a cluster tool comprising multiple reaction chambers, wherein each individual reaction chamber may be utilized to expose the substrate to an individual reactant gas and the substrate may be transferred between the different reaction chambers for exposure to multiple reactant gases, the transfer of the substrate being performed under a controlled environment to prevent oxidation/contamination of the substrate. in some embodiments of the disclosure, the deposition process may be performed in a cluster tool comprising multiple reaction chambers, wherein each individual reaction chamber may be configured to heat the substrate to a different deposition temperature. a stand-alone reactor can be equipped with a load-lock. in that case, it is not necessary to cool down the reaction space between each run. fig. 5 schematically illustrates a reactor system 500 in accordance with at least one embodiment of the disclosure. reactor system 500 can be used to, for example, perform the cyclic deposition (e.g., ald) methods as described herein and/or to form the structures, films, compounds and/or materials as described herein. in the illustrated example, reactor system 500 includes an optional substrate handling system 502 , a reaction chamber 504 , a gas distribution system 506 , and optionally a wall 508 disposed between reaction chamber 504 and substrate handling system 502 . system 500 can also include a first gas-phase reactant source 512 , a second gas-phase reactant source 514 , and an exhaust source 510 . although illustrated with two gas sources 512 , 514 , reactor system 500 can include any suitable number of reactant gas sources. by way of examples, exemplary reactor systems can include at least two reactant gas sources (e.g., sources that include compounds that become the first or second gas-phase reactant) and optionally one or more carrier and/or purge gas sources 516 . reactor system 500 also includes a susceptor 518 to hold one or more substrates 520 during processing. reactor system 500 can include any suitable number of reaction chambers 104 and substrate handling systems 502 . by way of example, reaction chamber 504 of reactor system 500 includes a cross-flow, hot-wall epitaxial reaction chamber. an exemplary reactor system including a horizontal flow reactor is available as a system from asm. it should be noted that fig. 5 is a simplified schematic version of reactor system 500 and does not contain each and every element, such as, but not limited to, valves, electrical connections, mass flow controllers, seals, and gas conduits, that may be utilized in the reactor system 500 . in some embodiments of the disclosure, one or more reactant source vessels 522 , 524 are in fluid communication, via conduits or other appropriate means 526 , 528 , to the reaction chamber 504 and may further be coupled to gas distribution system 506 disposed between reactant source vessels 522 , 524 and reaction chamber 504 . gas distribution system 506 can include, for example, a manifold, valve control systems, mass flow control systems, and/or other mechanism to control a gaseous reactant originating reactant source vessels 522 or 524 . reactant source vessels 522 , 524 may be configured for storing a metal-containing compound (e.g., an organometallic or metal organic compound) that is or that upon heating becomes the first gas-phase reactant and the second gas-phase reactant, respectively. in some embodiments, the reactant source vessels 522 , 524 may comprise a quartz material, which may be substantially chemically inert to the respective first and second reactants stored within source vessels 522 , 524 . in alternative embodiments of the disclosure, reactant source vessels 522 , 524 may be fabricated from a corrosion resistant metal or metal alloy, such as, for example, hastelloy, monel, or a combination thereof. in some embodiments of the disclosure, reactant source vessels 522 , 524 may further comprise one or more heating units 526 , 528 configured for heating the compound stored in reactant source vessels 522 , 524 to a desired temperature. in some embodiments, the one or more heating units may be utilized to heat the compound to a temperature of approximately greater than 0° c., or approximately greater than 20° c., or approximately greater than 100° c., or approximately greater than 150° c., or approximately greater than 200° c., or approximately greater than 200° c., or approximately greater than 300° c., or even approximately greater than 400° c. in some embodiments, the one or more heating units 526 , 528 may be configured to heat the compound stored in the reactant source vessels 522 , 524 to a temperature of approximately about 25° c. to about 200° c., about 25° c. to about 300° c., or about 25° c. to about 400° c. by way of particular examples, when a gas-phase reactant includes bu 3 snh, the temperature could range from about 20° c. to about 40° c., or be about 30° c.; when a reactant includes cocl 2 (tmeda), the temperature could range from about 150° c. to about 190° c., or be about 170° c.; when the reactant includes nicl 2 (tmpda), the temperature could range from about 140° c. to about 180° c., or be about 157° c.; and when the reactant included ni(dmap) 2 , the temperature could range from about 50° c. to about 70° c., or be about 62° c. in some embodiments, one or more heating units 526 , 528 associated with reactant source vessels 522 , 524 are configured for converting a compound from a solid to either a liquid or a gas to form the first gas-phase reactant or the second gas-phase reactant. in some embodiments, the one or more heating units 526 , 528 associated with reactant source vessels 522 , 524 , respectively, may be utilized to control the viscosity of the reactant compound stored in reactant source vessels 522 , 524 . in some embodiments, the one or more heating units 526 , 528 associated with the respective reactant source vessels 522 , 524 may be configured for controlling the vapor pressure generated by the compound stored within reactant source vessels 522 , 524 . in some embodiments of the disclosure, the compound may have a vapor pressure greater than 0.01 mbar at a temperature greater than 25° c., or greater than 50° c., or even greater than 100° c. in some embodiments of the disclosure, the compound may have a vapor pressure greater than 0.01 mbar at a temperature of less than 350° c., or less than 250° c., or less than 200° c., or even less than 150° c. in some embodiments of the disclosure, the compound may have a vapor pressure greater than 0.1 mbar at a temperature greater than 25° c., or even greater than 100° c. in some embodiments of the disclosure, the compound may have a vapor pressure greater than 0.1 mbar at a temperature of less than 400° c., or less than 200° c., or even less than 100° c. in some embodiments of the disclosure, the compound may have a vapor pressure greater than 1 mbar at a temperature of greater than 25° c., or even greater than 100° c. for example, the compound may be heated to a temperature greater than 150° c., generating a vapor pressure of greater than 0.001 mbar. in some embodiments of the disclosure, a vapor passageway 530 may be connected to the reactant source vessel 522 (and/or reactant source vessel 524 ), such that one or more carrier gases (e.g., from source 516 or another source) may be transported from a carrier gas storage vessel into reactant source vessel 522 via the vapor passageway 530 . in some embodiments, a mass flow controller (not shown) may be placed on vapor passageway 530 and disposed proximate to reactant source vessel 522 . for example, a mass flow controller may be calibrated to control the mass flux of the carrier gas entering reactant source vessel 522 , thereby allowing greater control over the subsequent flow of the reactant vapor from out of the reactant source vessel 522 to the reaction chamber 504 . in some embodiments, the carrier gas (e.g., hydrogen, nitrogen, helium, argon, or any mixtures thereof) may be flowed over an exposed surface of the compound, thereby picking up a portion of the vapor from the compound and transporting the compound (now a first or second gas-phase reactant), along with the carrier gas, to reaction chamber 504 . in alternative embodiments of the disclosure, the carrier gas may be “bubbled” through the compound, e.g., by optional vapor passageway (not illustrated), thereby agitating and picking up a portion of metal-containing compound and transporting metal-containing compound vapor (now the first or second gas-phase reactant) to reaction chamber 504 via gas conduit 526 . in some embodiments of the disclosure, reactor system 500 may further comprise a system operation and control mechanism 532 that provides electronic circuitry and mechanical components to selectively operate valves, manifold, pumps, and other equipment associated with reactor system 500 . such circuitry and compounds operate to introduce reactants, purge gas, and/or carrier gases from the respective reactant source vessels, 522 , 524 and purge gas vessel 534 . the system operation and control mechanism 532 may also control the timing of gas pulse sequences, the temperature of the substrate and/or reaction chamber, and the pressure of the reaction chamber and various other operations necessary to provide proper operation to reactor system 500 . operation and control mechanism 532 may include control software and electrically or pneumatically controlled valves to control the flow of reactants, carrier gases, and/or purge gases into and out of reaction chamber 504 . system operation and control mechanism 532 can include modules, such as software and/or hardware components, e.g., a fpga or asic, which perform certain tasks. a module can adversely be configured to reside on the addressable storage medium of system operation and control mechanism 532 and be configured to execute one or more processes. various other configurations of reactor systems are possible, including different number and kind of reactant sources and purge gas sources. further, there are many arrangements of valves, conduits, reactant sources, purge gas sources that may be used to accomplish the goal of selectively feeding gases into reaction chamber 504 . examples the examples provide below illustrate particular processes, films, and structures in accordance with exemplary embodiments of the disclosure. these examples are illustrative and are not meant to limit the scope of the disclosure. 1. a cyclic deposition process for depositing an intermetallic compound, the cyclic deposition method comprising the steps of: providing a first gas-phase reactant comprising a first metal to a reaction chamber to react with a surface of a substrate to form a first metal species; and providing a second gas-phase reactant comprising a second metal to the reaction chamber to react with the first metal species to thereby form the intermetallic compound. 2. the cyclic deposition process of example 1, further comprising repeating the steps of providing the first gas-phase reactant and providing the second gas-phase reactant until a desired film thickness is achieved. 3. the cyclic deposition process of example 1, further comprising one or more purging steps, wherein at least one of the purging steps occurs after the step of providing the first gas-phase reactant and before the step of providing the second gas-phase reactant. 4. the cyclic deposition process of example 1, wherein the cyclic deposition process comprises atomic layer deposition. 5. the cyclic deposition process of example 1, wherein the cyclic deposition process comprises cyclic chemical vapor deposition. 6. the cyclic deposition process of example 1, wherein a temperature within a reaction chamber during the steps of providing the first gas-phase reactant and providing the second gas-phase reactant is greater than 0° c. and less than 600° c., less than 500° c., less than 400° c., less than 300° c. or less than 250° c., or between about 20° c. to about 700° c., about 50° c. to about 500° c., or about 50° c. to about 400° c., about 75° c. to about 300° c. or about 100° c. to about 250° c. 7. the cyclic deposition process of example 1, wherein the second gas-phase reactant comprises a metal-containing organic compound. 8. the cyclic deposition process of example 1, wherein the second gas-phase reactant is selected from the group consisting of compounds having formula of r-m-h wherein r is an organic group and m is a metal. 9. the cyclic deposition process of example 1, wherein the second metal is selected from the group consisting of sn, in, al, ga, ge, as, sb, pb and bi. 10. the cyclic deposition process of example 1, wherein the second metal is selected from the group consisting of sn, ge, as, sb, pb and bi. 11. the cyclic deposition process of example 1, wherein the second metal comprises sn. 12. the cyclic deposition process of example 1, wherein the second metal comprises in. 13. the cyclic deposition process of example 1, wherein the second metal comprises ga. 14. the cyclic deposition process of example 8, wherein the group consisting of compounds having formula of r-m-h have formula of r (x-n)-m x -h n , wherein x is the formal oxidation state of the metal and n is 1 to 5. 15. the cyclic deposition process of any of examples 8 and 14, wherein r comprises an alkyl group or other organic group. 16. the cyclic deposition process of any of examples 8 and 14, wherein r is independently selected from the group consisting of c1-c5 alkyl groups. 17. the cyclic deposition process of any of examples 8 and 14, wherein r is cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionalities. 18. the cyclic deposition process of example 1, wherein the second gas-phase reactant comprises a metallic reducing agent. 19. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of transition metals. 20. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of group 3-6 metals. 21. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of group 7-12 metals. 22. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of lanthanides. 23. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of group 8-11 metals. 24. the cyclic deposition process of example 1, wherein the first metal is selected from the group consisting of group 9-10 metals. 25. the cyclic deposition process of example 1, wherein the first gas-phase reactant is selected from the group consisting of metal halides. 26. the cyclic deposition process of example 1, wherein the first gas-phase reactant comprises m(dmap) x (dmap=dimethylamino-2-propoxide), wherein m is a metal. 27. the cyclic deposition process of example 1, wherein the first gas-phase reactant is selected from the group consisting of metal hydrides and alanes. 28. the cyclic deposition process of example 1, wherein the first gas-phase reactant comprises a diamine adduct of a corresponding metal chloride. 29. the cyclic deposition process of example 1, wherein the first gas-phase reactant comprises a metal halide compound comprising a bidentate nitrogen containing adduct ligand. 30. the cyclic deposition process of example 29, wherein the adduct ligand comprises two nitrogen atoms, and wherein each of nitrogen atoms bonded to at least one carbon atom. 31. the cyclic deposition process of example 1, wherein the first gas-phase reactant comprises at least one of cobalt chloride (tmeda) and nickel chloride (tmpda). 32. the cyclic deposition process of example 1, wherein the second gas-phase reactant comprises tbth. 33. the cyclic deposition process of example 1, wherein the intermetallic compound does not include al, ga, and/or in and a transition metal. 34. a cyclic deposition process for forming a metal-containing material, the cyclic deposition process comprising: providing a first gas-phase precursor comprising a first metal to a reaction chamber to form a first metal species; and providing a second gas-phase reactant comprising a compound having a general formula of r-m-h, wherein r is an organic group and m is a metal to react with the first metal species to thereby form the metal-containing material. 35. the cyclic deposition process of example 34, wherein the first metal and the second metal are the same. 36. the cyclic deposition process of example 34, wherein the metal-containing material comprises elemental metal. 37. the cyclic deposition process of example 1 or 34, wherein the metal-containing material comprises a mixture of, for example, in and ge or other first and/or second metals. 38. the cyclic deposition process of example 34, further comprising repeating the steps of providing the first gas-phase reactant and providing the second gas-phase reactant until a desired film thickness is achieved. 39. the cyclic deposition process of example 34, further comprising one or more purging steps, wherein at least one of the purging steps occurs after the step of providing the first gas-phase reactant and before the step of providing the second gas-phase reactant. 40. the cyclic deposition process of example 34, wherein the cyclic deposition process comprises atomic layer deposition. 41. the cyclic deposition process of example 34, wherein the cyclic deposition process comprises cyclic chemical vapor deposition. 42. the cyclic deposition process of example 34, wherein a temperature within a reaction chamber during the steps of providing the first gas-phase reactant and providing the second gas-phase reactant is greater than 0° c. and less than 600° c., less than 500° c., less than 400° c., less than 300° c. or less than 250° c., or between about 20° c. to about 700° c., about 50° c. to about 500° c., or about 50° c. to about 400° c., about 75° c. to about 300° c. or about 100° c. to about 250° c. 43. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of sn, in, ga, al, ge, as, sb, pb and bi. 44. the cyclic deposition process of example 34, wherein the second metal is selected from the group consisting of sn, in, ge, as, sb, pb and bi. 45. the cyclic deposition process of example 34, wherein the second metal comprises sn. 46. the cyclic deposition process of example 34, wherein the second metal comprises in. 47. the cyclic deposition process of example 34, wherein the second metal comprises ga. 48. the cyclic deposition process of example 34, wherein the metal-containing material comprises one or more of a metal mixture, an alloy, and an intermetallic compound. 49. the cyclic deposition process of example 34, wherein the metal-containing material is one or more of metallic, conductive, non-conductive, semiconductive, superconductive, catalytic, ferromagnetic and magnetoresistive. 50. the cyclic deposition process of example 34, wherein the compound having a general formula of r-m-h has formula of r (x-n) -m x -h n , wherein x is the formal oxidation state of the metal and n is 1 to 5. 51. the cyclic deposition process of example 34, wherein r comprises an alkyl group or other organic group. 52. the cyclic deposition process of example 34, wherein r is independently selected from the group consisting of c1-c5 alkyl groups. 53. the cyclic deposition process of any of examples 34-52, wherein r is cyclopentadienyl, amido, alkoxy, amidinato, guanidinato, imido, carboxylato, β-diketonato, β-ketoiminato, malonato, β-diketiminato group with or without additional donor functionalities. 54. the cyclic deposition process of example 34, wherein the second gas-phase reactant comprises a metallic reducing agent. 55. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of transition metals. 56. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of group 3-6 metals. 57. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of group 7-12 metals. 58. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of lanthanides. 59. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of group 8-11 metals. 60. the cyclic deposition process of example 34, wherein the first metal is selected from the group consisting of group 9-10 metals. 61. the cyclic deposition process of example 34, wherein the first gas-phase reactant is selected from the group consisting of metal halides. 62. the cyclic deposition process of example 34, wherein the first gas-phase reactant comprises m(dmap) x (dmap=dimethylamino-2-propoxide), wherein m is a metal. 63. the cyclic deposition process of example 34, wherein the first gas-phase reactant is selected from the group consisting of metal hydrides and alanes. 64. the cyclic deposition process of example 34, wherein the first gas-phase reactant comprises a diamine adduct of a corresponding metal chloride. 65. the cyclic deposition process of example 34, wherein the first gas-phase reactant comprises a metal halide compound comprising a bidentate nitrogen containing adduct ligand. 66. the cyclic deposition process of example 65, wherein the adduct ligand comprises two nitrogen atoms, and wherein each of nitrogen atoms bonded to at least one carbon atom. 67. the cyclic deposition process of example 34, wherein the first gas-phase reactant comprises at least one of cobalt chloride (tmeda) and nickel chloride (tmpda). 68. the cyclic deposition process of example 34, wherein the second gas-phase reactant comprises tbth. 69. a film formed according to a process of any of examples 1-33. 70. the film of example 69, wherein the film is metallic, conductive, semiconductive, or non-conductive. 71. the film of example 69, wherein the film is superconductive. 72. the film of example 69, wherein the film is magnetoresistive. 73. the film of example 69, wherein the film is ferromagnetic. 74. the film of example 69, wherein the film is a catalyst. 75. a film formed according to a process of any of examples 34-68. 76. the film of example 75, wherein the film comprises one or more of a metal mixture, an alloy, and an intermetallic compound. 77. a device structure including the film according to one or more of examples 69 and 76. the example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. any equivalent embodiments are intended to be within the scope of this invention. indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent from the description. such modifications and embodiments are also intended to fall within the scope of the appended claims.
|
039-251-270-502-345
|
DE
|
[
"DE",
"US"
] |
H04R25/00,H04B5/00,H04B7/005
| 2007-03-12T00:00:00 |
2007
|
[
"H04"
] |
transmission method with dynamic transmission power adjustment and corresponding hearing device system
|
with the date transmission in a hearing device system, overloads are to be avoided and the energy consumption during transmission is to be kept as low as possible. to this end, a transmission method and a corresponding system for the inductive transmission is proposed, in which the receiver returns an item of quality information relating to the received signal back to the transmitter. the transmission power of the transmitter is then dynamically varied as a function of the item of quality information. with unidirectional transmission, the transmitter can obtain an item of distance information relating to the distance of the receiver from the transmitter and thereupon adjust the transmission power accordingly.
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1 .- 9 . (canceled) 10 . a transmission method for the inductive transmission in hearing devices and hearing device accessories, comprising transmitting a signal from a transmitter to a receiver with a specific transmission power; returning an item of quality information via the received signal from the receiver to the transmitter; and dynamically modifying the transmission power as a function of the item of quality information. 11 . the transmission method as claimed in claim 10 , wherein the item of quality information includes an item of information relating to the received signal strength. 12 . the transmission method as claimed in claim 10 , wherein the item of quality information includes an item of information relating to the bit error rate of the received signal. 13 . the transmission method as claimed in claim 10 , wherein the transmission power being reduced or increased until the received signal has reached a predetermined minimal quality. 14 . a hearing device system, comprising: a transmitter that inductively transmits a signal to a receiver with a specific transmission power, wherein the receiver inductively returns an item of quality information via the received signal to the transmitter, and wherein the transmission power of the transmitter is dynamically modified as a function of the item of quality information. 15 . the hearing device system as claimed in claim 14 , wherein the item of quality information includes an item of information relating to the received signal strength. 16 . the hearing device system as claimed in claim 14 , wherein the item of quality information includes an item of information relating to the bit error rate of the received signal. 17 . the hearing device system as claimed in claim 14 , wherein the transmission power being reduced or increased until the received signal has reached a predetermined minimal quality. 18 . a transmission method for the inductive transmission in hearing devices and hearing device accessories, comprising: transmitting a signal from a transmitter to a receiver with a specific transmission power, detecting an item of distance information through the transmitter relating to a distance of the receiver from the transmitter; and dynamic modifying the transmission power as a function of the distance information. 19 . the transmission method as claimed in claim 15 , wherein the detection of the distance information being carried out on the basis of a misalignment of a transmitting coil of the transmitter. 20 . the transmission method as claimed in claim 15 , wherein the detection of the distance information being carried out on the basis of a radiated transmission power. 21 . a hearing device system, comprising a transmitter that inductive transmits a signal to a receiver with a specific transmission power; and a sensor for detecting distance information relating to a distance of the receiver from the transmitter is connected to the transmitter; wherein the transmission power of the transmitter being able to be dynamically modified as a function of the distance information. 22 . the hearing device system as claimed in claim 21 , wherein the detection of the distance information being carried out on the basis of a misalignment of a transmitting coil of the transmitter. 23 . the hearing device system as claimed in claim 21 , wherein the detection of the distance information being carried out on the basis of a radiated transmission power.
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cross reference to related applications this application claims priority of german application no. 10 2007 011 841.6 de filed mar. 12, 2007, which is incorporated by reference herein in its entirety. field of invention the present invention relates to a transmission method for the inductive transmission in hearing devices and hearing device accessories by transmitting a signal from a transmitter to a receiver with a specific transmission power. the present invention also relates to a corresponding hearing device system. background of invention hearing devices are portable hearing apparatuses which are used to supply the hard-of-hearing. to accommodate the numerous individual requirements, different configurations of hearing devices such as behind-the-ear hearing devices (bte), in-the-ear hearing devices (ite), e.g. including conch hearing devices or channel hearing devices (cic), are provided. the hearing devices given here as examples are worn on the outer ear or in the auditory canal. furthermore, bone conduction hearing aids, implantable or vibrotactile hearing aids are also available on the market. the damaged hearing is stimulated either mechanically or electrically in such devices. essential components of the hearing devices include in principal an input converter, an amplifier and an output converter. the input converter is generally a receiving transducer, e.g. a microphone and/or an electromagnetic receiver, e.g. an induction coil. the output converter is mostly realized as an electroacoustic converter, e.g. a miniature loudspeaker, or as an electromechanical converter, e.g. a bone conduction receiver. the amplifier is usually integrated into a signal processing unit. this basic configuration is shown in the example in fig. 1 of a behind-the-ear hearing device. one or more microphones 2 for recording the ambient sound are incorporated in a hearing device housing 1 to be worn behind the ear. a signal processing unit 3 , which is similarly integrated into the hearing device housing 1 , processes the microphone signals and amplifies them. the output signal of the signal processing unit 3 is transmitted to a loudspeaker and/or receiver 4 , which outputs an acoustic signal. the sound is optionally transmitted to the ear drum of the device wearer via a sound tube, which is fixed with an otoplastic in the auditory canal. the power supply of the hearing device and in particular of the signal processing unit 3 is provided by a battery 5 which is likewise integrated into the hearing device housing 1 . the power of a transmitter in a data transmission system must be configured such that a level which is sufficient for demodulating the signal reaches the receiver even in the case of a maximum admissible distance between the transmitter and receiver. in this way, the attenuation of the signal, the interference and external faults are taken into consideration. the attenuation is very heavily dependent on the distance between the transmitter and receiver, so that under some circumstances a significantly stronger signal level reaches the receiver with shorter transmission distances than would be necessary for transmission purposes. this can lead to overloading and non-linear distortions in the receiver and to unnecessary energy consumption in the transmitter. excessively high distortions can render the transmission completely impossible in the case of very short distances. furthermore, in extreme cases, a very high reception level can damage the receiver. this behavior is particularly pronounced in the case of inductive transmission systems, such as in hearing devices and hearing device accessories, because the dependency of the signal attenuation on the distance is greater here than in the case of electromagnetic systems (e.g. bluetooth, cellular radio). with hearing devices, the unnecessary energy consumption during transmission was previously often accepted. on the receiver side, an automatic gain control (agc) is mostly implemented, which reduces overloading and distortions. also known from the cellular radio field is increasing the transmission power with poor availability, which is equivalent to reducing the transmission power with good availability (see eberspächer, j.; vögel, h.-j.: gsm global system for mobile communication. stuttgart: teubner, 1997, pages 100-111. isbn 3-519-06192-9). the publication de 102005005603 a1 discloses a data transmission apparatus for wireless data transmission for hearing devices and a corresponding method. so that hearing devices can be reached over longer transmission paths, a converter unit with a high frequency receiving device for receiving high-frequency signals of an external transmitting unit is proposed. the converter unit also has a mixer unit for mixing the high-frequency signal with a reference signal, so that an output signal can be generated, the frequency of which is lower by at least one order of magnitude and which is suited to inductive transmission. the output signal is then transmitted inductively from the converter to the hearing device. summary of invention the object of the present invention consists in proposing a transmission method for the inductive transmission in hearing devices and hearing device accessories, as well as a corresponding hearing device system, in which artifacts due to overloading and distortions are reduced on the one hand and the most minimal power consumption possible can be ensured on the other hand during transmission. in accordance with the invention, this object is achieved by a transmission method for the inductive transmission in hearing devices and hearing device accessories, by transmitting a signal from a transmitter to a receiver with a specific transmission power, by returning an item of quality information relating to the received signal from the receiver back to the transmitter and dynamically modifying the transmission power as a function of the item of quality information. a corresponding hearing device system with a transmitter for the inductive transmission of a signal to a receiver with a specific transmission power is also provided in accordance with the invention, with the receiver being embodied to inductively return an item of quality information relating to the received signal back to the transmitter and the transmission power of the transmitter being dynamically modifiable as a function of the item of quality information. it is advantageously possible to dynamically adjust the transmission power to the current conditions of a transmission channel. in this process, the actual attenuation of the transmitted signal is taken into consideration. the item of quality information advantageously contains an item of information relating to the received signal strength. it is thus possible for a predetermined minimum level of the received signal to be aimed for at the receiver, which provides for high-quality further processing. alternatively or in addition, the item of quality information can contain an item of information relating to a bit error rate of the received signal. the quality of the transmission channel is thus actually measured by the reliability with which information can be transmitted. it is particularly advantageous if the transmission power is modified to such an extent, i.e. reduced or increased, until the received signal has reached a predetermined minimum quality. in this way, the transmission power can be reduced to a minimum, which on the one hand still ensures acceptable transmission quality and on the other hand does not result in unnecessary power consumption. the aforementioned object is also achieved by a transmission method for the inductive transmission in hearing devices and hearing device accessories by transmitting a signal from a transmitter to a receiver with a specific transmission power, by detection of an item of distance information through the transmitter relating to a distance of the receiver from the transmitter and dynamically modifying the transmission power as a function of the distance information. provision is also made here for a corresponding hearing device system with a transmitter for the inductive transmission of a signal to a receiver with a specific transmission power, with a sensor for detecting distance information relating to a distance of the transmitter from the receiver being connected to the transmitter and the transmission power of the transmitter being dynamically modifiable as a function of distance information. the advantage of this dynamic transmission power adjustment of the wireless data transmission systems lies in the fact that no feedback from the receiver to the transmitter is necessary. instead, a purely transmitter-side control of the transmission power takes place here. the distance information can preferably be detected on the basis of a misalignment of a transmitting coil of the transmitter. the misalignment is an indirect item of information relating to a distance at which a receiver coil is located adjacent to the transmitting coil for instance. if the distance of both coils is very close, the resonant frequency of an oscillating circuit changes in the transmitter for instance. the detection of distance information can however also be carried out on the basis of a radiated transmission power. a principle of the transponder technology is thus used, in which the presence of a transponder coil in a magnetic field can be detected on the basis of the radiated power. brief description of the drawings the present invention is described in more detail with referenced to the appended drawings, in which; fig. 1 shows a basic circuit diagram of a hearing device according to the prior art; fig. 2 shows a circuit diagram of a data transmission system according to the invention with dynamic transmission power adjustment according to a first embodiment and fig. 3 shows a circuit diagram of a data transmission system with dynamic transmission power adjustment according to a second embodiment. detailed description of invention the exemplary embodiments illustrated in more detail below represent preferred embodiments of the present invention. for overview purposes, the exemplary embodiment of an inventive hearing device system illustrated in fig. 2 only shows the essential transmission system having a transmitting unit 10 and a receiving unit 20 . each of these units is either integrated in a hearing device or in a hearing device accessory, e.g. a remote controller or a microphone which is external to the hearing device. here the transmitting unit 10 includes a power amplifier 11 , the output power of which can be controlled and/or regulated. the output signal of the power amplifier 11 is applied to a transmitting coil 13 by way of a switch 12 . during transmission, the switch connects the output of the power amplifier 11 to the coil 13 . the receiving unit 20 has a corresponding receiving coil 23 , which is connected to an amplifier 21 with low noise by way of a switch 22 . this amplifier 21 can be controlled and/or regulated. in the case of reception, the switch 22 connects the receiving coil 23 to the minimally noisy amplifier 21 . a measuring unit 24 is connected to the output of the minimally noisy amplifier 21 , which measures the received signal strength or establishes a bit error rate. this bit error rate or signal strength is now to be transmitted to the transmitting unit 10 for dynamic transmission power adjustment purposes. to this end, the switch 22 of the receiving unit 20 is reversed at a suitable point in time such that it connects the output of the measuring unit 24 to the receiving coil 23 . the receiving coil 23 is now used for transmission purposes. to be able to apply the corresponding transmission power, a suitable power amplifier is integrated into the measuring unit 24 . on the transmit side, the coil 13 is now used to receive signals and the switch 12 connects the coil 13 to the input of a controller 14 . this receives the signal strength information from the receiver and controls the power amplifier 11 accordingly. attempts are always made here to minimize the transmission power as far as possible, but to guarantee a required minimum signal strength on the receiver in this process. the adjustment of the transmission power can be carried out iteratively in a number of steps, with current signal strength data being transmitted back to the transmitter during intervals in transmission. the dynamic transmission power adjustment according to the exemplary embodiment in fig. 2 is based on a bidirectional connection. the receiver 20 is namely able to inform the transmitter 10 about the received signal strength or the bit error rate during signal reception or both. the transmitter 10 can then reduce the transmission power in the case of an excessively large signal strength or increase the transmission power in the case of an excessively large bit error rate. fig. 3 shows a further exemplary embodiment of a transmitting unit 30 and a receiving unit 40 of an inventive hearing device system. the transmitting unit 30 also has a controllable and/or regulatable power amplifier 31 . its output is permanently connected here to a transmitting coil 32 . the transmitting unit 40 has a corresponding transmitting coil 42 , the receive signal of which is permanently fed into the input of a minimally noisy amplifier 41 . in order to adjust the transmission power, the transmitter 30 has a sensor 33 , which detects a distance 34 from the transmitter 30 to the receiver 40 . the distance 34 does not have to explicitly concern a distance specification. instead, the distance 34 can also be an item of information which indirectly stands for the distance between the transmitter 30 and receiver 40 . in particular, the distance 34 need also not represent the shortest distance between the transmitter 30 and the receiver 40 . the distance 34 can thus also illustrate a detour for instance, which the signal takes during data transmission as a result of obstacles. by way of example the distance 34 does not represent the shortest distance between the hearing devices worn on the ears, in the case of a binaural hearing device supply, but instead the signal transmission path around the head, when the signals take this path. the sensor 33 supplies the determined distance signal 34 to a control unit 35 , which now controls the power amplifier 31 as a function of the distance 34 . the sensor 33 can also obtain an item of distance information, by establishing that the transmitting field through the receiver 40 has changed. the change can be used as a measure for the distance. this principle is also used with transponders. alternatively, the transmission power can also be detected by the sensor 33 , which likewise changes as a function of the distance of the receiver 40 from the transmitter 30 . furthermore, it is likewise possible in accordance with transponder technology to herewith establish the distance of the receiver 40 , and to which extent the receiver 40 e.g. the oscillation amplitude of the transmitter 30 modulates due to its presence. in each exemplary embodiment illustrated in conjunction with fig. 3 , only the distance between the transmitter 30 and receiver 40 is taken into consideration for the dynamic transmission power adjustment. this distance is determined by the transmitter 30 irrespective of the receiver 40 on the basis of sensor data. the method can thus also be applied to purely unidirectional transmitter-receiver systems. it is common to all afore-described exemplary embodiments that the transmitter is able to dynamically adjust the transmission power to the distance and/or noise level, instead of permanently operating with maximum transmission power. consequently, the energy consumption in the transmitter can be reduced by the reduced transmission power and in the receiver by avoiding overloads respectively. reduced, non-linear distortions resulting herefrom enable the transmission even with very short distances. furthermore, the reduced transmission power does not result in damages to the receiver.
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039-465-475-544-016
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JP
|
[
"US",
"JP",
"KR",
"TW"
] |
G11C5/06,G11C11/00,G11C11/404,G11C14/00,G11C19/28,H01L27/12,H03K3/356,H01L21/8242,H01L27/10,H01L27/108,H01L29/786,G11C7/10,G11C7/12,G11C8/08,G11C16/06
| 2011-05-20T00:00:00 |
2011
|
[
"G11",
"H01",
"H03"
] |
register circuit including a volatile memory and a nonvolatile memory
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a semiconductor device capable of assessing and rewriting data at a desired timing is provided. a semiconductor device includes a register circuit, a bit line, and a data line. the register circuit includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit. the data line is electrically connected to the flip-flop circuit. the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit. the selection circuit selectively stores data based on a potential of the data line or a potential of the bit line in the nonvolatile memory circuit.
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1. a semiconductor device comprising: a register circuit including a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit; a bit line; and a data line, wherein the data line is electrically connected to the flip-flop circuit, wherein the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit, and wherein the selection circuit selectively stores data, which is based on a potential of the data line or a potential of the bit line, in the nonvolatile memory circuit. 2. the semiconductor device according to claim 1 , wherein the selection circuit selects any of a first operation mode for storing data based on a potential of the data line in the nonvolatile memory circuit through the flip-flop circuit, a second operation mode for supplying data stored in the nonvolatile memory circuit to the flip-flop circuit, a third operation mode for storing data based on the bit line in the nonvolatile memory circuit, and a fourth operation mode for supplying data stored in the nonvolatile memory circuit to the bit line. 3. the semiconductor device according to claim 1 , wherein the nonvolatile memory circuit includes a transistor including an oxide semiconductor in a channel formation region and a capacitor including one electrode electrically connected to a first electrode of the transistor and the other electrode that is grounded, and wherein a potential of the data line or a potential of the bit line is stored in a node where the first electrode of the transistor and the one electrode of the capacitor are electrically connected to each other. 4. a semiconductor device comprising: a register circuit including a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit; a bit line; a data line; a word line; and a memory write enable line, wherein the word line and the memory write enable line are electrically connected to the selection circuit, wherein the data line is electrically connected to the flip-flop circuit, wherein the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit, and wherein the selection circuit includes a first switch for determining electrical connection between the nonvolatile memory circuit and the word line or the memory write enable line, and a second switch for determining electrical connection between the nonvolatile memory circuit and the data line or the bit line. 5. the semiconductor device according to claim 4 , wherein the selection circuit selects any of a first operation mode for storing data based on a potential of the data line in the nonvolatile memory circuit through the flip-flop circuit, a second operation mode for supplying data stored in the nonvolatile memory circuit to the flip-flop circuit, a third operation mode for storing data based on the bit line in the nonvolatile memory circuit, and a fourth operation mode for supplying data stored in the nonvolatile memory circuit to the bit line. 6. the semiconductor device according to claim 4 , wherein the nonvolatile memory circuit includes a transistor including an oxide semiconductor in a channel formation region and a capacitor including one electrode electrically connected to a first electrode of the transistor and the other electrode that is grounded, and wherein a potential of the data line or a potential of the bit line is stored in a node where the first electrode of the transistor and the one electrode of the capacitor are electrically connected to each other. 7. a semiconductor device comprising: a plurality of register circuits provided in a matrix; a bit line; and a data line, wherein each of the register circuits includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit, wherein the data line is electrically connected to the flip-flop circuit, wherein the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit, and wherein the selection circuit selectively stores data, which is based on a potential of the data line or a potential of the bit line, in the nonvolatile memory circuit. 8. the semiconductor device according to claim 7 , wherein the selection circuit selects any of a first operation mode for storing data based on a potential of the data line in the nonvolatile memory circuit through the flip-flop circuit, a second operation mode for supplying data stored in the nonvolatile memory circuit to the flip-flop circuit, a third operation mode for storing data based on the bit line in the nonvolatile memory circuit, and a fourth operation mode for supplying data stored in the nonvolatile memory circuit to the bit line. 9. the semiconductor device according to claim 7 , wherein the nonvolatile memory circuit includes a transistor including an oxide semiconductor in a channel formation region and a capacitor including one electrode electrically connected to a first electrode of the transistor and the other electrode that is grounded, and wherein a potential of the data line or a potential of the bit line is stored in a node where the first electrode of the transistor and the one electrode of the capacitor are electrically connected to each other. 10. a semiconductor device comprising: a plurality of register circuits provided in a matrix; a bit line; a data line; a word line; and a memory write enable line, wherein each of the register circuits includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit, wherein the word line and the memory write enable line are electrically connected to the selection circuit, wherein the data line is electrically connected to the flip-flop circuit, wherein the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit, and wherein the selection circuit includes a first switch for determining electrical connection between the nonvolatile memory circuit and the word line or the memory write enable line, and a second switch for determining electrical connection between the nonvolatile memory circuit and the data line or the bit line. 11. the semiconductor device according to claim 10 , wherein the selection circuit selects any of a first operation mode for storing data based on a potential of the data line in the nonvolatile memory circuit through the flip-flop circuit, a second operation mode for supplying data stored in the nonvolatile memory circuit to the flip-flop circuit, a third operation mode for storing data based on the bit line in the nonvolatile memory circuit, and a fourth operation mode for supplying data stored in the nonvolatile memory circuit to the bit line. 12. the semiconductor device according to claim 10 , wherein the nonvolatile memory circuit includes a transistor including an oxide semiconductor in a channel formation region and a capacitor including one electrode electrically connected to a first electrode of the transistor and the other electrode that is grounded, and wherein a potential of the data line or a potential of the bit line is stored in a node where the first electrode of the transistor and the one electrode of the capacitor are electrically connected to each other.
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background of the invention 1. field of the invention the present invention relates to a semiconductor device and a method for driving the semiconductor device. 2. description of the related art signal processing circuits such as central processing units (cpus) vary in configuration depending on the intended use. a signal processing circuit generally has a main memory for storing data or program and other memory units such as a register and a cache memory. a register has a function of temporarily holding data for carrying out arithmetic processing, holding a program execution state, or the like. in addition, a cache memory is located between an arithmetic circuit and a main memory in order to reduce access to the main memory and speed up the arithmetic processing. a memory device such as a register or a cache memory needs to write data at higher speed than a main memory. for this reason, in general, a flip-flop circuit or the like is used as a register, while a static random access memory (sram) or the like is used as a cache memory. in other words, a volatile memory circuit is used as such a register, a cache memory, or the like. data in the volatile memory is lost when supply of a power supply voltage is stopped. in order to reduce power consumption, a method for temporarily stopping supply of a power supply voltage to a signal processing circuit in a period during which data is not input and output has been suggested. in the method, a nonvolatile memory device is located in the periphery of a volatile memory device such as a register or a cache memory, so that the data is temporarily stored in the nonvolatile memory device. thus, data stored in the register, the cache memory, or the like can be held even while supply of power supply voltage is stopped in the signal processing circuit (for example, see patent document 1). in addition, in the case where supply of a power supply voltage is stopped for a long time in a signal processing circuit, data in a volatile memory device is transferred to an external memory device such as a hard disk or a flash memory before the supply of the power supply voltage is stopped, so that the data can be prevented from being lost. reference [patent document 1] japanese published patent application no. h10-078836 summary of the invention as described above, in the case of providing an external memory device for storing data while supply of a power supply voltage is stopped, there is a problem in that it takes time to write data from a signal processing circuit to the external memory device, which is not suitable for a short-time stop of power supply. in addition, in the case where data in the signal processing circuit has problems, it takes time to assess and rewrite the data, so that the signal processing circuit cannot rapidly return from a state in which the supply of power supply voltage is stopped. in view of the above, an object is to provide a semiconductor device capable of transferring data of a signal processing circuit to a nonvolatile memory device at high speed, stopping supply of power with high frequency, and therefore reducing the power consumption. further, another object is to provide a semiconductor device capable of assessing and rewiring data at a desired timing. a nonvolatile memory circuit is provided for each flip-flop circuit included in a semiconductor device. data is transmitted and received between the flip-flop circuit and the nonvolatile memory circuit, whereby data can be transferred at high speed. in addition, the nonvolatile memory circuit is provided with a wiring which directly writes and reads data to/from the nonvolatile memory circuit, so that data stored in the semiconductor device can be assessed and rewritten through the wiring at a desired timing. one embodiment of the present invention is a semiconductor device which includes a register circuit including a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit; a bit line; and a data line. the data line is electrically connected to the flip-flop circuit. the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit. the selection circuit selectively stores data, which is based on a potential of the data line or a potential of the bit line, in the nonvolatile memory circuit. another embodiment of the present invention is a semiconductor device which includes a register circuit including a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit; a bit line; a data line; a word line; and a memory write enable line. the word line and the memory write enable line are electrically connected to the selection circuit. the data line is electrically connected to the flip-flop circuit. the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit. the selection circuit includes a first switch for determining electrical connection between the nonvolatile memory circuit and the word line or the memory write enable line, and a second switch for determining electrical connection between the nonvolatile memory circuit and the data line or the bit line. another embodiment of the present invention is a semiconductor device including a plurality of register circuits provided in a matrix, a bit line, and a data line. each of the register circuits includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit. the data line is electrically connected to the flip-flop circuit. the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit. the selection circuit selectively stores data, which is based on a potential of the data line or a potential of the bit line, in the nonvolatile memory circuit. still another embodiment of the present invention is a semiconductor device including a plurality of register circuits provided in a matrix, a bit line, a data line, a word line, and a memory write enable line. each of the register circuits includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit electrically connected to the flip-flop circuit through the selection circuit. the word line and the memory write enable line are electrically connected to the selection circuit. the data line is electrically connected to the flip-flop circuit. the bit line is electrically connected to the nonvolatile memory circuit through the selection circuit. the selection circuit includes a first switch for determining electrical connection between the nonvolatile memory circuit and the word line or the memory write enable line, and a second switch for determining electrical connection between the nonvolatile memory circuit and the data line or the bit line. the selection circuit used in the semiconductor device of one embodiment of the present invention selects any of a first operation mode for storing data based on a potential of the data line in the nonvolatile memory circuit through the flip-flop circuit, a second operation mode for inputting data stored in the nonvolatile memory circuit to the flip-flop circuit, a third operation mode for storing data based on the bit line in the nonvolatile memory circuit, and a fourth operation mode for inputting data stored in the nonvolatile memory circuit to the bit line. the nonvolatile memory circuit used in the semiconductor device of one embodiment of the present invention is a semiconductor device which includes a transistor including an oxide semiconductor in a channel formation region and a capacitor including one electrode electrically connected to a first electrode of the transistor and the other electrode that is grounded. a potential of the data line or a potential of the bit line is stored in a node where the first electrode of the transistor and the one electrode of the capacitor are electrically connected to each other. a semiconductor device with low power consumption can be provided. in the semiconductor device, a nonvolatile memory circuit is provided for each flip-flop circuit included in a register circuit, and data can be stored even when supply of power is stopped; therefore, power comsumption can be reduced. further, with a wiring for directly transmitting and receiving data between the nonvolatile memory circuit and an external portion of the register circuit, the semiconductor device can assess and rewrite data at a desired timing. brief description of the drawings figs. 1a and 1b are diagrams of a semiconductor device that is one embodiment of the present invention. fig. 2 is a diagram of a flip-flop circuit included in a semiconductor device that is one embodiment of the present invention. fig. 3 is a timing chart of operation of a semiconductor device that is one embodiment of the present invention. figs. 4a and 4b are timing charts of operation of a semiconductor device that is one embodiment of the present invention. figs. 5a and 5b are timing charts of operation of a semiconductor device that is one embodiment of the present invention. fig. 6 is a diagram of a semiconductor device that is one embodiment of the present invention. figs. 7a to 7e are diagrams of crystal structures of an oxide material which can be used for a transistor. figs. 8a to 8c are diagrams of a crystal structure of an oxide material which can be used for a transistor. figs. 9a to 9c are diagrams of a crystal structure of an oxide material which can be used for a transistor. figs. 10a and 10b are diagrams of crystal structures of oxide materials which can be used for a transistor. fig. 11 shows the gate voltage dependence of mobility obtained by calculation. figs. 12a to 12c each show the gate voltage dependence of drain current and mobility obtained by calculation. figs. 13a to 13c each show the gate voltage dependence of drain current and mobility obtained by calculation. figs. 14a to 14c each show the gate voltage dependence of drain current and mobility obtained by calculation. figs. 15a and 15b are diagrams of cross-sectional structures of transistors used for calculation. figs. 16a to 16c each show the characteristics of a transistor including an oxide semiconductor film. figs. 17a and 17b each show the gate voltage dependence of drain current after a bt test of a transistor of sample 1. figs. 18a and 18b each show the gate voltage dependence of drain current after a bt test of a transistor of sample 2. fig. 19 shows the gate voltage dependence of drain current and mobility. fig. 20a shows the relation between substrate temperature and threshold voltage and fig. 20b shows the relation between substrate temperature and field-effect mobility. fig. 21 shows xrd spectra of sample a and sample b. fig. 22 shows the relation between off-state current and substrate temperature in measurement of a transistor. figs. 23a to 23d are cross-sectional views of transistors. fig. 24 is a diagram of a signal processing circuit according to one embodiment of the present invention. detailed description of the invention hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. note that the present invention is not limited to the description below, and it is easily understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. therefore, the present invention should not be limited to the descriptions of the embodiments below. note that in structures of the invention described below, the same portions or portions having similar functions are denoted by the same reference numerals in different drawings, and description thereof is not repeated. note that in each drawing described in this specification, the size, the layer thickness, or the region of each component is exaggerated for clarity in some cases. therefore, embodiments of the present invention are not limited to such scales. note that in this specification and the like, the term “electrically connected” includes the case where components are connected through an “object having any electric function”. there is no particular limitation on an “object having any electric function” as long as electric signals can be transmitted and received between components that are connected through the object. examples of an “object having any electric function” include a switching element such as a transistor, a resistor, a coil, a capacitor, and an element with a variety of functions in addition to an electrode and a wiring. note that voltage generally refers to a difference between potentials at two points (also referred to as a potential difference). however, levels of voltage and potentials are represented using volt (v) in a circuit diagram or the like in some cases, so that it is difficult to discriminate between them. this is why in this specification, a potential difference between a potential at one point and a potential to be the reference (also referred to as the reference potential) is used as voltage at the point in some cases. functions of a source and a drain might interchange when a transistor of opposite polarity is used or the direction of current flow is changed in circuit operation, for example. therefore, the terms “source” and “drain” can interchange in this specification. in this specification and the like, one of a source and a drain of a transistor is referred to as a “first electrode” and the other of the source and the drain is referred to as a “second electrode” in some cases. embodiment 1 in this embodiment, a semiconductor device of one embodiment of the present invention will be described. <basic circuit> first, one mode of a register circuit that is a semiconductor device in this embodiment and the operation thereof will be described. fig. 1a is a block diagram of the register circuit. a register circuit 100 shown in fig. 1a includes a flip-flop circuit 101 , a selection circuit 103 , and a nonvolatile memory circuit 105 . in fig. 1a , a data line (data) is electrically connected to the flip-flop circuit 101 and a bit line (bit) is electrically connected to the nonvolatile memory circuit 105 through the selection circuit 103 . the flip-flop circuit 101 is electrically connected to an output signal line (q). a potential of the data line (data) is input to the flip-flop circuit 101 . the flip-flop circuit 101 stores data corresponding to the input potential as its internal state and outputs the data to an external portion through the output signal line (q). note that data corresponding to a potential means a 1-bit data with a potential corresponding to data “1” or “0”. either of two different potentials is selectively supplied and one of the potentials (e.g., high potential or high level) is made to correspond to data “1” and the other of the potentials (e.g., low potential or low level) is made to correspond to data “0”. further, a potential may be selected from three or more different potentials so that multivalued (multi-bit) data is written, which results in an increase in the memory capacity of the semiconductor device. in general, a flip-flop circuit includes at least two arithmetic circuits. the flip-flop circuit can have a configuration with a feedback loop in which output of one arithmetic circuit is input to the other arithmetic circuit and output of the other arithmetic circuit is input to the one arithmetic circuit. thus, the flip-flop circuit is a volatile memory circuit that stores and outputs data corresponding to a potential input from the data line (data). in the register circuit 100 , output of the flip-flop circuit 101 is input to the selection circuit 103 . output of the flip-flop circuit 101 and a potential of the bit line (bit) are input to the selection circuit 103 . an output terminal of the selection circuit 103 is electrically connected to an input terminal of the nonvolatile memory circuit 105 . the nonvolatile memory circuit 105 transmits and receives data to/from the flip-flop circuit 101 or the bit line (bit) depending on the operation mode selected by the selection circuit 103 . here, description will be given of the operation modes of the semiconductor device which are selected by the selection circuit 103 . the selection circuit 103 selects one of four operation modes of the semiconductor device. the four operation modes are a first operation mode for storing data based on a potential of the data line (data) in the nonvolatile memory circuit 105 through the flip-flop circuit 101 , a second operation mode for inputting data stored in the nonvolatile memory circuit 105 to the flip-flop circuit 101 , a third operation mode for storing data based on the potential of the bit line (bit) in the nonvolatile memory circuit 105 , and a fourth operation mode for inputting data stored in the nonvolatile memory circuit 105 to the bit line (bit). the four operation modes are combined to enable a reduction of the power consumption of the semiconductor device. the operation method will be described. in the semiconductor device of this embodiment, a potential of the data line (data) is input to the flip-flop circuit 101 and data based on the potential is stored in the flip-flop circuit 101 . as described above, since the flip-flop circuit 101 is a volatile memory circuit, supply of power is needed to hold data stored in the flip-flop circuit 101 . thus, continuous power supply is needed in order to hold data stored in the flip-flop circuit 101 even in a period during which the internal state of the flip-flop circuit 101 is not rewritten. however, in the semiconductor device of this embodiment, each register circuit 100 includes the nonvolatile memory circuit 105 electrically connected to the flip-flop circuit 101 . thus, the internal state of the flip-flop circuit 101 can be held even when supply of power is stopped by storing data in the nonvolatile memory circuit 105 in the period during which the internal state of the flip-flop circuit 101 is not changed. the internal state of the flip-flop circuit 101 can be stored in the nonvolatile memory circuit 105 when the selection circuit 103 selects the first operation mode. next, the selection circuit 103 selects the second operation mode so that data stored in the nonvolatile memory circuit 105 is stored in the flip-flop circuit 101 , whereby the flip-flop circuit 101 can return to the state before supply of power is stopped. in addition, the selection circuit combines the four operation modes, so that the semiconductor device can assess the internal state of the flip-flop circuit 101 at a desired timing. the operation method will be described. the selection circuit 103 selects the first operation mode, whereby the internal state of the flip-flop circuit 101 is stored in the nonvolatile memory circuit 105 . in this state, the selection circuit 103 selects the fourth operation mode so that the data stored in the nonvolatile memory circuit 105 is input to the bit line (bit); thus, a potential based on the internal state of the flip-flop circuit 101 is input to the bit line (bit). consequently, the internal state of the flip-flop circuit 101 can be assessed by reading the potential input to the bit line (bit). further, in the case where the internal state of the flip-flop circuit 101 is assessed and problems are founded, the internal state of the flip-flop circuit 101 can be easily rewritten in the semiconductor device of this embodiment. the operation methods will be described. in order to rewrite the internal state of the flip-flop circuit 101 , first, the third operation mode is selected by the selection circuit 103 . in the third operation mode, a potential based on data to be rewritten is input to the bit line (bit) and data based on the potential of the bit line (bit) is stored in the nonvolatile memory circuit 105 . next, the second operation mode is selected by the selection circuit 103 , so that a potential based on the data stored in the nonvolatile memory circuit 105 is input to the flip-flop circuit 101 . thus, the data to be rewritten which is input from the bit line (bit) is input to the flip-flop circuit 101 . in the semiconductor device of this embodiment, data of the flip-flop circuit 101 is stored in the nonvolatile memory circuit 105 , and therefore can be directly written and read through the bit line (bit); consequently, the internal state of the flip-flop circuit 101 can be assessed and rewritten at a desired timing a register circuit 200 in which more specific configurations of the selection circuit 103 and the nonvolatile memory circuit 105 are shown will be described. the register circuit 200 is shown in fig. 1b . as shown in fig. 1b , a circuit including a first switch 202 and a second switch 203 can form the selection circuit 103 . the first switch 202 is electrically connected to a word line (word) and a write enable line (we). output of the first switch 202 is input to the nonvolatile memory circuit 105 . the first switch 202 is a switch that outputs a potential of the word line (word) or a potential of the write enable line (we) to the nonvolatile memory circuit 105 . the second switch 203 is electrically connected to an output terminal of the flip-flop circuit 101 and a bit line (bit). output of the second switch 203 is input to the nonvolatile memory circuit 105 . the second switch 203 is a switch that outputs a potential based on the internal state of the flip-flop circuit 101 or a potential of the bit line (bit) to the nonvolatile memory circuit 105 . the second switch 203 determines electrical connection between the nonvolatile memory circuit 105 and the flip-flop circuit 101 or the bit line (bit). the nonvolatile memory circuit 105 shown in fig. 1b includes a transistor 204 and a capacitor 205 . a first electrode of the transistor 204 is electrically connected to one electrode of the capacitor 205 and the other electrode of the capacitor 205 is grounded. data is stored in a node where the first electrode of the transistor 204 and the one electrode of the capacitor 205 are electrically connected to each other (hereinafter also simply denoted as a node). a gate electrode of the transistor 204 is electrically connected to the first switch 202 included in the selection circuit 103 and a potential of the word line (word) or a potential of the write enable line (we) is input to the gate electrode of the transistor 204 . that is, the transistor 204 switches between on and off depending on the potentials of the word line (word) and the write enable line (we). a second electrode of the transistor 204 is electrically connected to the second switch 203 included in the selection circuit 103 . when the transistor 204 is on, a potential based on the internal state of the flip-flop circuit 101 or a potential of the bit line (bit) is input from the second switch 203 and input to the node where the first electrode of the transistor 204 and the one electrode of the capacitor 205 are electrically connected to each other. a transistor with small off-state current is used as the transistor 204 . in the case of using a transistor with small off-state current as the transistor 204 , data stored in the node can be held for a long time by turning off the transistor 204 even when supply of power is stopped. to write data to the nonvolatile memory circuit 105 , a charge corresponding to either of two different potentials (hereinafter a charge supplying a low potential is referred to as a charge q l and a charge supplying a high potential is referred to as a charge q h ) is selectively supplied to the capacitor 205 , for example. one of q l and q h is made to correspond to data “1” and the other is made to correspond to data “0”, so that 1-bit data can be written to the nonvolatile memory circuit 105 . note that a charge may be selected from charges corresponding to three or more different potentials, which results in an increase in the memory capacity of the nonvolatile memory circuit 105 . note that the transistor with small off-state current that is used for the transistor 204 can be a transistor including an oxide semiconductor material (a transistor in which a channel is formed in an oxide semiconductor layer), for example. since the off-state current of the transistor including an oxide semiconductor material is one hundred thousandth parts of that of a transistor in which a channel is formed in silicon, it is possible to neglect the loss of charges accumulated in the capacitor 205 caused by the leakage of charges from the transistor 204 which is turned off. thus, a potential stored in the node can be held for a long time. in fig. 1b , “os” is written beside the transistor 204 in order to indicate that the transistor 204 is a transistor including an oxide semiconductor. with the nonvolatile memory circuit 105 having the above configuration, in the case of writing new data, erasing of the written data is not needed and the written data can be directly rewritten by writing another data. thus, a decrease in operation speed due to erasing of data can be suppressed. in other words, the semiconductor device can be operated at high speed. further, the semiconductor device of the disclosed invention does not have a problem of deterioration of a gate insulating layer (a tunnel insulating layer), which has been a problem of a conventional floating-gate transistor. that is, the problem of deterioration of a gate insulating layer due to injection of electrons into a floating gate, which has been regarded as a problem, can be solved. this means that there is no limit on the number of times of writing in principle. furthermore, a high voltage needed for writing or erasing in the conventional floating gate transistor is not necessary. the operation of the register circuit 200 shown in fig. 1b will be described in detail with reference to a timing chart. first, a specific circuit configuration of a flip-flop circuit used to describe the operation of the register circuit 200 shown in fig. 1b will be described. fig. 2 shows the flip-flop circuit 101 used in the register circuit 200 . note that the configuration of a flip-flop circuit that can be used in the semiconductor device of this embodiment is not limited to the configuration in fig. 2 . the flip-flop circuit 101 shown in fig. 2 includes an inverter circuit 251 , a switch circuit 252 , an inverter circuit 253 , a clocked inverter circuit 254 , a clocked inverter circuit 255 , a switch circuit 256 , a clocked inverter circuit 257 , and a clocked inverter circuit 258 . a potential of a data line (data) is input to the flip-flop circuit 101 . the potential of the data line (data) is input to the clocked inverter circuit 254 through the switch circuit 252 . the potential of the data line (data) is inverted by the clocked inverter circuit 254 and input to a signal line (l) and the switch circuit 256 . note that the potential input to the signal line (l) is read out as the internal state of the flip-flop circuit 101 . the potential input to the switch circuit 256 is inverted again by the clocked inverter circuit 257 and becomes equal to the potential of the data line (data) and is output from an output signal line (q). the potential of the output signal line (q) is an output potential of the flip-flop circuit 101 and is a potential obtained by inverting the potential of the internal state of the flip-flop circuit 101 . the conducting states of the switch circuit 252 and the switch circuit 256 are controlled by a clock signal (clk). a clock signal inverted by the inverter circuit 251 is input to the switch circuit 252 and a clock signal is directly input to the switch circuit 256 , so that when one of the switch circuit 252 and the switch circuit 256 is opened, the other thereof is closed. here, the switch circuit 252 is closed and the switch circuit 256 is opened when a low-level potential is input to a clock signal line (clk) and the switch circuit 252 is opened and the switch circuit 256 is closed when a high-level potential is input to the clock signal line (clk). a latch circuit with a feedback loop in which output of the clocked inverter circuit 254 is input to the clocked inverter circuit 255 and output of the clocked inverter circuit 255 is input to the clocked inverter circuit 254 is formed. output of the clocked inverter circuit 254 is input to the clocked inverter circuit 255 and output of the clocked inverter circuit 255 is input to the clocked inverter circuit 254 ; thus, data can be held in the latch circuit. a clock signal (clk) is input to the clocked inverter circuit 255 and the clocked inverter circuit 255 operates only when the clock signal (clk) is at a high level. thus, when the switch circuit 252 is opened and the switch circuit 256 is closed by input of a high-level potential as the clock signal (clk), the clocked inverter circuit 255 operates and the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 holds the potential. a latch circuit with a feedback loop in which output of the clocked inverter circuit 257 is input to the clocked inverter circuit 258 and output of the clocked inverter circuit 258 is input to the clocked inverter circuit 257 is formed. output of the clocked inverter circuit 257 is input to the clocked inverter circuit 258 and output of the clocked inverter circuit 258 is input to the clocked inverter circuit 257 ; thus, data can be held in the latch circuit. a clock signal inverted by the inverter circuit 251 is input to the clocked inverter circuit 258 and the clocked inverter circuit 258 operates only when the clock signal is at a low level. thus, when the switch circuit 252 is closed and the switch circuit 256 is opened by input of a low-level potential as the clock signal (clk), the clocked inverter circuit 258 operates and the latch circuit including the clocked inverter circuit 257 and the clocked inverter circuit 258 holds the potential. a potential of a read enable line (re) is input to the clocked inverter circuit 254 through the inverter circuit 253 . when a high-level potential is input to the read enable line (re), a low-level potential inverted by the inverter circuit 253 is input to the clocked inverter circuit 254 and the operation of the clocked inverter circuit 254 is stopped. thus, when a high-level potential is input to the read enable line (re), the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 does not hold data. the above is the configuration and operations of the flip-flop circuit 101 shown in fig. 2 . next, the operation of the register circuit 200 in fig. 1b will be described. the case of using the flip-flop circuit 101 in fig. 2 as the flip-flop circuit 101 will be described here. fig. 3 , figs. 4a and 4b , and figs. 5a and 5b show timing charts of the register circuit 200 . in the timing charts shown in fig. 3 , figs. 4a and 4b , and figs. 5a and 5b , mem shows the potential of a selection signal line; bit, the potential of the bit line; word, the potential of the word line; re, the potential of the read enable line; we, the potential of the write enable line; clk, the potential of the clock signal; data, the potential of the data line; l, the potential of the signal line; q, the potential of the output signal line of the flip-flop circuit; and mem_d, the potential of data stored in the nonvolatile memory circuit 105 (the data stored in the node of the nonvolatile memory circuit 105 ). first, a timing chart of the normal operation of the flip-flop circuit in the register circuit will be described. the timing chart in fig. 3 shows the normal operation of the flip-flop circuit. in the normal operation of the flip-flop circuit, the selection circuit 103 may select any operation modes. thus, the potential of each of the selection signal line (mem), the bit line (bit), the word line (word), the read enable line (re), and the write enable line (we) can be a given potential. in the timing chart, a given potential is shown by a dashed line and denoted by the symbol (x). when the clock signal (clk) is at a low level, in the flip-flop circuit 101 , the switch circuit 252 is closed, so that data based on the potential of the data line (data) is input to the clocked inverter circuit 254 . the data based on the potential of the data line (data) is inverted by the clocked inverter circuit 254 and transmitted to the signal line (l). then, when the clock signal (clk) is at a high level, the switch circuit 252 is opened and the clocked inverter circuit 255 operates, so that the potential of the signal line (l) is held in the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 . further, when the clock signal (clk) is at a high level, the switch circuit 256 is closed, so that data inverted by the clocked inverter circuit 254 is input to the clocked inverter circuit 257 . when the inverted data is input to the clocked inverter circuit 257 , the data is inverted again by the clocked inverter circuit 257 and is output through the output signal line (q) of the flip-flop circuit 101 . then, when the clock signal (clk) is at a low level, the switch circuit 256 is opened and the clocked inverter circuit 258 operates, so that the potential of the output signal line (q) of the flip-flop circuit is held in the latch circuit including the clocked inverter circuit 257 and the clocked inverter circuit 258 . next, description will be given of the operation for storing data based on the data line (data) in the nonvolatile memory circuit 105 through the flip-flop circuit 101 when the selection circuit 103 selects the first operation mode. fig. 4a shows a timing chart of the first operation mode. the potential of the selection signal line (mem) is set at a high level so that the selection circuit 103 selects the first operation mode. when the selection signal line (mem) is at the high level, the gate electrode of the transistor 204 is electrically connected to the write enable line (we) through the first switch 202 . in addition, the output terminal of the flip-flop circuit 101 is electrically connected to the second electrode of the transistor 204 through the second switch 203 . when the clock signal (clk) is at a low level while the first operation mode is selected by the selection circuit 103 , the potential of the data line (data) is inverted by the clocked inverter circuit 254 and is input to the signal line (l). then, when the clock signal (clk) is at a high level, the switch circuit 252 is opened, so that the potential of the signal line (l) is held in the clocked inverter circuit 254 and the clocked inverter circuit 255 . in addition, the switch circuit 256 is closed, so that a potential (the potential of the data line (data)) that is the potential of the signal line (l) inverted by the clocked inverter circuit 257 is output to the output signal line (q). at this time, the write enable line (we) is set at a high level, whereby a high-level potential is input to the gate electrode of the transistor 204 to turn on the transistor 204 . consequently, the internal state of the flip-flop circuit 101 is stored in the node of the nonvolatile memory circuit 105 . then, the write enable line (we) is set at a low level, whereby the transistor 204 is turned off. since the off-state current of the transistor 204 is extremely small, the potential stored in the node can be held for an extremely long time by turning off the transistor 204 . through the above operation, the internal state of the flip-flop circuit 101 can be stored in the nonvolatile memory circuit 105 ; thus, the semiconductor device can hold the internal state of the flip-flop circuit 101 even when supply of power is stopped. in the semiconductor device of this embodiment, the nonvolatile memory circuit capable of storing data even when supply of power is stopped is provided for each flip-flop circuit; therefore, supply of power can be stopped when the internal state of the flip-flop circuit is not changed, which results in a reduction in the power consumption. next, description will be given of the operation for inputting data stored in the nonvolatile memory circuit 105 to the flip-flop circuit 101 when the second operation mode is selected by the selection circuit 103 . fig. 4b shows a timing chart of the second operation mode. the potential of the selection signal line (mem) is set at a high level so that the selection circuit 103 selects the second operation mode. when the selection signal line (mem) is at the high level, the gate electrode of the transistor 204 is electrically connected to the write enable line (we) through the first switch 202 . in addition, the output terminal of the flip-flop circuit 101 is electrically connected to the second electrode of the transistor 204 through the second switch 203 . when the clock signal (clk) is at a low level in the second operation mode, the potential of the data line (data) is input to the clocked inverter circuit 254 and the potential of the data line (data) which is inverted is input to the signal line (l). here, when the clock signal (clk) is at a high level, the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 operates and the potential of the signal line (l) is held. in addition, the switch circuit 256 is closed, so that data inverted by the clocked inverter circuit 254 is input to the clocked inverter circuit 257 . the data input to the clocked inverter circuit 257 is inverted by the clocked inverter circuit 257 and is output from the output terminal of the flip-flop circuit 101 . at this time, when the read enable line (re) is set at a high level, the operation of the clocked inverter circuit 254 is stopped and the operation of the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 is stopped. when the write enable line (we) is set at a high level to turn on the transistor 204 while the operation of the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 is stopped, the potential stored in the node between the transistor 204 and capacitor 205 (mem_d) is input to the clocked inverter circuit 255 through the signal line (l). the potential stored in the node is held in the signal line (l) even when the potential of the write enable line (we) is returned to the low level after the above operation. thus, when the read enable line (re) is set at a low level to restart the operation of the clocked inverter circuit 254 and the operation of the latch circuit including the clocked inverter circuit 254 and the clocked inverter circuit 255 , the potential stored in the node is held in the latch circuit. then, when the clock signal (clk) is at a low level, the switch circuit 252 is closed and the potential of the data line (data) is input to the clocked inverter circuit 254 , so that the normal operation of the flip-flop circuit 101 is restarted. note that in the semiconductor device of this embodiment, a transistor including an oxide semiconductor material (a transistor in which a channel is formed in an oxide semiconductor layer) is used as the transistor 204 . a transistor including an oxide semiconductor material has a characteristic of extremely small off-state current. hence, the potential of the capacitor 205 can be held for an extremely long time by turning off the transistor 204 . next, description will be given of the operation for storing data based on the potential of the bit line (bit) in the nonvolatile memory circuit 105 when the selection circuit 103 selects the third operation mode. fig. 5a shows the third operation mode. the selection signal line (mem) is set at a low level so that the selection circuit 103 selects the third operation mode. when the selection signal line (mem) is at the low level, the gate electrode of the transistor 204 is electrically connected to the word line (word) through the first switch 202 . in addition, the bit line (bit) is electrically connected to the second electrode of the transistor 204 through the second switch 203 . note that in the third operation mode, output of each of the read enable line (re), the clock signal line (clk), the data line (data), the signal line (l), and the flip-flop circuit can be a given potential. in the third operation mode, the word line (word) is set at a high level, so that the transistor 204 is turned on and the potential based on the potential of the bit line (bit) is stored in the node where the first electrode of the transistor 204 and the one electrode of the capacitor 205 are electrically connected to each other. the timing of inputting the potential to be stored in the nonvolatile memory circuit 105 to the bit line (bit) is before the word line (word) is set at the high level and the potential of the bit line (bit) is input to the node. next, description will be given of the operation for inputting the potential stored in the nonvolatile memory circuit 105 to the bit line (bit) when the fourth operation mode is selected by the selection circuit 103 . fig. 5b shows the fourth operation mode. the selection signal line (mem) is set at a low level so that the selection circuit 103 selects the fourth operation mode. when the selection signal line (mem) is at the low level, the gate electrode of the transistor 204 is electrically connected to the word line (word) through the first switch 202 . in addition, the bit line (bit) is electrically connected to the second electrode of the transistor 204 through the switch 203 . in the fourth operation mode, a middle-level potential is input to the bit line (bit). then, the word line (word) is set at a high level to turn on the transistor 204 , so that the potential stored in the node between the transistor 204 and the capacitor 205 is input to the bit line (bit). at this time, the potential of the bit line (bit) rises from the middle level to a high level in the case where the potentials stored in the transistor 204 and the capacitor 205 are at high levels. in the case where the potentials stored in the transistor 204 and the capacitor 205 are at low levels, the potential of the bit line (bit) does not rise. thus, the potential stored in the nonvolatile memory circuit 105 can be read by identifying the level of the potential of the bit line (bit). for example, a level shifter is connected to a tip of the bit line (bit), in which case the potential of the bit line (bit) that is close to the high-level potential can be fixed to the high level, so that the potential can be read completely. given combination of the four operation modes makes it possible to stop supply of power when the internal state of the flip-flop circuit is not changed, which results in a reduction in the power consumption. further, the potential of the nonvolatile memory circuit is directly read out from an external portion of the register circuit, whereby the internal state of the flip-flop circuit can be assessed at a desired timing. furthermore, the internal state of the flip-flop circuit can be easily rewritten. application example next, a semiconductor device including a plurality of register circuits that is described above and the operations thereof will be described. fig. 6 shows a semiconductor device of one embodiment of the present invention, which includes a plurality of register circuits that is described above and provided in a matrix. the semiconductor device in fig. 6 includes the register circuits arranged in a matrix of m (rows) and n (columns), n bit lines, m word lines, a memory controller, a bit column decoder, a word row decoder, and a core (core io). the register circuits in fig. 6 each have a configuration similar to that of the register circuit 100 shown in fig. 1b . that is, each of the register circuits includes a flip-flop circuit, a selection circuit, and a nonvolatile memory circuit. in addition, each of the selection circuits includes a first switch and a second switch, and each of the nonvolatile memory circuits includes a transistor with small off-state current (e.g., a transistor including an oxide semiconductor) and a capacitor. the register circuits in one column share one bit line electrically connected to each of the selection circuits and the register circuits in one row share one word line. in this embodiment, the nonvolatile memory circuits included in the plurality of register circuits are not connected to each other in series and each of the nonvolatile memory circuits is connected to the bit line and the word line; however, a method for arranging the register circuits in a matrix is not limited to this. note that a write enable line (we), a selection signal line (mem), a data line (data), a clock signal line (clk), and the like can have configurations similar to those in fig. 1b , and thus are not shown in fig. 6 . the n bit lines are electrically connected to the bit column decoder, and the bit line in a k-th column (k is an integer greater than or equal to 1 and less than or equal to n) is electrically connected to the selection circuit and the second switch which are included in the register circuit in the k-th column. the m word lines are electrically connected to the word row decoder, and the word line in a q-th row (q is an integer greater than or equal to 1 and less than or equal to m) is electrically connected to the selection circuit and the first switch which are included in the register circuit in the q-th row. the memory controller determines the register circuit to/from which data is written or read depending on the internal state of the core or an arithmetic result. for example, when the memory controller determines the register circuit to which data is written, the selection circuit selects the third operation mode and a predetermined potential is input to the bit column decoder and the word row decoder from the memory controller. for example, an address data of the register circuit to/from which data is written or read is transmitted to the word row decoder. then, the word row decoder inputs a predetermined potential to the word lines in response to the address data, so that the register circuit which writes and reads data is in an active state. data to be written to the register circuit is transmitted to the bit column decoder. then, a potential corresponding to the data to be written is input from the bit column decoder to the bit lines. the potential supplied from the bit column decoder is stored in the register circuit which is made to be in the active state by the word row decoder. an input terminal and an output terminal of the flip-flop circuit included in the register circuit are connected to a logic operation circuit, a main memory, or the like, and the flip-flop circuits arranged in a matrix form a signal processing circuit. in the signal processing circuit, the flip-flop circuit has a function of carrying out arithmetic processing or temporarily holding a program execution state. in the semiconductor device of the present invention, since the nonvolatile memory circuit is provided for each flip-flop circuit, data can be read out at high speed even a plurality of register circuits is provided. further, data can be directly written to or read from the nonvolatile memory circuit, so that the internal state of the signal processing circuit can be easily assessed and rewritten. this embodiment can be combined with any of the other embodiments as appropriate. embodiment 2 a transistor with small off-state current included in the nonvolatile memory circuit described in embodiment 1 will be described. as the transistor with small off-state current, a transistor including an oxide semiconductor material is given. structures of transistors in this embodiment will be described with reference to figs. 23a to 23d . note that figs. 23a to 23d are schematic cross-sectional views each showing an example of the structure of the transistor. a transistor shown in fig. 23a is provided over an insulating layer 600 ( a ) and embedded insulators 612 a (a) and 612 b (a) which are formed to be embedded in the insulating layer 600 ( a ). the transistor shown in fig. 23a includes a gate electrode 601 ( a ), a gate insulating layer 602 ( a ), an oxide semiconductor layer 603 ( a ), a source electrode 605 a (a), and a drain electrode 605 b (a). the oxide semiconductor layer 603 ( a ) includes an impurity region 604 a (a) and an impurity region 604 b (a). the impurity region 604 a (a) and the impurity region 604 b (a) are apart from each other and dopants (impurities) are imparted thereto. a region between the impurity region 604 a (a) and the impurity region 604 b (a) serves as a channel formation region. the oxide semiconductor layer 603 ( a ) is provided over the insulating layer 600 ( a ). the impurity region 604 a (a) and the impurity region 604 b (a) are not necessarily provided. note that in the transistor shown in fig. 23a , the impurity region 604 a (a) and the impurity region 604 b (a) are semiconductor regions having n + -type conductivity. a sidewall insulator 616 a (a) and a sidewall insulator 616 b (a) are provided on both side surfaces of the gate electrode 601 ( a ), and an insulating layer 606 ( a ) is provided in an upper portion of the gate electrode 601 ( a ) to prevent short circuit of the gate electrode 601 ( a ) and another wiring. the source electrode 605 a (a) and the drain electrode 605 b (a) are provided over the oxide semiconductor layer 603 ( a ) and electrically connected to the oxide semiconductor layer 603 ( a ). the source electrode 605 a (a) overlaps with part of the impurity region 604 a (a). when the source electrode 605 a (a) overlaps with part of the impurity region 604 a (a), resistance between the source electrode 605 a (a) and the impurity region 604 a (a) can be low. the drain electrode 605 b (a) overlaps with part of the impurity region 604 b (a). when the drain electrode 605 b (a) overlaps with part of the impurity region 604 b (a), resistance between the drain electrode 605 b (a) and the impurity region 604 b (a) can be low. the gate insulating layer 602 ( a ) is provided over the oxide semiconductor layer 603 ( a ). the gate electrode 601 ( a ) overlaps with the oxide semiconductor layer 603 ( a ) with the gate insulating layer 602 ( a ) provided therebetween. a region in the oxide semiconductor layer 603 ( a ), which overlaps with the gate electrode 601 ( a ) with the gate insulating layer 602 ( a ) provided therebetween serves as the channel formation region. a transistor shown in fig. 23b is formed over an insulating layer 600 ( b ) and embedded insulators 612 a (b) and 612 b (b) which are formed to be embedded in the insulating layer 600 ( b ). the transistor shown in fig. 23b includes a gate electrode 601 ( b ), a gate insulating layer 602 ( b ), an oxide semiconductor layer 603 ( b ), a source electrode 605 a (b), and a drain electrode 605 b (b). the oxide semiconductor layer 603 ( b ) includes an impurity region 604 a (b) and an impurity region 604 b (b). the impurity region 604 a (b) and the impurity region 604 b (b) are apart from each other and dopants (impurities) are imparted thereto. a region between the impurity region 604 a (b) and the impurity region 604 b (b) serves as a channel formation region. the oxide semiconductor layer 603 ( b ) is provided over the insulating layer 600 ( b ). note that the impurity region 604 a (b) and the impurity region 604 b (b) are not necessarily provided. note that in the transistor shown in fig. 23b , the impurity region 604 a (b) and the impurity region 604 b (b) are semiconductor regions each having n + -type conductivity. a sidewall insulator 616 a (b) and a sidewall insulator 616 b (b) are provided on both side surfaces of the gate electrode 601 ( b ), and an insulating layer 606 ( b ) is provided in an upper portion of the gate electrode 601 ( b ) to prevent short circuit of the gate electrode 601 ( b ) and another wiring. the source electrode 605 a (b) and the drain electrode 605 b (b) are provided over the oxide semiconductor layer 603 ( b ) and electrically connected to the oxide semiconductor layer 603 ( b ). the source electrode 605 a (b) overlaps with the impurity region 604 a (b). when the source electrode 605 a (b) overlaps with the impurity region 604 a (b), resistance between the source electrode 605 a (b) and the impurity region 604 a (b) can be low. the drain electrode 605 b (b) overlaps with the impurity region 604 b (b). when the drain electrode 605 b (b) overlaps with part of the impurity region 604 b (b), resistance between the drain electrode 605 b (b) and the impurity region 604 b (b) can be low. the gate insulating layer 602 ( b ) is provided over the oxide semiconductor layer 603 ( b ). the gate electrode 601 ( b ) overlaps with the oxide semiconductor layer 603 ( b ) with the gate insulating layer 602 ( b ) provided therebetween. a region in the oxide semiconductor layer 603 ( b ), which overlaps with the gate electrode 601 ( b ) with the gate insulating layer 602 ( b ) provided therebetween serves as the channel formation region. in the transistor shown in fig. 23a , the impurity region 604 a (a) and the impurity region 604 b (a) are provided to overlap with the sidewall insulator 616 a (a) and the sidewall insulator 616 b (a), respectively. on the other hand, in the transistor shown in fig. 23b , the impurity region 604 a (b) and the impurity region 604 b (b) are provided not to overlap with the sidewall insulator 616 a (b) and the sidewall insulator 616 b (b), respectively. the transistor shown in fig. 23c includes a gate electrode 601 ( c ), a gate insulating layer 602 ( c ), an oxide semiconductor layer 603 ( c ), a source electrode 605 a (c), and a drain electrode 605 b (c). the oxide semiconductor layer 603 ( c ) includes an impurity region 604 a (c) and an impurity region 604 b (c). the impurity region 604 a (c) and the impurity region 604 b (c) are apart from each other and dopants (impurities) are imparted thereto. a region between the impurity region 604 a (c) and the impurity region 604 b (c) serves as a channel formation region. the oxide semiconductor layer 603 ( c ) is provided over the insulating layer 600 ( c ). note that the impurity region 604 a (c) and the impurity region 604 b (c) are not necessarily provided. the source electrode 605 a (c) and the drain electrode 605 b (c) are provided over the oxide semiconductor layer 603 ( c ) and electrically connected to the oxide semiconductor layer 603 ( c ). side surfaces of the source electrode 605 a (c) and the drain electrode 605 b (c) are tapered. the source electrode 605 a (c) overlaps with part of the impurity region 604 a (c); however, this embodiment is not limited thereto. when the source electrode 605 a (c) overlaps with part of the impurity region 604 a (c), resistance between the source electrode 605 a (c) and the impurity region 604 a (c) can be low. an entire region of the oxide semiconductor layer 603 ( c ) which overlaps with the source electrode 605 a (c) may be the impurity region 604 a (c). the drain electrode 605 b (c) overlaps with part of the impurity region 604 b (c); however, this embodiment is not limited thereto. when the drain electrode 605 b (c) overlaps with part of the impurity region 604 b (c), resistance between the drain electrode 605 b (c) and the impurity region 604 b (c) can be low. an entire region of the oxide semiconductor layer 603 ( c ) which overlaps with the drain electrode 605 b (c) may be the impurity region 604 b (c). the gate insulating layer 602 ( c ) is provided over the oxide semiconductor layer 603 ( c ), the source electrode 605 a (c), and the drain electrode 605 b (c). the gate electrode 601 ( c ) overlaps with the oxide semiconductor layer 603 ( c ) with the gate insulating layer 602 ( c ) provided therebetween. a region in the oxide semiconductor layer 603 ( c ), which overlaps with the gate electrode 601 ( c ) with the gate insulating layer 602 ( c ) provided therebetween serves as the channel formation region. a transistor shown in fig. 23d includes a gate electrode 601 ( d ), a gate insulating layer 602 ( d ), an oxide semiconductor layer 603 ( d ), a source electrode 605 a (d), and a drain electrode 605 b (d). the source electrode 605 a (d) and the drain electrode 605 b (d) are provided over an insulating layer 600 ( d ). the side surfaces of the source electrode 605 a (d) and the drain electrode 605 b (d) are tapered. the oxide semiconductor layer 603 ( d ) includes an impurity region 604 a (d) and an impurity region 604 b (d). the impurity region 604 a (d) and the impurity region 604 b (d) are apart from each other and dopants are imparted thereto. a region between the impurity region 604 a (d) and the impurity region 604 b (d) serves as a channel formation region. for example, the oxide semiconductor layer 603 ( d ) is provided over the source electrode 605 a (d), the drain electrode 605 b (d), and the insulating layer 600 ( d ), and is electrically connected to the source electrode 605 a (d) and the drain electrode 605 b (d). note that the impurity region 604 a (d) and the impurity region 604 b (d) are not necessarily provided. the impurity region 604 a (d) is electrically connected to the source electrode 605 a (d). the impurity region 604 b (d) is electrically connected to the drain electrode 605 b (d). the gate insulating layer 602 ( d ) is provided over the oxide semiconductor layer 603 ( d ). the gate electrode 601 ( d ) overlaps with the oxide semiconductor layer 603 ( d ) with the gate insulating layer 602 ( d ) provided therebetween. a region in the oxide semiconductor layer 603 ( d ), which overlaps with the gate electrode 601 ( d ) with the gate insulating layer 602 ( d ) provided therebetween serves as the channel formation region. further, components shown in figs. 23a to 23d will be described. as each of the insulating layers 600 ( a ) to 600 ( d ), an insulating oxide, a substrate having an insulating surface, or the like can be used, for example. further, a layer over which an element is formed in advance can be used as each of the insulating layers 600 ( a ) to 600 ( d ). each of the gate electrodes 601 ( a ) to 601 ( d ) has a function of a gate of the transistor. note that a layer having a function of a gate of the transistor can be called a gate wiring. as the gate electrodes 601 ( a ) to 601 ( d ), a layer of a metal such as molybdenum, magnesium, titanium, chromium, tantalum, tungsten, aluminum, copper, neodymium, or scandium or an alloy containing any of these metals as a main component can be used, for example. alternatively, the gate electrodes 601 ( a ) to 601 ( d ) can be formed by stacking layers of any of materials that can be used for the gate electrodes 601 ( a ) to 601 ( d ). each of the gate insulating layers 602 ( a ) to 602 ( d ) can be, for example, a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a silicon nitride oxide layer, an aluminum oxide layer, an aluminum nitride layer, an aluminum oxynitride layer, an aluminum nitride oxide layer, a hafnium oxide layer, or a lanthanum oxide layer. each of the gate insulating layers 602 ( a ) to 602 ( d ) can be formed by stacking layers of any of materials that can be used for the gate insulating layers 602 ( a ) to 602 ( d ). alternatively, the gate insulating layers 602 ( a ) to 602 ( d ), an insulating layer of a material containing, for example, an element that belongs to group 13 in the periodic table and oxygen can be used. when the oxide semiconductor layers 603 ( a ) to 603 ( d ) contain an element that belongs to group 13, the use of insulating layers each containing an element that belongs to group 13 as insulating layers in contact with the oxide semiconductor layers 603 ( a ) to 603 ( d ) makes the state of interfaces between the insulating layers and the oxide semiconductor layers favorable. examples of the material containing an element that belongs to group 13 include gallium oxide, aluminum oxide, aluminum gallium oxide, and gallium aluminum oxide. note that aluminum gallium oxide refers to a substance in which the amount of aluminum is larger than that of gallium in atomic percent, and gallium aluminum oxide refers to a substance in which the amount of gallium is larger than or equal to that of aluminum in atomic percent. as the gate insulating layers 602 ( a ) to 602 ( d ), a material represented by al 2 o x (x=3+α, where α is larger than or equal to 0 and smaller than 1), ga 2 o x (x=3+α, where α is larger than 0 and smaller than 1), or ga x al 2-x o 3+α , (x is larger than 0 and smaller than 2 and α is larger than 0 and smaller than 1) can be used, for example. each of the gate insulating layers 602 ( a ) to 602 ( d ) can be formed by stacking layers of any of materials which can be used for the gate insulating layers 602 ( a ) to 602 ( d ). for example, the gate insulating layers 602 ( a ) to 602 ( d ) can be formed by stacking layers containing gallium oxide represented by ga 2 o x . alternatively, the gate insulating layers 602 ( a ) to 602 ( d ) may be a stack of layers of an insulating layer containing gallium oxide represented by ga 2 o x and an insulating layer containing aluminum oxide represented by al 2 o x . the gate insulating layers 602 ( a ) to 602 ( d ) each contain oxygen at least in a portion in contact with the oxide semiconductor layer and are each preferably formed using an insulating oxide from which part of oxygen is eliminated by heating. when the portion of the gate insulating layers 602 ( a ) to 602 ( d ) each of which is in contact with the oxide semiconductor layer are each formed using silicon oxide, oxygen can be diffused to the oxide semiconductor layer and a reduction in the resistance of the transistor can be prevented. note that the gate insulating layers 602 ( a ) to 602 ( d ) may be formed using a high-k material such as hafnium silicate (hfsio x ), hafnium silicate to which nitrogen is added (hfsi x o y n z ), hafnium aluminate to which nitrogen is added (hfal x o y n z ), hafnium oxide, yttrium oxide, or lanthanum oxide, whereby gate leakage current can be reduced. here, gate leakage current refers to leakage current which flows between a gate electrode and a source or drain electrode. in addition, a layer formed using the high-k material and a layer formed using silicon oxide, silicon oxynitride, silicon nitride, silicon nitride oxide, aluminum oxide, aluminum oxynitride, or gallium oxide may be stacked. note that even in the case where the gate insulating layers 602 ( a ) to 602 ( d ) each have a stacked-layer structure, the portion in contact with the oxide semiconductor layer is preferably formed using an insulating oxide. further, when the channel length of the transistor is 30 nm, the thickness of each of the oxide semiconductor layers 603 ( a ) to 603 ( d ) may be approximately 5 nm, for example. in this case, if the oxide semiconductor layers 603 ( a ) to 603 ( d ) are oxide semiconductor layers of caac-os films (described later), a short channel effect in the transistor can be suppressed. dopants (impurities) imparting n-type or p-type conductivity are added to the impurity regions 604 a (a) to 604 a (d) and the impurity regions 604 b (a) to 604 b (d), and each of the impurity regions serves as a source region or a drain region of the transistor. as the dopants, for example, one or more of elements of group 13 in the periodic table (e.g., boron), of group 15 in the periodic table (e.g., one or more of nitrogen, phosphorus, and arsenic), and of rare gas (e.g., one or more of helium, argon, and xenon) can be used. here, the dopant may be added by an ion implantation method or an ion doping method. alternatively, the dopant may be added by performing plasma treatment in an atmosphere of a gas containing the dopant. by addition of the dopants to the impurity regions 604 a (a) to 604 a (d) and the impurity regions 604 b (a) to 604 b (d), connection resistance between the impurity region and the source electrode or the drain electrode can be reduced, resulting in miniaturization of the transistor. the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) function as the source or the drain of the transistor. note that a layer functioning as a source of the transistor is also referred to as a source electrode or a source wiring, and a layer functioning as a drain of the transistor is also referred to as a drain electrode or a drain wiring. each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) can be formed using, for example, a metal such as aluminum, magnesium, chromium, copper, tantalum, titanium, molybdenum, or tungsten; or an alloy which contains any of the above metals as a main component. for example, each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) can be formed using a stacked-layer structure including a layer of an alloy containing copper, magnesium, and aluminum. alternatively, each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) can be formed by stacking layers of any of materials that can be used for the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d). for example, each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) can be formed using a stacked-layer structure including a layer of an alloy containing copper, magnesium, and aluminum and a layer containing copper. further, a layer containing a conductive metal oxide can be used for each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d). examples of the conductive metal oxide include indium oxide, tin oxide, zinc oxide, indium oxide-tin oxide, and indium oxide-zinc oxide. note that the conductive metal oxide that can be used for each of the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) may contain silicon oxide. the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to 605 b (d) may be selectively formed in such a manner that, for example, a conductive film (e.g., a metal film or a silicon film to which an impurity element imparting one conductivity type is added) is formed by a sputtering method, an etching mask is formed over the conductive film, and etching is performed. alternatively, an ink-jet method may be used. the conductive film serving as the source electrodes 605 a (a) to 605 a (d) and the drain electrodes 605 b (a) to the 605 b (d) may be formed to have a single-layer structure or a stacked-layer structure. for example, the conductive film is formed to have a three-layer structure in which an al layer is sandwiched between ti layers. each of the insulating layers 600 ( a ) to 600 ( d ) can be formed by stacking layers of any of materials that can be used for the gate insulating layers 602 ( a ) to 602 ( d ), for example. further, the insulating layers 600 ( a ) to 600 ( d ) may be formed by stacking layers of any of materials that can be used for the gate insulating layers 602 ( a ) to 602 ( d ). for example, the insulating layers 600 ( a ) to 600 ( d ) formed by stacking an aluminum oxide layer and a silicon oxide layer can prevent elimination of oxygen contained in the insulating layers 600 ( a ) to 600 ( d ) through the oxide semiconductor layers 603 ( a ) to 603 ( d ). a single layer or a stack of layers of any of materials that can be used for the gate insulating layers 602 ( a ) to 602 ( d ) can be used for the insulating layer 606 ( a ), the insulating layer 606 ( b ), the embedded insulator 612 a (a), the embedded insulator 612 b (a), the embedded insulator 612 a (b), the embedded insulator 612 b (b), the sidewall insulator 616 a (a), the sidewall insulator 616 b (a), the sidewall insulator 616 a (b), and the sidewall insulator 616 b (b). when the insulating layer which is in contact with each of the oxide semiconductor layers 603 ( a ) to 603 ( d ) contains oxygen excessively, the oxide semiconductor layers 603 ( a ) to 603 ( d ) are easily supplied with oxygen. as a result, an oxygen defect in the oxide semiconductor layers 603 ( a ) to 603 ( d ) or at an interface between each of the oxide semiconductor layers 603 ( a ) to 603 ( d ) and the insulating layer can be reduced, which results in further reduction in the carrier concentration in each of the oxide semiconductor layers 603 ( a ) to 603 ( d ). without limitation thereon, in the case where the oxide semiconductor layer 603 ( a ) contains oxygen excessively by the manufacturing steps, elimination of oxygen from the oxide semiconductor layer 603 ( a ) can be prevented by the insulating layer in contact with the oxide semiconductor layer 603 ( a ). a base insulating layer may be provided between the oxide semiconductor layers 603 ( a ) to 603 ( d ) and the insulating layers 600 ( a ) to 600 ( d ). the base insulating layer contains oxygen at least in its surface and may be formed using an insulating oxide in which part of the oxygen is eliminated by heat treatment. as an insulating oxide in which part of oxygen is eliminated by heat treatment, a material containing more oxygen than that in the stoichiometric proportion is preferably used. this is because an oxide semiconductor layer in contact with the base insulating layer can be supplied with oxygen by the heat treatment. as an insulating oxide containing more oxygen than that in the stoichiometric proportion, silicon oxide represented by sio x where x>2 can be given, for example. note that there is no limitation thereon, and the base insulating layer may be formed using silicon oxide, silicon oxynitride, silicon nitride oxide, aluminum oxynitride, gallium oxide, hafnium oxide, yttrium oxide, or the like. the base interlayer insulating layer may be a stack of a plurality of films. the base insulating layer may have a stacked-layer structure in which a silicon oxide film is formed over a silicon nitride film, for example. in an insulating oxide containing more oxygen than that in the stoichiometric proportion, part of oxygen is easily eliminated by heat treatment. the amount of eliminated oxygen (the value converted into that of oxygen atoms) obtained by tds analysis when part of oxygen is easily eliminated by heat treatment is greater than or equal to 1.0×10 18 atoms/cm 3 , preferably greater than or equal to 1.0×10 20 atoms/cm 3 , more preferably greater than or equal to 3.0×10 20 atoms/cm 3 . the base insulating layer may be formed by a sputtering method, a cvd method, or the like. the base insulating layer is preferably formed by a sputtering method. in the case where a silicon oxide film is formed as the base insulating layer, a quartz (preferably, synthesized quartz) target may be used as a target, and an argon gas may be used as a sputtering gas. alternatively, a silicon target and a gas containing oxygen may be used as a target and a sputtering gas, respectively. as the gas containing oxygen, a mixed gas of an argon gas and an oxygen gas may be used or only an oxygen gas may be used. after the base insulating layer is formed, a first heat treatment is performed before an oxide semiconductor layer serving as the oxide semiconductor layers 603 ( a ) to 603 ( d ) is formed. the first heat treatment is performed to remove water and hydrogen contained in the base insulating layer. the temperature of the first heat treatment is higher than or equal to a temperature at which water and hydrogen contained in the base insulating layer are eliminated (a temperature at which the amount of eliminated water and hydrogen has a peak) and lower than a temperature at which the substrate is changed in quality, preferably higher than or equal to 400° c. and lower than or equal to 750° c. for example, it is sufficient that the temperature of the first heat treatment is lower than the temperature of a second heat treatment performed later. then, the second heat treatment is performed after the oxide semiconductor layer is formed. the second heat treatment is performed to supply oxygen to the oxide semiconductor layer from the base insulating layer which serves as a source of oxygen. the timing of the second heat treatment is not limited to this timing, and the second heat treatment may be performed after the oxide semiconductor layer is processed. note that it is preferable that the second heat treatment be performed in a nitrogen gas atmosphere or a rare gas atmosphere including helium, neon, argon, or the like and the atmosphere do not contain hydrogen, water, a hydroxyl group, hydride, and the like. alternatively, the purity of a nitrogen gas or a rare gas such as helium, neon, or argon that is introduced into a heat treatment apparatus is preferably higher than or equal to 6n (99.9999%), more preferably higher than or equal to 7n (99.99999%) (that is, the impurity concentration be lower than or equal to 1 ppm, preferably lower than or equal to 0.1 ppm). in some cases, the oxide semiconductor layer may be crystallized into a microcrystalline oxide semiconductor layer or a polycrystalline oxide semiconductor layer, depending on the conditions of the second heat treatment or the material of the oxide semiconductor layer. for example, the oxide semiconductor layer may be crystallized into a microcrystalline oxide semiconductor layer having a degree of crystallization of greater than or equal to 90%, or greater than or equal to 80%. further, the oxide semiconductor layer may be an amorphous oxide semiconductor layer without containing a crystalline component, depending on the conditions of the second heat treatment or the material of the oxide semiconductor layer. furthermore, a microcrystal (the grain size of the crystal is greater than or equal to 1 nm and less than or equal to 20 nm) is contained in the amorphous layer in some cases. in the case of a crystalline oxide semiconductor layer, the average surface roughness (r a ) of a surface where the oxide semiconductor film is formed is preferably greater than or equal to 0.1 nm and less than 0.5 nm. the oxide semiconductor film may be formed over a surface with the average surface roughness (r a ) of less than or equal to 1 nm, preferably less than or equal to 0.3 nm, more preferably less than or equal to 0.1 nm. note that here, the average surface roughness (r a ) is obtained by three-dimensional expansion of arithmetic mean surface roughness (r a ) which is defined by jis b 0601:2001 (iso 4287:1997) so that r a can be applied to a curved surface, and is an average value of the absolute values of deviations from a reference surface to a specific surface. here, the arithmetic mean surface roughness (r a ) is shown by the following formula (1) assuming that a portion of a roughness curve is withdrawn in a length corresponding to an evaluation length l o , the direction of the mean line of the roughness curve of the picked portion is represented by an x-axis, the direction of longitudinal magnification (direction perpendicular to the x-axis) is represented by a y-axis, and the roughness curve is expressed as y=f(x). when a curved surface obtained by cutting off a long-wavelength component from a measured surface is expressed as z 0 =f(x,y), the average surface roughness (r a ) is an average value of the absolute values of deviations from the reference surface to the specific surface and is shown by the following formula (2). here, the specific surface is a surface which is a target of roughness measurement, and is a quadrilateral region which is surrounded by four points represented by the coordinates (x 1 ,y 1 ,f(x 1 ,y 1 )), (x 1 ,y 2 ,f(x 1 ,y 2 )), (x 2 ,y 1 ,f(x 2 ,y 1 )), and (x 2 , y 2 , f(x 2 ,y 2 )). s 0 represents the area of the specific surface when the specific surface is flat ideally. in addition, the reference surface is a surface parallel to an x-y plane at the average height of the specific surface. that is, when the average value of the height of the specific surface is expressed as z 0 , the height of the reference surface is also expressed as z 0 . chemical mechanical polishing (cmp) treatment may be performed so that the average surface roughness of a surface where the oxide semiconductor layer is formed can be greater than or equal to 0.1 nm and less than 0.5 nm. the cmp treatment may be performed before formation of the oxide semiconductor layer but is preferably performed before the first heat treatment. the cmp treatment may be performed at least once. when the cmp treatment is performed in plural times, it is preferable that the first polishing step be performed at a high polishing rate and be followed by a final polishing step at a low polishing rate. instead of the cmp treatment, dry etching or the like may be performed in order to planarize the surface where the oxide semiconductor layer is formed. as an etching gas, a chlorine-based gas such as a chlorine gas, a boron chloride gas, a silicon chloride gas, or a carbon tetrachloride gas, a fluorine-based gas such as a carbon tetrafluoride gas, a sulfur fluoride gas, or a nitrogen fluoride gas, or the like can be used as appropriate. instead of the cmp treatment, plasma treatment or the like may be performed in order to planarize the surface where the oxide semiconductor layer is formed. a rare gas may be used in the plasma treatment. in the plasma treatment, a surface to be processed is irradiated with ions of an inert gas, and minute projections and depressions on the surface to be processed are planarized by a sputtering effect. such plasma treatment is also referred to as reverse sputtering. note that any of the above treatments may be employed in order to planarize the surface where the oxide semiconductor layer is formed. for example, only reverse sputtering may be performed. alternatively, dry etching may be performed after the cmp treatment. note that it is preferable that dry etching or reverse sputtering be used so that water can be prevented from entering the surface where the oxide semiconductor layer is formed. in particular, in the case where planarization treatment is performed after the first heat treatment, dry etching or reverse sputtering is preferably used. the oxide semiconductor layer preferably contains at least indium (in) or zinc (zn). in particular, both in and zn are preferably contained. in addition, gallium (ga) is preferably contained. when gallium (ga) is contained, variations in the transistor characteristics can be reduced. such an element capable of reducing variations in the transistor characteristics is referred to as a stabilizer. as a stabilizer, tin (sn), hafnium (hf), or aluminum (al), can be given. as another stabilizer, a lanthanoid such as lanthanum (la), cerium (ce), praseodymium (pr), neodymium (nd), samarium (sm), europium (eu), gadolinium (gd), terbium (tb), dysprosium (dy), holmium (ho), erbium (er), thulium (tm), ytterbium (yb), and lutetium (lu) can be given. one or a plurality of these elements can be contained. as the oxide semiconductor, for example, any of the following can be used: indium oxide; tin oxide; zinc oxide; a two-component metal oxide such as an in—zn-based oxide, a sn—zn-based oxide, an al—zn-based oxide, a zn—mg-based oxide, a sn—mg-based oxide, an in—mg-based oxide, or an in—ga-based oxide; a three-component metal oxide such as an in—ga—zn-based oxide (also referred to as igzo), an in—al—zn-based oxide, an in—sn—zn-based oxide, a sn—ga—zn-based oxide, an al—ga—zn-based oxide, a sn—al—zn-based oxide, an in—hf—zn-based oxide, an in—la—zn-based oxide, an in—ce—zn-based oxide, an in—pr—zn-based oxide, an in—nd—zn-based oxide, an in—sm—zn-based oxide, an in—eu—zn-based oxide, an in—gd—zn-based oxide, an in—tb—zn-based oxide, an in—dy—zn-based oxide, an in—ho—zn-based oxide, an in—er—zn-based oxide, an in—tm—zn-based oxide, an in—yb—zn-based oxide, or an in—lu—zn-based oxide; or a four-component metal oxide such as an in—sn—ga—zn-based oxide, an in—hf—ga—zn-based oxide, an in—al—ga—zn-based oxide, an in—sn—al—zn-based oxide, an in—sn—hf—zn-based oxide, or an in—hf—al—zn-based oxide. note that here, for example, an “in—ga—zn-based oxide” means an oxide containing in, ga, and zn as its main component and there is no particular limitation on the ratio of in:ga:zn. the in—ga—zn-based oxide may contain a metal element other than the in, ga, and zn. for example, an in—ga—zn-based oxide with an atomic ratio of in:ga:zn=1:1:1 (=1/3:1/3:1/3) or in:ga:zn=2:2:1 (=2/5:2/5:1/5), or any of oxides whose composition is in the neighborhood of the above compositions can be used. alternatively, an in—sn—zn-based oxide with an atomic ratio of in:sn:zn=1:1:1 (=1/3:1/3:1/3), in:sn:zn=2:1:3 (=1/3:1/6:1/2), or in:sn:zn=2:1:5 (=1/4:1/8:5/8), or any of oxides whose composition is in the neighborhood of the above compositions may be used. however, the oxide semiconductor layer which can be used in one embodiment of the present invention is not limited to those described above, and an oxide semiconductor film including an appropriate composition may be used in accordance with needed semiconductor characteristics (the mobility, the threshold voltage, the variation, and the like). in accordance with needed transistor characteristics (semiconductor characteristics), the carrier density, the impurity concentration, the defect density, the atomic ratio of a metal element and oxygen, the interatomic distance, the density, and the like may be appropriately adjusted. for example, relatively high mobility can be obtained with the use of an in—sn—zn-based oxide. however, mobility can be increased by reducing the defect density in a bulk also in the case of using an in—ga—zn-based oxide. note that for example, the expression “the composition of an oxide including in, ga, and zn at the atomic ratio, in:ga:zn=a:b:c (a+b+c=1), is in the neighborhood of the composition of an oxide containing in, ga, and zn at the atomic ratio, in:ga:zn=a:b:c (a+b+c=1)” means that a, b, and c satisfy the following relation: (a−a) 2 +(b−b) 2 +(c−c) 2 ≦r 2 , and r may be 0.05, for example. the oxide semiconductor may be either single crystal or non-single-crystal. in the case where the oxide semiconductor is non-single-crystal, the oxide semiconductor may be either amorphous or polycrystalline. further, the oxide semiconductor may have a structure including a crystal part in an amorphous part. alternatively, the oxide semiconductor may be non-amorphous. note that the metal oxide preferably contains oxygen in excess of the stoichiometric proportion. when excess oxygen is contained, generation of carriers due to oxygen deficiency in the oxide semiconductor layer to be formed can be prevented. note that for example, in the case where the oxide semiconductor layer is formed using an in—zn-based metal oxide, the atomic ratio of in/zn is 1 to 100, preferably 1 to 20, more preferably 1 to 10 in an atomic ratio. when the atomic ratio of in to zn is in the above preferred range, the field-effect mobility can be improved. here, when the atomic ratio of the metal oxide is in:zn:o=x:y:z, it is preferable to satisfy the relation of z>1.5x+y so that excess oxygen is contained. the packing ratio of a sitering body used for the target of the target is greater than or equal to 90% and less than or equal to 100%, preferably greater than or equal to 95% and less than or equal to 100%. with the target having a high filling factor, a dense oxide semiconductor layer can be formed. note that the energy gap of a metal oxide which can be applied to the oxide semiconductor layer is preferably 2 ev or more, more preferably 2.5 ev or more, still more preferably 3 ev or more. in this manner, the off-state current of a transistor can be reduced by using a metal oxide having a wide band gap. note that the oxide semiconductor layer contains hydrogen. note that the hydrogen may be contained in the oxide semiconductor layer in the form of a hydrogen molecule, water, a hydroxyl group, or hydride in some cases, in addition to a hydrogen atom. it is preferable that hydrogen contained in the oxide semiconductor film be as little as possible. note that the concentrations of an alkali metal and an alkaline earth metal in the oxide semiconductor layer are preferably low, and these concentrations are preferably lower than or equal to 1×10 18 atoms/cm 3 , more preferably lower than or equal to 2×10 16 atoms/cm 3 . when an alkali metal and an alkaline earth metal are bonded to an oxide semiconductor, carriers may be generated, which causes increase in the off-state current of the transistor. note that there is no particular limitation on the formation method and the thickness of the oxide semiconductor layer, and they can be determined in consideration of the size or the like of a transistor to be manufactured. examples of the formation method of the oxide semiconductor layer include a sputtering method, a molecular beam epitaxy method, a coating method, a printing method, a pulsed laser deposition method, and the like. the thickness of the oxide semiconductor layer is preferably 3 nm or more and 50 nm or less. this is because the transistor might be normally on when the oxide semiconductor layer has a large thickness of 50 nm or more. in a transistor having a channel length of 30 nm, when the oxide semiconductor film has a thickness of 5 nm or less, a short-channel effect can be suppressed. here, as a preferable example, a method for forming the oxide semiconductor layer by a sputtering method using an in—ga—zn-based metal oxide target will be described. a rare gas (e.g., an argon gas), an oxygen gas, or a mixed gas of a rare gas and an oxygen gas may be used as a sputtering gas. it is preferable that a high-purity gas from which hydrogen, water, a hydroxyl group, or hydride is removed be used as the sputtering gas for the formation of the oxide semiconductor layer. in order to keep the high purity of a sputtering gas, it is preferable that a gas adsorbed on the inner wall or the like of a process chamber be removed, and a surface where the oxide semiconductor layer is formed be subjected to heat treatment before the formation. in addition, a high-purity sputtering gas may be introduced to the treatment chamber. in that case, the purity of an argon gas may be 9n (99.9999999%) or higher, the dew point thereof may be −121° c. or less, the concentration of water may be 0.1 ppb or less, and the concentration of hydrogen may be 0.5 ppb or less. the purity of an oxygen gas may be 8n (99.999999%) or higher, the dew point thereof may be −112° c. or less, the concentration of water may be 1 ppb or less, and the concentration of hydrogen may be 1 ppb or less. the oxide semiconductor layer is formed while the surface where the oxide semiconductor layer is formed is heated and temperature is kept high, whereby the concentration of impurities such as water contained in the oxide semiconductor layer can be reduced. in addition, with the use of a sputtering method, damage to the oxide semiconductor layer can be reduced. further, oxygen may be supplied by ion implantation in order to contain oxygen excessively in the oxide semiconductor layer. here, description will be given of a c-axis aligned crystalline oxide semiconductor (caac-os) film that is one mode of a structure of an oxide semiconductor. the caac-os film is not completely single crystal nor completely amorphous. the caac-os film is an oxide semiconductor film with a crystal-amorphous mixed phase structure where crystal parts and amorphous parts are included. note that in most cases, the crystal part fits inside a cube whose one side is less than 100 nm. from an observation image obtained with a transmission electron microscope (tem), a boundary between an amorphous part and a crystal part in the caac-os film is not clear. further, with the tem, a grain boundary in the caac-os film is not found. thus, in the caac-os film, a reduction in electron mobility due to the grain boundary is suppressed. in each of the crystal parts included in the caac-os film, a c-axis is aligned in a direction parallel to a normal vector of a surface where the caac-os film is formed or a normal vector of a surface of the caac-os film, triangular or hexagonal atomic arrangement which is seen from the direction perpendicular to the a-b plane is formed, and metal atoms are arranged in a layered manner or metal atoms and oxygen atoms are arranged in a layered manner when seen from the direction perpendicular to the c-axis. note that, among crystal parts, the directions of the a-axis and the b-axis of one crystal part may be different from those of another crystal part. in this specification, a simple term “perpendicular” includes a range from 85° to 95°. in addition, a simple term “parallel” includes a range from −5° to 5°. in the caac-os film, distribution of crystal parts is not necessarily uniform. for example, in the formation process of the caac-os film, in the case where crystal growth occurs from a surface side of the oxide semiconductor film, the ratio of crystal parts in the vicinity of the surface of the oxide semiconductor film is higher than that in the vicinity of the surface where the oxide semiconductor film is formed in some cases. further, when an impurity or the like is added to the caac-os film, the crystal part in a region to which the impurity is added becomes amorphous in some cases. since the c-axes of the crystal parts included in the caac-os film are aligned in the direction parallel to a normal vector of a surface where the caac-os film is formed or a normal vector of a surface of the caac-os film, the directions of the c-axes may be different from each other depending on the shape of the caac-os film (the cross-sectional shape of the surface where the caac-os film is formed or the cross-sectional shape of the surface of the caac-os film). note that when the caac-os film is formed, the direction of c-axis of the crystal part is the direction parallel to a normal vector of the surface where the caac-os film is formed or a normal vector of the surface of the caac-os film. the crystal part is formed by film formation or by performing treatment for crystallization such as heat treatment after film formation. with the use of the caac-os film, drifting in the electric characteristics of a transistor due to irradiation with visible light or ultraviolet light can be reduced. thus, a highly reliable transistor can be fabricated. an example of a crystalline structure included in the caac-os film will be described in detail with reference to figs. 7a to 7e , figs. 8a to 8c , figs. 9a to 9c , and figs. 10a and 10b . in figs. 7a to 7e , figs. 8a to 8c , figs. 9a to 9c , and figs. 10a and 10b , the vertical direction corresponds to the c-axis direction and a plane perpendicular to the c-axis direction corresponds to the a-b plane, unless otherwise specified. when the expressions “an upper half” and “a lower half” are simply used, they refer to an upper half above the a-b plane and a lower half below the a-b plane (an upper half and a lower half with respect to the a-b plane). furthermore, in figs. 7a to 7e , o surrounded by a circle represents a tetracoordinate o atom and a double circle represents a tricoordinate o atom. fig. 7a shows a structure including one hexacoordinate in atom and six tetracoordinate oxygen (hereinafter referred to as tetracoordinate o) atoms proximate to the in atom. here, a structure including one metal atom and oxygen atoms proximate thereto is referred to as a small group. the structure in fig. 7a is actually an octahedral structure, but is shown as a planar structure for simplicity. note that three tetracoordinate o atoms exist in each of an upper half and a lower half in fig. 7a . in the small group shown in fig. 7a , total electric charge is 0. fig. 7b shows a structure including one pentacoordinate ga atom, three tricoordinate oxygen (hereinafter referred to as tricoordinate o) atoms proximate to the ga atom, and two tetracoordinate o atoms proximate to the ga atom. all the tricoordinate o atoms exist on the a-b plane. one tetracoordinate o atom exists in each of an upper half and a lower half in fig. 7b . an in atom can also have the structure shown in fig. 7b because an in atom can have five ligands. in the small group shown in fig. 7b , total electric charge is 0. fig. 7c shows a structure including one tetracoordinate zn atom and four tetracoordinate o atoms proximate to the zn atom. in fig. 7c , one tetracoordinate o atom exists in an upper half and three tetracoordinate o atoms exist in a lower half. alternatively, three tetracoordinate o atoms may exist in the upper half and one tetracoordinate o atom may exist in the lower half in fig. 7c . in the small group shown in fig. 7c , total electric charge is 0. fig. 7d shows a structure including one hexacoordinate sn atom and six tetracoordinate o atoms proximate to the sn atom. in fig. 7d , three tetracoordinate o atoms exist in each of an upper half and a lower half in the small group shown in fig. 7d , total electric charge is +1. fig. 7e shows a small group including two zn atoms. in fig. 7e , one tetracoordinate o atom exists in each of an upper half and a lower half. in the small group shown in fig. 7e , total electric charge is −1. here, a plurality of small groups form a medium group, and a plurality of medium groups form a large group. now, a rule of bonding between the small groups will be described. the three o atoms in the upper half with respect to the hexacoordinate in atom in fig. 7a each have three proximate in atoms in the downward direction, and the three o atoms in the lower half each have three proximate in atoms in the upward direction. the one o atom in the upper half with respect to the pentacoordinate ga atom in fig. 7b has one proximate ga atom in the downward direction, and the one o atom in the lower half has one proximate ga atom in the upward direction. the one o atom in the upper half with respect to the tetracoordinate zn atom in fig. 7c has one proximate zn atom in the downward direction, and the three o atoms in the lower half each have three proximate zn atoms in the upward direction. similarly, the number of the tetracoordinate o atoms below the metal atom is equal to the number of the metal atoms proximate to and above each of the tetracoordinate o atoms. since the coordination number of the tetracoordinate o atom is four, the sum of the number of the metal atoms proximate to and below the o atom and the number of the metal atoms proximate to and above the o atom is four. therefore, when the sum of the number of tetracoordinate o atoms above a metal atom and the number of tetracoordinate o atoms below another metal atom is four, the two kinds of small groups including the metal atoms can be bonded. for example, in the case where the hexacoordinate metal (in or sn) atom is bonded through three tetracoordinate o atoms in the upper half, it is bonded to the pentacoordinate metal (ga or in) atom or the tetracoordinate metal (zn) atom. a metal atom having the above coordination number is bonded to another metal atom having the above coordination number through a tetracoordinate o atom in the c-axis direction. in addition to the above, a medium group can be formed in a different manner by combining a plurality of small groups so that the total electric charge of the layered structure is 0. fig. 8a shows a model of a medium group included in a layered structure of an in—sn—zn—o system oxide. fig. 8b shows a large group including three medium groups. note that fig. 8c shows an atomic arrangement in the case where the layered structure in fig. 8b is observed from the c-axis direction. in fig. 8a , for simplicity, a tricoordinate o atom is omitted and tetracoordinate o atoms are shown by a circle; the number in the circle shows the number of tetracoordinate o atoms. for example, three tetracoordinate o atoms existing in each of an upper half and a lower half with respect to a sn atom are denoted by circled 3. similarly, in fig. 8a , one tetracoordinate o atom existing in each of an upper half and a lower half with respect to an in atom is denoted by circled 1. fig. 8a also shows a zn atom proximate to three tetracoordinate o atoms in an upper half and one tetracoordinate o atom in a lower half, and a zn atom proximate to one tetracoordinate o atom in an upper half and three tetracoordinate o atoms in a lower half. in the medium group included in the layered structure of an in—sn—zn—o system oxide in fig. 8a , in the order starting from the top, a sn atom proximate to three tetracoordinate o atoms in each of an upper half and a lower half is bonded to an in atom proximate to one tetracoordinate o atom in each of an upper half and a lower half, the in atom is bonded to a zn atom proximate to three tetracoordinate o atoms in an upper half, the zn atom is bonded to an in atom proximate to three tetracoordinate o atoms in each of an upper half and a lower half through one tetracoordinate o atom in a lower half with respect to the zn atom, the in atom is bonded to a small group that includes two zn atoms and is proximate to one tetracoordinate o atom in an upper half, and the small group is bonded to a sn atom proximate to three tetracoordinate o atoms in each of an upper half and a lower half through one tetracoordinate o atom in a lower half with respect to the small group. a plurality of such medium groups are bonded, so that a large group is formed. here, electric charge for one bond of a tricoordinate o atom and electric charge for one bond of a tetracoordinate o atom can be assumed to be −0.667 and −0.5, respectively. for example, electric charge of a (hexacoordinate or pentacoordinate) in atom, electric charge of a (tetracoordinate) zn atom, and electric charge of a (pentacoordinate or hexacoordinate) sn atom are +3, +2, and +4, respectively. accordingly, total electric charge in a small group including a sn atom is +1. therefore, electric charge of −1, which cancels +1, is needed to form a layered structure including a sn atom. as a structure having electric charge of −1, the small group including two zn atoms as shown in fig. 7e can be given. for example, with one small group including two zn atoms, electric charge of one small group including a sn atom can be cancelled, so that the total electric charge of the layered structure can be 0. when the large group shown in fig. 8b is repeated, a crystal of an in—sn—zn—o system oxide (in 2 snzn 3 o 8 ) can be obtained. note that the layered structure of an in—sn—zn—o system oxide which is obtained can be expressed as a composition formula, in 2 snzn 2 o 7 (zno) m (m is 0 or a natural number). the above-described rule also applies to the following oxides: a four-component metal oxide such as an in—sn—ga—zn—o system oxide; a three-component metal oxide such as an in—ga—zn—o system oxide (also referred to as igzo), an in—al—zn—o system oxide, a sn—ga—zn—o system oxide, an al—ga—zn—o system oxide, a sn—al—zn—o system oxide, an in—hf—zn—o system oxide, an in—la—zn—o system oxide, an in—ce—zn—o system oxide, an in—pr—zn—o system oxide, an in—nd—zn—o system oxide, an in—sm—zn—o system oxide, an in—eu—zn—o system oxide, an in—gd—zn—o system oxide, an in—tb—zn—o system oxide, an in—dy—zn—o system oxide, an in—ho—zn—o system oxide, an in—er—zn—o system oxide, an in—tm—zn—o system oxide, an in—yb—zn—o system oxide, or an in—lu—zn—o system oxide; a two-component metal oxide such as an in—zn—o system oxide, a sn—zn—o system oxide, an al—zn—o system oxide, a zn—mg—o system oxide, a sn—mg—o system oxide, an in—mg—o system oxide, or an in—ga—o system oxide; and the like. as an example, fig. 9a shows a model of a medium group included in a layered structure of an in—ga—zn—o system oxide. in the medium group included in the layered structure of an in—ga—zn—o system oxide in fig. 9a , in the order starting from the top, an in atom proximate to three tetracoordinate o atoms in each of an upper half and a lower half is bonded to a zn atom proximate to one tetracoordinate o atom in an upper half, the zn atom is bonded to a ga atom proximate to one tetracoordinate o atom in each of an upper half and a lower half through three tetracoordinate o atoms in a lower half with respect to the zn atom, and the ga atom is bonded to an in atom proximate to three tetracoordinate o atoms in each of an upper half and a lower half through one tetracoordinate o atom in a lower half with respect to the ga atom. a plurality of such medium groups are bonded to form a large group. fig. 9b shows a large group including three medium groups. note that fig. 9c shows an atomic arrangement in the case where the layered structure in fig. 9b is observed from the c-axis direction. here, since electric charge of a (hexacoordinate or pentacoordinate) in atom, electric charge of a (tetracoordinate) zn atom, and electric charge of a (pentacoordinate) ga atom are +3, +2, +3, respectively, electric charge of a small group including any of an in atom, a zn atom, and a ga atom is 0. as a result, the total electric charge of a medium group having a combination of such small groups is always 0. in order to form the layered structure of an in—ga—zn—o system oxide, a large group can be formed using not only the medium group shown in fig. 9a but also a medium group in which the arrangement of the in atom, the ga atom, and the zn atom is different from that in fig. 9a . when the large group shown in fig. 9b is repeated, a crystal of an in—ga—zn—o system oxide can be obtained. note that the layered structure of an in—ga—zn—o system oxide which is obtained can be expressed as a composition formula, ingao 3 (zno) n (n is a natural number). in the case where n=1 (ingazno 4 ), a crystal structure shown in fig. 10a can be obtained, for example. note that in the crystal structure in fig. 10a , a ga atom and an in atom each have five ligands as described with reference to fig. 7b , a structure in which ga is replaced with in can be obtained. in the case where n=2 (ingazn 2 o 5 ), a crystal structure shown in fig. 10b can be obtained, for example. note that in the crystal structure in fig. 10b , a ga atom and an in atom each have five ligands as described with reference to fig. 7b , a structure in which ga is replaced with in can be obtained. here, a method for forming the caac-os film will be described. first, the oxide semiconductor layer is formed by a sputtering method or the like. note that by forming an oxide semiconductor layer while keeping the surface where the oxide semiconductor layer is formed at high temperature, the ratio of a crystal part to an amorphous part can be high. at this time, the temperature of the surface where the oxide semiconductor layer is formed may be, for example, higher than or equal to 150° c. and lower than or equal to 450° c., preferably higher than or equal to 200° c. and lower than or equal to 350° c. here, the formed oxide semiconductor layer may be subjected to heat treatment. through this heat treatment, the ratio of a crystal part to an amorphous part can be high. the temperature of this heat treatment is higher than or equal to 200° c. and lower than a temperature at which the surface where the oxide semiconductor layer is formed is not changed in quality or shape, preferably higher than or equal to 250° c. and lower than or equal to 450° c. the time for the heat treatment may be longer than or equal to 3 minutes, and preferably shorter than or equal to 24 hours. this is because the time for the heat treatment decreases the productivity although the ratio of a crystal part to an amorphous part can be high. note that the heat treatment may be performed in an oxidation atmosphere or an inert atmosphere; however, there is no limitation thereon. this heat treatment may also be performed under a reduced pressure. the oxidation atmosphere is an atmosphere containing an oxidizing gas. as an example of the oxidizing gas, oxygen, ozone, and nitrous oxide can be given. it is preferable that components (e.g., water and hydrogen) which are not preferably contained in the oxide semiconductor layer be removed from the oxidation atmosphere as much as possible. for example, the purity of oxygen, ozone, or nitrous oxide is higher than or equal to 8n (99.999999%), preferably higher than or equal to 9n (99.9999999%). the oxidation atmosphere may be an inert gas such as a rare gas containing an oxidizing gas. note that the oxidation atmosphere contains an oxidizing gas at a concentration of higher than or equal to 10 ppm. an inert atmosphere contains an inert gas (a nitrogen gas, a rare gas, or the like) and contains a reactive gas such as an oxidizing gas at a concentration of less than 10 ppm. it is sufficient that a rapid thermal anneal (rta) apparatus is used for all the heat treatments. with the use of an rta apparatus, only in a short time, the heat treatments can be performed at high temperature. thus, the oxide semiconductor layer in which the ratio of a crystal part to an amorphous part is high can be formed and a decrease in productivity can be suppressed. however, the apparatus used for all the heat treatments is not limited to an rta apparatus; for example, an apparatus provided with a unit that heats an object by thermal conduction or thermal radiation from a resistance heater or the like may be used. for example, an electric furnace or an rta apparatus such as a gas rapid thermal anneal (grta) apparatus or a lamp rapid thermal anneal (lrta) apparatus can be given as the heat treatment apparatus used for all the heat treatments. an lrta apparatus is an apparatus for heating an object by radiation of light (an electromagnetic wave) emitted from a lamp such as a halogen lamp, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, a high pressure sodium lamp, or a high pressure mercury lamp. a grta apparatus is an apparatus for heating an object using a high-temperature gas as a heat medium. with the use of an in—ga—zn-based metal oxide in which the nitrogen concentration is higher than or equal to 1×10 17 atoms/cm 3 and lower than or equal to 5×10 19 atoms/cm 3 , a metal oxide film having a c-axis-aligned hexagonal crystal structure is formed and one or more layers containing ga and zn are provided between two layers of the in—o crystal planes (crystal planes containing indium and oxygen). in order to form an in—sn—zn-based metal oxide, for example, a target in which the atomic ratio of in:sn:zn is 1:2:2, 2:1:3, 1:1:1, or 20:45:35 may be used. as described above, the caac-os film can be formed. the caac-os film has high orderliness of a bond between metal and oxygen as compared to an oxide semiconductor layer having an amorphous. in other words, in the case of an oxide semiconductor layer having an amorphous structure, the number of oxygen atoms coordinated around a metal atom may vary among atoms. in contrast, in the case of the caac-os film, the number of oxygen atoms coordinated around a metal atom is substantially the same. thus, oxygen deficiency is hardly observed even at a microscopic level, and electric charge transfer and instability of electric conductivity due to hydrogen atoms (including hydrogen ions), alkali metal atoms, or the like can be suppressed. thus, when a transistor in which a channel formation region is formed using a caac-os film is formed, the amount of change in the threshold voltage of the transistor before and after light irradiation or a bias-temperature stress (bt) test performed on the transistor can be suppressed, and the transistor can have stable electric characteristics. as the gate insulating layers 602 ( a ) to 602 ( d ), a film may be formed by, for example, a sputtering method using an insulating material (e.g., silicon nitride, silicon nitride oxide, silicon oxynitride, or silicon oxide). the gate insulating layers 602 ( a ) to 602 ( d ) may be formed to have a single-layer structure of a stacked-layer structure. a stacked-layer structure of two layers in which a silicon oxynitride layer is stacked over a silicon nitride layer is employed here, for example. a transistor including an oxide semiconductor can have high field effect mobility. note that the field-effect mobility of a transistor including the actual oxide semiconductor is lower than the mobility of the bulk. reduction of the mobility is caused by defects inside a semiconductor or defects at the interface between a semiconductor and an insulating layer. with the levinson model, theoretical calculation of the field-effect mobility of the transistor on the assumption that no defects exist inside the semiconductor is possible. assuming that the original mobility and the measured field-effect mobility of a semiconductor are μ 0 and μ, respectively, and a potential barrier (such as a grain boundary) exists in the semiconductor, the measured field-effect mobility can be expressed as the following formula. here, e represents the height of the potential barrier, k represents the boltzmann constant, and t represents the absolute temperature. assuming that the potential barrier is attributed to a defect, the height of the potential barrier can be expressed as the following formula according to the levinson model. here, e represents the elementary charge, n represents the average defect density per unit area in a channel, ε represents the permittivity of the semiconductor, n represents the number of carriers per unit area in the channel, c ox represents the capacitance per unit area, v g represents the gate voltage, and t represents the thickness of the channel. in the case where the thickness of the semiconductor layer is less than or equal to 30 nm, the thickness of the channel may be regarded as being the same as the thickness of the semiconductor layer. the drain current i d in a linear region can be expressed as the following formula. here, l represents the channel length and w represents the channel width, and l and w are each 10 μm. in addition, v d represents the drain voltage. when dividing both sides of the above equation by v g and then taking logarithms of both sides, the following formula can be obtained. the right side of formula 6 is a function of v g . from formula 6, it is found that the defect density n can be obtained from the slope of a line in which ln(i d /v g ) is the ordinate and 1/v g is the abscissa. that is, the defect density can be evaluated from the i d −v g characteristics of the transistor. the defect density n of an oxide semiconductor in which the ratio of indium (in), tin (sn), and zinc (zn) is 1:1:1 is approximately 1×10 12 /cm 2 . on the basis of the defect density obtained in this manner, or the like, μ 0 can be calculated to be 120 cm 2 /vs from formula (3) and formula (4). the measured mobility of an in—sn—zn oxide with defects is approximately 40 cm 2 /vs. however, according to the calculated result, the mobility μ 0 of the oxide semiconductor with no defects inside a semiconductor and at the interface between the semiconductor and an insulating layer is 120 cm 2 /vs. note that a transport property of the transistor is affected by the scattering at the interface between a channel and a gate insulating layer even when no defect exists inside a semiconductor. in other words, the mobility μ 1 at a position that is distance x away from the interface between the channel and the gate insulating layer can be expressed as the following formula (7). here, d represents the electric field in the gate direction, and b and l are constants. b and l can be obtained from actual measurement results; according to the above measurement results, b is 4.75×10 7 cm/s and/is 10 nm (the depth to which the influence of interface scattering reaches). when d is increased (i.e., when the gate voltage is increased), the second term of formula 7 is increased and accordingly the mobility μ 1 is decreased. fig. 11 shows calculation results of the mobility of a transistor in which an ideal oxide semiconductor without a defect inside the semiconductor is used for a channel. for the calculation, device simulation software sentaurus device manufactured by synopsys, inc. was used, and the bandgap, the electron affinity, the relative permittivity, and the thickness of the oxide semiconductor were assumed to be 2.8 ev, 4.7 ev, 15, and 15 nm, respectively. in addition, the work functions of a gate, a source, and a drain were assumed to be 5.5 ev, 4.6 ev, and 4.6 ev, respectively. the thickness of a gate insulating layer was assumed to be 100 nm, and the relative permittivity thereof was assumed to be 4.1. the channel length and the channel width were each assumed to be 10 μm, and the drain voltage v d was assumed to be 0.1 v. as shown in fig. 11 , the mobility has a peak of more than 100 cm 2 /vs at a gate voltage that is a little over 1 v and is decreased as the gate voltage becomes higher because the influence of interface scattering is increased. note that in order to reduce interface scattering, as described with reference to formula 1 and the like, it is preferable that a surface of the semiconductor layer be flat at the atomic level (atomic layer flatness). calculation results of characteristics of minute transistors which are manufactured using an oxide semiconductor having such a mobility are shown in figs. 12a to 12c , figs. 13a to 13c , and figs. 14a to 14c . figs. 15a and 15b show cross-sectional structures of the transistors used for the calculation. the transistors shown in figs. 15a and 15b each include a semiconductor region 303 a and a semiconductor region 303 c which have n + -type conductivity in an oxide semiconductor layer. in the calculation, the resistivity of the semiconductor region 303 a and the semiconductor region 303 c was 2×10 −3 ωcm. a transistor shown in fig. 15a corresponds to fig. 16a described in the above embodiment, and a transistor shown in fig. 15b corresponds to fig. 16b described in the above embodiment. the transistor shown in fig. 15a is formed over a base insulating layer 301 and an embedded insulator 302 which is embedded in the base insulating layer 301 and formed of aluminum oxide. the transistor includes the semiconductor region 303 a , the semiconductor region 303 c , an intrinsic semiconductor region 303 b serving as a channel region therebetween, and a gate electrode 305 . the width of the gate electrode 305 is 33 nm a gate insulating layer 304 is formed between the gate electrode 305 and the semiconductor region 303 b . in addition, a sidewall insulator 306 a and a sidewall insulator 306 b are formed on both side surfaces of the gate electrode 305 , and an insulating layer 307 is formed over the gate electrode 305 so as to prevent a short circuit between the gate electrode 305 and another wiring. the width of the sidewall insulator is 5 nm a source electrode 308 a and a drain electrode 308 b are provided in contact with the semiconductor region 303 a and the semiconductor region 303 c , respectively. the transistor of fig. 15b is the same as the transistor of fig. 15a in that it is formed over the base insulating layer 301 and the embedded insulator 302 formed of aluminum oxide and that it includes the semiconductor region 303 a , the semiconductor region 303 c , the intrinsic semiconductor region 303 b therebetween, the gate electrode 305 having a width of 33 nm, the gate insulating layer 304 , the sidewall insulator 306 a , the sidewall insulator 306 b , the insulating layer 307 , the source electrode 308 a , and the drain electrode 308 b. the transistor shown in fig. 15a is different from the transistor shown in fig. 15b in the conductivity type of semiconductor regions which are directly below the sidewall insulator 306 a and the sidewall insulator 306 b . the semiconductor regions directly below the sidewall insulator 306 a and the sidewall insulator 306 b in the transistor shown in fig. 15a are regions having n + -type conductivity. the semiconductor regions directly below the sidewall insulator 306 a and the sidewall insulator 306 b in the transistor shown in fig. 15b are intrinsic semiconductor regions. in other words, in the semiconductor layer of fig. 15b , a region having a width of l off which overlaps with neither the semiconductor region 303 a (the semiconductor region 303 c ) nor the gate electrode 305 is provided. this region is called an offset region, and the width l off is called an offset length. the offset length is equal to the width of the sidewall insulator 306 a (the sidewall insulator 306 b ). the other parameters used in calculation are as described above. for the calculation, device simulation software sentaurus device manufactured by synopsys, inc. was used. figs. 12a to 12c show the gate voltage (v g : a potential difference between the gate and the source that is a reference potential) dependence of the drain current (i d , a solid line) and the mobility (μ, a dotted line) of the transistor having the structure shown in fig. 15a . the drain current i d is obtained by calculation under the assumption that the drain voltage v d . (a potential difference between the drain and the source that is a reference potential) is +1 v, and the mobility μ is obtained by calculation under the assumption that the drain voltage v d is +0.1 v. in fig. 12a , the thickness of the gate insulating layer is 15 nm; in fig. 12b , 10 nm; and in fig. 12c , 5 nm as the gate insulating layer is thinner, the drain current i d (off-state current) particularly in an off state is significantly decreased. in contrast, there is no noticeable change in the peak value of the mobility μ and the drain current i d (on-state current) in an on state. figs. 13a to 13c show the gate voltage v g dependence of the drain current i d (a solid line) and the mobility μ (a dotted line) of the transistor having the structure shown in fig. 15b and where the offset length l off is 5 nm. the drain current i d is obtained by calculation under the assumption that the drain voltage is +1 v and the mobility μ is obtained by calculation under the assumption that the drain voltage is +0.1 v. in fig. 13a , the thickness of the gate insulating layer is 15 nm; in fig. 13b , 10 nm; and in fig. 13c , 5 nm. figs. 14a to 14c show the gate voltage dependence of the drain current i d (a solid line) and the mobility μ(a dotted line) of the transistor having the structure shown in fig. 15b where the offset length l off is 15 nm. the drain current i d is obtained by calculation under the assumption that the drain voltage is +1 v and the mobility μ is obtained by calculation under the assumption that the drain voltage is +0.1 v. in fig. 14a , the thickness of the gate insulating layer is 15 nm; in fig. 14b , 10 nm; and in fig. 14c , 5 nm in any of the structures, as the gate insulating layer is thinner, the off-state current is significantly decreased, whereas no noticeable change arises in the peak value of the mobility μ and the on-state current. note that the peak of the mobility μ is approximately 80 cm 2 /vs in figs. 12a to 12c , approximately 60 cm 2 /vs in figs. 13a to 13c , and approximately 40 cm 2 /vs in figs. 14a to 14c ; thus, the peak of the mobility μ is decreased as the offset length l off is increased. further, the same applies to the off-state current. the on-state current is also decreased as the offset length l off is increased; however, the decrease in the on-state current is much more gradual than the decrease in the off-state current. as described above, the mobility of a transistor in which an oxide semiconductor is included in a channel can be very high. the transistor described in this embodiment as a transistor in which an oxide semiconductor is included in a channel is an example, and without limitation thereon, various modes can be employed for the transistor in which an oxide semiconductor is included in a channel. a transistor in which an oxide semiconductor including in, sn, and zn as main components is used as a channel formation region can have favorable characteristics by forming the oxide semiconductor while heating a substrate or by performing heat treatment after an oxide semiconductor film is formed. note that a main component refers to an element included in composition at 5 atomic % or more. by intentionally heating the substrate after formation of the oxide semiconductor film including in, sn, and zn as main components, the field-effect mobility of the transistor can be improved. further, the threshold voltage of the transistor can be positively shifted to make the transistor normally off. as an example, figs. 16a to 16c are graphs each showing characteristics of a transistor in which an oxide semiconductor film containing in, sn, and zn as main components and having a channel length l of 3 μm and a channel width w of 10 μm, and a gate insulating layer with a thickness of 100 nm are used. note that v d was set to 10v. fig. 16a is a graph showing characteristics of a transistor whose oxide semiconductor film containing in, sn, and zn as main components was formed by a sputtering method without heating a substrate intentionally. the field-effect mobility of the transistor was 18.8 cm 2 /vsec. on the other hand, when the oxide semiconductor film containing in, sn, and zn as main components is formed while heating the substrate intentionally, the field-effect mobility can be improved. fig. 16b shows characteristics of a transistor whose oxide semiconductor film containing in, sn, and zn as main components was formed while heating a substrate at 200° c. the field-effect mobility of the transistor was 32.2 cm 2 /vsec. the field-effect mobility can be further improved by performing heat treatment after formation of the oxide semiconductor film containing in, sn, and zn as main components. fig. 16c shows characteristics of a transistor whose oxide semiconductor film containing in, sn, and zn as main components was formed by sputtering at 200° c. and then subjected to heat treatment at 650° c. the field-effect mobility of the transistor was 34.5 cm 2 /vsec. the intentional heating of the substrate is expected to have an effect of reducing moisture taken into the oxide semiconductor film during the film formation by sputtering. further, the heat treatment after film formation enables hydrogen, a hydroxyl group, or moisture to be released and removed from the oxide semiconductor film. in this manner, the field-effect mobility can be improved. such an improvement in field-effect mobility is presumed to be achieved not only by removal of impurities by dehydration or dehydrogenation but also by a reduction in interatomic distance due to an increase in density. in addition, the oxide semiconductor can be crystallized by being highly purified by removal of impurities from the oxide semiconductor. in the case of using such a highly purified non-single-crystal oxide semiconductor, ideally, a field-effect mobility exceeding 100 cm 2 /vsec is expected to be realized. the oxide semiconductor containing in, sn, and zn as main components may be crystallized in the following manner: oxygen ions are implanted into the oxide semiconductor, hydrogen, a hydroxyl group, or moisture included in the oxide semiconductor is released by heat treatment, and the oxide semiconductor is crystallized through the heat treatment or by another heat treatment performed later. a non-single-crystal oxide semiconductor having favorable crystallinity can be obtained by such crystallization treatment or recrystallization treatment. the intentional heating of the substrate during film formation and/or the heat treatment after the film formation contributes not only to improving field-effect mobility but also to making the transistor normally off. in a transistor in which an oxide semiconductor film which contains in, sn, and zn as main components and is formed without heating a substrate intentionally is used as a channel formation region, the threshold voltage tends to be negative. however, when the oxide semiconductor film formed while heating the substrate intentionally is used, the problem of the negative threshold voltage can be solved. that is, the threshold voltage is higher than that in the case where the channel formation layer is not heated; this tendency can be confirmed by comparison between figs. 16a and 16b . note that the threshold voltage can also be controlled by changing the ratio of in, sn, and zn; when the composition ratio of in, sn, and zn is 2:1:3, a normally off transistor is expected to be formed. in addition, an oxide semiconductor film having high crystallinity can be obtained by setting the composition ratio of a target as follows: in:sn:zn=2:1:3. the temperature of the intentional heating of the substrate or the temperature of the heat treatment is 150° c. or higher, preferably 200° c. or higher, further preferably 400° c. or higher. when film formation or heat treatment is performed at a high temperature, the transistor can be normally off. by intentionally heating the substrate during film formation and/or by performing heat treatment after the film formation, the stability against a gate-bias stress can be increased. for example, when a gate bias is applied with an electric field of 2 mv/cm at 150° c. for one hour, drift of the threshold voltage can be less than ±1.5 v, preferably less than ±1.0 v. a bt test was performed on the following two transistors: sample 1 on which heat treatment was not performed after formation of an oxide semiconductor film, and sample 2 on which heat treatment at 650° c. was performed after formation of an oxide semiconductor film. first, v g −i d characteristics of the transistors were measured at a substrate temperature of 25° c. and v d of 10 v. then, the substrate temperature was set to 150° c. and v d was set to 0.1 v. after that, v g was applied so that the intensity of an electric field applied to gate insulating layer was 2 mv/cm, and the condition was kept for one hour. next, v g was set to 0 v. then, v g −i d characteristics of the transistors were measured at a substrate temperature of 25° c. and v d of 10 v. this process is called a positive bt test. in a similar manner, first, v g −i d characteristics of the transistors were measured at a substrate temperature of 25° c. and v d of 10 v. then, the substrate temperature was set to 150° c. and v d was set to 0.1 v. after that, v g of −20 v was applied so that the intensity of an electric field applied to the gate insulating layer was −2 mv/cm, and the condition was kept for one hour. next, v g was set to 0 v. then, v g i d characteristics of the transistors were measured at a substrate temperature of 25° c. and v d of 10 v. this process is called a negative bt test. figs. 17a and 17b show results of the positive bt test and the negative bt test, respectively, of sample 1. figs. 18a and 18b show results of the positive bt test and the negative bt test, respectively, of sample 2. the amount of change in threshold voltage of sample 1 due to the positive bt test and that due to the negative bt test were 1.80 v and −0.42 v, respectively. the amount of change in threshold voltage of sample 2 due to the positive bt test and that due to the negative bt test were 0.79 v and 0.76 v, respectively. it is found that, in each of sample 1 and sample 2, the amount of change in threshold voltage due to the bt tests is small and the reliability of each transistor is high. the heat treatment can be performed in an oxygen atmosphere; alternatively, the heat treatment may be performed first in an atmosphere of nitrogen or an inert gas or under reduced pressure, and then in an atmosphere including oxygen. oxygen is supplied to the oxide semiconductor after dehydration or dehydrogenation, whereby the effect of the heat treatment can be further increased. as a method for supplying oxygen after dehydration or dehydrogenation, a method in which oxygen ions are accelerated by an electric field and implanted into the oxide semiconductor film may be employed. a defect due to oxygen deficiency is easily caused in the oxide semiconductor or at an interface between the oxide semiconductor and a film in contact with the oxide semiconductor; however, when excess oxygen is included in the oxide semiconductor by the heat treatment, oxygen deficiency caused constantly can be compensated for with excess oxygen. the excess oxygen is mainly oxygen existing between lattices. when the concentration of oxygen is set in the range of 1×10 16 /cm 3 to 2×10 20 /cm 3 , excess oxygen can be included in the oxide semiconductor without causing crystal distortion or the like. when heat treatment is performed so that at least part of the oxide semiconductor includes crystal, a more stable oxide semiconductor film can be obtained. for example, when an oxide semiconductor film which is formed by sputtering using a target having a composition ratio of in:sn:zn=1:1:1 without heating a substrate intentionally is analyzed by x-ray diffraction (xrd), a halo pattern is observed. the formed oxide semiconductor film can be crystallized by being subjected to heat treatment. the temperature of the heat treatment can be set as appropriate; when the heat treatment is performed at 650° c., for example, a clear diffraction peak can be observed in x-ray diffraction. an xrd measurement of an in—sn—zn—o film was conducted. the xrd measurement was conducted using an x-ray diffractometer d8 advance manufactured by bruker axs, and measurement was performed by an out-of-plane method. sample a and sample b were prepared and the xrd analysis was performed thereon. a method for manufacturing sample a and sample b will be described below. an in—sn—zn—o film with a thickness of 100 nm was formed over a quartz substrate that had been subjected to dehydrogenation treatment. the in—sn—zn—o film was formed with a sputtering apparatus with a power of 100 w (dc) in an oxygen atmosphere. an in—sn—zn—o target having an atomic ratio of in: sn: zn=1:1:1 was used as a target. note that the substrate heating temperature in film formation was set at 200° c. a sample manufactured in this manner was used as sample a. next, a sample manufactured by a method similar to that of sample a was subjected to heat treatment at 650° c. as the heat treatment, heat treatment in a nitrogen atmosphere was first performed for one hour and heat treatment in an oxygen atmosphere was further performed for one hour without lowering the temperature. a sample manufactured in this manner was used as sample b. fig. 21 shows xrd spectra of sample a and sample b. no peak derived from crystal was observed in sample a, whereas peaks derived from crystal were observed when 2θ was around 35 deg. and at 37 deg. to 38 deg. in sample b. as described above, by intentionally heating a substrate during film formation of an oxide semiconductor containing in, sn, and zn as main components and/or by performing heat treatment after the film formation, characteristics of a transistor can be improved. these substrate heating and heat treatment have an effect of preventing hydrogen and a hydroxyl group, which are unfavorable impurities for an oxide semiconductor, from being included in the film or an effect of removing hydrogen and a hydroxyl group from the film. that is, an oxide semiconductor can be highly purified by removing hydrogen serving as a donor impurity from the oxide semiconductor, whereby a normally-off transistor can be obtained. the high purification of an oxide semiconductor enables the off-state current of the transistor to be 1 aa/μm or lower. here, the unit of the off-state current represents current per micrometer of a channel width. fig. 22 shows a relation between the off-state current of a transistor and the inverse of substrate temperature (absolute temperature) at measurement. here, for simplicity, a value (1000/t) obtained by multiplying the inverse of substrate temperature at measurement by 1000 is indicated in the horizontal axis. specifically, as shown in fig. 22 , the off-state current can be 1 aa/μm (1×10 −18 a/μm) or lower, 100 za/μm (1×10 −19 a/μm) or lower, and 1 za/μm (1×10 −21 a/μm) or lower when the substrate temperature is 125° c., 85° c., and room temperature (27° c.), respectively. preferably, the off-state current can be 0.1 aa/μm (1×10 −19 a/μm) or lower, 10 za/μm (1×10 −20 a/μm) or lower, and 0.1 za/μm (1×10 −22 a/μm) or lower at 125° c., 85° c., and room temperature, respectively. note that in order to prevent hydrogen and moisture from being included in the oxide semiconductor film during formation thereof, it is preferable to increase the purity of a sputtering gas by sufficiently suppressing leakage from the outside of a deposition chamber and degasification through an inner wall of the deposition chamber. for example, a gas with a dew point of −70° c. or lower is preferably used as the sputtering gas in order to prevent moisture from being included in the film. in addition, it is preferable to use a target which is highly purified so as not to include impurities such as hydrogen and moisture. although it is possible to remove moisture from a film of an oxide semiconductor including in, sn, and zn as main components by heat treatment, a film which does not include moisture originally is preferably formed because moisture is released from the oxide semiconductor including in, sn, and zn as main components at a higher temperature than from an oxide semiconductor including in, ga, and zn as main components. the relation between the substrate temperature and electric characteristics of a transistor of a sample, on which heat treatment at 650° c. was performed after formation of the oxide semiconductor film, was evaluated. the transistor used for the measurement has a channel length l of 3 μm, a channel width w of 10 μm, lov of 0 μm, and dw of 0 μm. note that v d was set to 10 v. note that the substrate temperature was −40° c., −25° c., 25° c., 75° c., 125° c., and 150° c. here, in a transistor, the width of a portion where a gate electrode overlaps with one of a source electrode and a drain electrodes in the channel length direction is referred to as lov. fig. 19 shows the v g dependence of i d (a solid line) and field-effect mobility (a dotted line). fig. 20a shows a relation between the substrate temperature and the threshold voltage, and fig. 20b shows a relation between the substrate temperature and the field-effect mobility. from fig. 20a , it is found that the threshold voltage gets lower as the substrate temperature increases. note that the threshold voltage is decreased from 1.09 v to −0.23 v in the range from −40° c. to 150° c. from fig. 20b , it is found that the field-effect mobility gets lower as the substrate temperature increases. note that the field-effect mobility is decreased from 36 cm 2 /vs to 32 cm 2 /vs in the range from −40° c. to 150° c. thus, it is found that change in electric characteristics is small in the above temperature range. in a transistor in which such an oxide semiconductor containing in, sn, and zn as main components is used as a channel formation region, a field-effect mobility of 30 cm 2 /vsec or higher, preferably 40 cm 2 /vsec or higher, further preferably 60 cm 2 /vsec or higher can be obtained with the off-state current maintained at 1 aa/μm or lower, which can achieve on-state current needed for an lsi. for example, in an fet where l/w is 33 nm/40 nm, an on-state current of 12 μa or higher can flow when the gate voltage is 2.7 v and the drain voltage is 1.0 v. in addition, sufficient electrical characteristics can be ensured in a temperature range needed for operation of a transistor. this embodiment can be combined with any of the other embodiments as appropriate. embodiment 3 in this embodiment, a configuration of a cpu, which is one of signal processing circuits according to one embodiment of the present invention, will be described. fig. 24 shows the configuration of the cpu of this embodiment. the cpu in fig. 24 mainly includes an alu) 9901 , an alu controller 9902 , an instruction decoder 9903 , an interrupt controller 9904 , a timing controller 9905 , a register 9906 , a register controller 9907 , a bus i/f 9908 , a rewritable rom 9909 , and a rom i/f 9920 , over a substrate 9900 . note that “alu” means “arithmetic logic unit”, “bus i/f” means “bus interface”, and “rom i/f” means “rom interface”. further, the rom 9909 and the rom i/f 9920 may be provided over another chip. naturally, the cpu shown in fig. 24 is only an example in which the configuration is simplified, and an actual cpu may have various configurations depending on the uses. an instruction which is input to the cpu through the bus i/f 9908 is input to the instruction decoder 9903 and decoded therein, and then, input to the alu controller 9902 , the interrupt controller 9904 , the register controller 9907 , and the timing controller 9905 . the alu controller 9902 , the interrupt controller 9904 , the register controller 9907 , and the timing controller 9905 perform various controls based on the decoded instruction. specifically, the alu controller 9902 generates signals for controlling the drive of the alu 9901 . while the cpu is executing a program, the interrupt controller 9904 processes an interrupt request from an external input/output device or a peripheral circuit based on its priority or a mask state. the register controller 9907 generates an address of the register 9906 , and reads or writes data from/to the register 9906 depending on the state of the cpu. the timing controller 9905 generates signals for controlling operation timings of the alu 9901 , the alu controller 9902 , the instruction decoder 9903 , the interrupt controller 9904 , and the register controller 9907 . for example, the timing controller 9905 is provided with an internal clock generator for generating an internal clock signal clk 2 on the basis of a reference clock signal clk 1 , and inputs the clock signal clk 2 to the above circuits. in the cpu of this embodiment, a semiconductor memory device having the structure described in any of the above embodiments is provided in the register 9906 . in response to an instruction from the alu 9901 , the register controller 9907 can stop the supply of power supply voltage in the semiconductor memory device of the register 9906 without the necessity of saving and returning a data signal. in such a manner, even in the case where the operation of the cpu is temporarily stopped and the supply of the power supply voltage is stopped, a data signal can be held and power consumption can be reduced. specifically, for example, while a user of a personal computer does not input data to an input device such as a keyboard, the operation of the cpu can be stopped, so that the power consumption can be reduced. although the example of the cpu is described in this embodiment, the signal processing circuit of the present invention is not limited to the cpu and can be applied to an lsi such as a microprocessor, an image processing circuit, a digital signal processor (dsp), or a field programmable gate array (fpga). this application is based on japanese patent application serial no. 2011-114084 filed with japan patent office on may 20, 2011, the entire contents of which are hereby incorporated by reference.
|
039-666-180-204-859
|
US
|
[
"WO",
"US"
] |
B67D1/00,B01F5/06
| 2019-05-08T00:00:00 |
2019
|
[
"B67",
"B01"
] |
dispensing nozzle assemblies with static mixers
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the present application provides a dispensing nozzle assembly for mixing a first fluid and a second fluid. the dispensing nozzle assembly may include a target assembly with a number of fins and a number of channels and a static mixer positioned about the fins.
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claims i claim: 1. a dispensing nozzle assembly for mixing a first fluid and a second fluid, comprising: a target assembly; the target assembly comprising a plurality of fins and a plurality of channels; and a static mixer positioned about the plurality of fins. 2. the dispensing nozzle assembly of claim 1, wherein the target assembly comprises a tip and wherein the static mixer is positioned about the tip. 3. the dispensing nozzle assembly of claim 1, wherein the static mixer comprises an upper mixing tube portion and a lower mixing tube portion. 4. the dispensing nozzle assembly of claim 3, wherein the upper mixing tube portion comprises a first diameter, the lower mixing tube portion comprises a second diameter, and wherein the second diameter is smaller than the first diameter. 5. the dispensing nozzle assembly of claim 3, wherein the upper mixing tube portion surrounds the plurality of fins of the target assembly. 6. the dispensing nozzle assembly of claim 3, wherein the lower mixing tube portion extend below the plurality of fins of the target assembly. 7. the dispensing nozzle assembly of claim 1, wherein the static mixer comprises a plurality of baffles therein. 8. the dispensing nozzle assembly of claim 1, wherein the static mixer comprises a plurality of mixing fins therein. 9. the dispensing nozzle assembly of claim 1, wherein the target assembly comprises a plurality of slots in the plurality of channels. 10. the dispensing nozzle assembly of claim 1, wherein the target assembly comprises a hollow core. 11. the dispensing nozzle assembly of claim 1, wherein the target assembly comprises a plurality of slots in the plurality of channels and a hollow core. 12. the dispensing nozzle assembly of claim 11, wherein the hollow core comprises a conical shape. 13. the dispensing nozzle assembly of claim 1, wherein the target assembly comprises a tapered configuration. 14. the dispensing nozzle assembly of claim 1, wherein the static mixer comprises a plurality of twisted mixing fins. 15. a dispensing nozzle assembly for mixing a first fluid and a second fluid, comprising: a target assembly; the target assembly comprising a plurality of target fins and a plurality of target channels; and a twisted static mixer positioned about the plurality of target fins; the twisted static mixer comprising a plurality of twisted mixing fins.
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dispensing nozzle assemblies with static mixers technical field [0101] the present application and the resultant patent relate generally to dispensing nozzle assemblies for beverage dispensers and more particularly relate to multi-flavor or multi-fluid dispensing nozzle assemblies with a static mixer positioned about a target assembly for improved mixing with reduced carryover between pours. background of the invention [0102] current post-mix beverage dispensing nozzles generally mix streams of syrup, concentrate, sweetener, bonus flavors, other types of flavoring, and other ingredients with water or other types of diluent by flowing the syrup stream down the center of the nozzle with the water stream flowing around the outside. the syrup stream is directed downward with the water stream such that the streams mix as they fall into a consumer’s cup. [0103] there is a desire for a beverage dispensing system as a whole to provide as many different types and flavors of beverages as may be possible in a footprint that may be as small as possible. preferably, such a beverage dispensing system may provide as many beverages as may be available on the market in prepackaged bottles, cans, or other types of containers. [0104] in order to accommodate this variety, the dispensing nozzles need to accommodate fluids with different viscosities, flow rates, mixing ratios, temperatures, and other variables. current dispensing nozzle assemblies may not be able to accommodate multiple beverages with a single nozzle design and/or the dispensing nozzle assembly may be designed for specific types of fluid flow. one known means of accommodating differing flow characteristics is shown in commonly owned u.s. patent no. 7,383,966 that describes the use of replaceable fluid modules that are sized and shaped for specific flow characteristics. u.s. patent no. 7,383,966 is incorporated herein by reference in full. even more variety and more fluid streams may be employed in commonly owned u.s. patent no. 7,578,415 that shows the use of a number of tertiary flow assemblies. u.s. patent no. 7,578,415 also is incorporated herein by reference in full. [0105] one issue with the use of certain nozzle designs is brix stratification. (one degree brix is 1 gram of sucrose in 100 grams of solution and represents the strength of the solution as percentage by mass.) certain thicker or more viscous syrups may resist proper mixing with the other ingredients. as a result, the dispenser may provide an out of specification beverage with higher amounts of sugar at the bottom of the drink and lower amounts at the top. [0106] there is thus a desire for a dispensing nozzle assembly to accommodate even more and different types of fluids that may pass there through. the dispensing nozzle assembly preferably may accommodate this variety while still providing good mixing and easy cleaning. summary of the invention [0107] the present application and the resultant patent thus provide a dispensing nozzle assembly for mixing a first fluid and a second fluid. the dispensing nozzle assembly may include a target assembly with a number of fins and a number of channels and a static mixer positioned about the fins. [0108] the present application and the resultant patent further may provide a dispensing nozzle assembly for mixing a first fluid and a second fluid. the dispensing nozzle assembly may include a target assembly with a number of target fins and a number of target channels and a twisted static mixer positioned about the target fins. the twisted static mixer may include a number of twisted mixing fins. [0109] the present application and the resultant patent further provide a dispensing nozzle assembly. the dispensing nozzle assembly may include a diluent/sweetener module with a diluent chamber having a number of diluent chamber outlets defined by a number of projections and a target assembly positioned beneath the diluent/sweetener module. [0110] the present application and the resultant patent further provide a dispensing nozzle assembly. the dispensing nozzle assembly may include a diluent/sweetener module with a diluent chamber having a number of diluent chamber outlets defined by a number of projections and a target assembly having a tapered configuration and with a twisted static mixer positioned beneath the diluent/sweetener module. [0111] these and other features and improvements of the present application and the resultant patent will become apparent to one of ordinary skill in the art upon review of the following detailed description when taken in conjunction with the several drawings and the appended claims. brief description of the drawings [0112] fig. 1 is a perspective view of a dispensing nozzle assembly as described herein. [0113] fig. 2 is a side plan view of the dispensing nozzle assembly of fig. 1. [0114] fig. 3 is a top plan view of the injection ring assembly of the dispensing nozzle of fig. 1. [0115] fig. 4 is a bottom plan view of the injector ring assembly of the dispensing nozzle assembly of fig. 1. [0116] fig. 5 is a bottom perspective view of an upper injector ring of the injector ring assembly of fig. 3. [0117] fig. 6 is a partial sectional view of the upper injector ring of fig. 5. [0118] fig. 7 is a perspective view of a core module assembly of the dispensing nozzle assembly of fig. 1. [0119] fig. 8 is a partial sectional view of the core module assembly of fig. 7. [0120] fig. 9 is a side plan view of the core module assembly of fig. 7. [0121] fig. 10 is a bottom plan view of the core module assembly of fig. 7. [0122] fig. 11 is a partial section view of an alternative embodiment of an outlet tube as may be described herein. [0123] fig. 12 is a partial section view of an alternative embodiment of an outlet tube as may be described herein. [0124] fig. 13 is a partial bottom perspective view of an alternative embodiment of an upper injector ring of an injector ring assembly as may be described herein. [0125] fig. 14 is partial sectional view of a macro-ingredient outlet tube of the injector ring of fig. 13. [0126] fig. 15 is a perspective view of an alternative embodiment of a target assembly as may be described herein. [0127] fig. 16 is a perspective view of an alternative embodiment of a target assembly as may be described herein. [0128] fig. 17 is a perspective view of an alternative embodiment of a target assembly as may be described herein. [0129] fig. 18 is a partial bottom perspective view of an alternative embodiment of an upper injector ring of an injector ring assembly as may be described herein. [0130] fig. 19 is a side sectional view of the injector ring assembly of fig. 18. [0131] fig. 20 is a partial bottom perspective view of an alternative embodiment of an upper injector ring of an injector ring assembly as may be described herein. [0132] fig. 21 is a side sectional view of the injector ring assembly of fig. 20. [0133] figs. 22a - 22d show alternative configurations of macro-ingredient tubes as may be described herein. [0134] figs. 23a - 23b show alternative configurations of macro-ingredient tubes as may be described herein. [0135] fig. 24 is a perspective view of a target assembly with a static mixer as may be described herein. [0136] fig. 25 is an exploded perspective view of the target assembly with a static mixer of fig. 24. [0137] fig. 26 is a top view of the static mixer of fig. 24. [0138] fig. 27 is a side view of an alternative embodiment of a target assembly with a static mixer as may be described herein. [0139] fig. 28 is a section view of the target assembly of fig. 27. [0140] fig. 29 is a perspective view of an alternative embodiment of a target assembly with a static mixer as may be described herein. [0141] fig. 30 is a side view of an alternative embodiment of a target assembly with a twisted static mixer as may be described herein. [0142] fig. 31 is a side view of an alternative embodiment of a core module assembly as may be described herein. [0143] fig. 32 is a sectional view of the core module assembly of fig. 31. [0144] fig. 33 is a section view of a diluent/sweetener module of the core module assembly of fig. 31. detailed description [0145] referring now to the drawings, in which like numerals refer to like elements throughout the several views, fig. 1 shows an example of a dispensing nozzle assembly 100 as is described herein. the dispensing nozzle assembly 100 may be used as part of a beverage dispenser for dispensing many different types of beverages or other types of fluids. specifically, the dispensing nozzle assembly 100 may be used with diluents, macro-ingredients, micro-ingredients, and other types of fluids. the diluents generally include plain water (still water or non-carbonated water), carbonated water, and other fluids. the dispensing nozzle assembly 100 may be a common dispensing nozzle assembly. the term“common” is used herein to signify that the common dispensing nozzle assembly may be commonly used with many different types of beverages and beverage dispensers. [0146] generally described, the macro-ingredients may have reconstitution ratios in the range from full strength (no dilution) to about six (6) to one (1) (but generally less than about ten (10) to one (1)). the macro-ingredients may include sugar syrup, hfcs (“high fructose com syrup”), fis (“fully inverted sugar”), mis (“medium inverted sugar”), concentrated extracts, purees, and similar types of ingredients. other ingredients may include traditional bib (“bag-in-box”) flavored syrups, nutritive and non-nutritive sweetener blends, juice concentrates, dairy products, soy, and rice concentrates. similarly, a macro-ingredient base product may include the sweetener as well as flavorings, acids, and other common components of a beverage syrup. the beverage syrup with sugar, hfcs, or other macro-ingredient base products generally may be stored in a conventional bag-in-box container remote from the dispenser. the viscosity of the macro-ingredients may range from about 1 to about 10,000 centipoise and generally over 100 centipoises or so when chilled. other types of macro-ingredients may be used herein. [0147] the micro-ingredients may have reconstitution ratios ranging from about ten (10) to one (1) and higher. specifically, many micro-ingredients may have reconstitution ratios in the range of about 20: 1, to 50: 1, to 100: 1, to 300: 1, or higher. the viscosities of the micro-ingredients typically range from about one (1) to about six (6) centipoise or so, but may vary from this range. examples of micro-ingredients include natural or artificial flavors; flavor additives; natural or artificial colors; artificial sweeteners (high potency, nonnutritive, or otherwise); antifoam agents, nonnutritive ingredients, additives for controlling tartness, e.g., citric acid or potassium citrate; functional additives such as vitamins, minerals, herbal extracts, nutricuticals; and over the counter (or otherwise) medicines such as pseudoephedrine, acetaminophen; and similar types of ingredients. various types of alcohols may be used as either macro- or micro ingredients. the micro-ingredients may be in liquid, gaseous, or powder form (and/or combinations thereof including soluble and suspended ingredients in a variety of media, including water, organic solvents, and oils). other types of micro-ingredients may be used herein. [0148] the dispensing nozzle assembly 100 may be largely modular in nature. the dispensing nozzle assembly 100 may include an injector ring assembly 110. the injector ring assembly 110 may include an upper injector ring 120 and a lower injector ring 130. the respective injector rings 120, 130 may be made out of a thermoplastic such as polypropylene and the like. other types of food grade materials may be used herein. the injector rings 120, 130 may be injection molded or manufactured via other types of conventional techniques. the injector rings 120, 130 may be fastened together via laser welding techniques. the use of laser welding avoids the need for gaskets and the like. other types of fastening techniques may be used herein. [0149] the dispensing nozzle assembly 100 also may have a core module assembly 140. the core module assembly 140 may include a diluent/sweetener module 150 and a target assembly 160. the diluent/sweetener module 150 and the target assembly 160 also may be made out of a food grade thermoplastic such as polypropylene and the like. other types of food grade materials may be used herein. the diluent/sweetener module 150 and the target assembly 160 may be injection molded or manufactured via other types of conventional techniques. the diluent/sweetener module 150 and the target assembly 160 may be in communication with the upper and lower injector rings 120, 130 of the injector ring assembly 110 as will be described in more detail below. in some embodiments, the diluent/sweetener module 150 may be fastened with the upper injector ring 120 such as via laser welding or other types of fastening techniques. other components and other configurations may be used herein. [0150] the injector ring assembly 110 may define a number of macro-ingredient paths 170 and a number of micro-ingredient paths 180 therethrough. figs. 3-6 show an example of the injector ring assembly 110. the injector ring assembly 110 may be largely plate like in shape with a central aperture 190 extending therethrough. the lower injector ring 130 may be largely flat and planar like in shape. the upper injector ring 120 may have the macro-ingredient paths 170 and the micro-ingredient paths 180 extending therethrough. the central aperture 190 may be sized and shaped for the diluent/sweetener module 150 and the target assembly 160. one or more assembly flanges 195 may extend into the central aperture 190. other components and other configurations may be used herein. [0151] specifically, the upper injector ring 120 may include a number of macro ingredient ports 200 of the macro-ingredient paths 170. in this example, there may be twelve (12) macro-ingredient ports 200 encircling about the central aperture 190 in whole or in part. any number of the macro-ingredient ports 200 may be used herein in any position. the macro-ingredient ports 200 may be arranged in pairs with each pair sharing a macro-ingredient line fastener aperture 210. the macro-ingredient line fastener aperture 210 allows a macro-ingredient line to be secured thereto. the macro-ingredient ports 200 may be used and sized primarily for traditional beverage syrups that are typically housed in a bag-in-box container as described above although any type of macro-ingredient may be used herein. [0152] each macro-ingredient port 200 may include a macro-ingredient inlet chamber 220. the macro-ingredient inlet chamber 220 may be largely tube-like in shape. each macro-ingredient inlet chamber 220 may lead to a number of macro-ingredient outlet tubes 230. in this example, each macro-ingredient inlet chamber 220 extends to four (4) macro-ingredient outlet tubes 230. any number of the macro-ingredient outlet tubes 230 may be used herein in communication with each macro-ingredient inlet chamber 220. the number of macro-ingredient outlet tubes 230 may vary in each macro-ingredient inlet chamber 220. the macro-ingredient outlet tubes 230 may have an angled configuration 240. specifically, the macro-ingredient outlet tubes 230 may extend in the angled configuration 240 through the upper injector ring 120 to the central aperture 190 towards the target assembly 160. the angle may be about 40 to about 50 degrees although the angle may vary. the macro-ingredient outlet chambers 220 and the macro-ingredient outlet tubes 230 may have any suitable size, shape, or configuration. other components and other configurations may be used herein. [0153] the upper injector ring 120 also may include a number of micro-ingredient ports 250 of the micro-ingredient paths 180. the micro ingredient ports 250 may be used and sized primarily for use with the micro-ingredients. in this example, eleven (11) sets of four (4) micro-ingredient ports 250 are shown encircling the center aperture 190 concentrically with the macro-ingredient ports 200. any number of the micro-ingredient ports 250 may be used herein in any configuration. each set of the micro-ingredient ports 250 may have one or more micro-ingredient line fastener apertures 260 positioned there about. the micro-ingredient line fastener apertures 260 allow a micro-ingredient line to be secured thereto. the micro-ingredient ports 250 may be arranged in a quad configuration 270 of a set of four ports. the quad configuration 270 may accommodate a quad tube assembly 280 as shown in part in fig. 1 and shown in u.s. patent no. 7,866,509 referenced above. other components and other configurations may be used herein. [0154] each micro-ingredient port 250 may include a micro-ingredient inlet passage 290. the micro-ingredient inlet passages 290 may be largely tube-like in shape. the micro-ingredient inlet passages 290 may have any suitable size, shape, or configuration. each micro-ingredient inlet passage 290 may lead to a micro-ingredient dispensing chamber 300. the micro-ingredient inlet passages 290 may be in communication with the micro-ingredient dispensing chambers 300 via a micro-ingredient dispensing chamber inlet tube 310. the micro-ingredient dispensing chamber inlet tube 310 may have a reduced diameter as compared to the micro-ingredient inlet passage 290. each micro-ingredient dispensing chamber 300 may have a curved configuration 320 along the horizontal plane such that the upper injector ring 120 may accommodate as many micro-ingredient ports 250 as possible extending therethrough. each micro ingredient dispensing chamber 300 may be enclosed on the lower side by the lower injector ring 130. each micro-ingredient dispensing chamber 300 may include a micro ingredient dispensing chamber outlet tube 330. each of the micro-ingredient dispensing chamber outlet tubes 330 may include the angled configuration 240. specifically, the micro-ingredient dispensing chamber outlet tube 330 may extend in the angled configuration 240 from the micro-ingredient dispensing chamber 300 through the upper ring 120 and into the central aperture 190. the same or different angles may be used herein. the micro-ingredient dispensing chamber outlet tubes 330 may have a reduced diameter as compared to the micro-ingredient dispensing chamber inlet tubes 310. the micro-ingredient dispensing chamber outlet tubes 330 may extend below the macro ingredient outlet tubes 230 along the angled configuration 240 in whole or in part. the micro-ingredient inlet passage 290, the micro-ingredient dispensing chamber inlet tubes 310, the micro-ingredient dispensing chamber 300, and the micro-ingredient dispensing chamber outlet tubes 330 may have any suitable size, shape, or configuration. other components and other configurations may be used herein. [0155] the macro-ingredient outlet tubes 230 and the micro-ingredient dispensing chamber outlet tubes 330 may extend through a dispensing ring 340 of the upper injector ring 120. the dispensing ring 340 may be a molded, unitary element of the upper injector ring 120 or the dispensing ring 340 may be a separate, added component. if a separate component, the dispensing ring 340 may be modular in nature and may be divided into any number of pie shaped elements or otherwise configured. the dispensing ring 340 may be made out of a thermoplastic like the rest of the upper injector ring 120 or a different material such as stainless steel or a ceramic. the macro-ingredient outlet tubes 230 and/or the micro-ingredient dispensing chamber outlet tubes 330 may be laser drilled through the dispensing ring 340. other types of drilling techniques may be used herein. the use of a hydrophilic material such as stainless steel may prevent or limit fluid carryover, i.e., micro-ingredients may pool at the end of the micro-ingredient dispensing chamber outlet tube 330. such pooled micro-ingredients may drip and/or carry over into the next beverage. the use of the angled configuration 240 also may assist in reducing carryover. other components and other configurations may be used herein. [0156] figs. 7-10 show an example of the core module assembly 140 with the diluent/sweetener module 150 and the target assembly 160. the diluent/sweetener module 150 may be attached to the target assembly 160 in a snap fit and the like. the diluent/sweetener module 150 may include a diluent port 350 and a sweetener port 360. the diluent/sweetener module 150 may include a diluent/sweetener module fastener aperture 370 extend therefrom. a diluent line and a sweetener line may be attached thereto. the target assembly 160 may include a number of vertically extending fins 380 that extend into a largely star-shaped appearance as viewed from the bottom. the fins 380 may form a number of u or v shaped channels 390. [0157] when combined, the diluent/sweetener module 150 and the target assembly 160 may define a diluent/sweetener mixing chamber 400 therebetween. the target assembly 160 may have a number of diluent/sweetener dispensing ports 410 positioned about the diluent/sweetener mixing chamber 400. specifically, the diluent/sweetener mixing chamber 400 may extend from the diluent port 350 and the sweetener port 360 to the diluent/sweetener dispensing ports 410. the dispensing ports 410 may be positioned over the fins 380 and the channels 390 of the target assembly 160. an umbrella valve 415 and the like also may be used herein. [0158] the target assembly 160 may include an assembly track 420 formed thereon. the assembly track 420 may include a lower path 430 and an upper path 440. the assembly track 420 may be sized to accommodate the assembly flange 195 of the central aperture 190 of the injection ring assembly 110 so as to connect the core module assembly 140 to the injector ring assembly 110 (or vice versa). the assembly track 420 may have any suitable size, shape, or configuration. other components and other configurations may be used herein. [0159] in use, the upper injection ring 120 and the lower injection ring 130 may be combined so as to form the injector ring assembly 110. likewise, the diluent/sweetener module 150 and the target assembly 160 may be combined so as to form the core module assembly 140. the core module assembly 140 may be positioned within the central aperture 190 of the injector ring assembly 110. the assembly track 420 of the core module assembly 140 may accommodate the assembly flange 195 of the injector ring assembly 110 so as to attach the core module assembly 140 in a screw-like action. specifically, the assembly flange 195 may travel down the upper path 440 as the target assembly 160 is rotated clockwise. continued rotation pulls the target assembly 160 into a secure fit as the assembly flange 195 travels along the lower path 430. the use of the assembly track 420 also provides for easy removal of the core module assembly 140 for cleaning the central aperture 190 of the injector ring assembly 110. any order of assembly may be used herein. any type of fasteners or joinders techniques also may be used herein. other components and other configurations may be used herein. [0160] a sweetener or other fluid may flow into the sweetener port 360 of the core module assembly 140 with a diluent flowing into the diluent port 350. the sweetener and the surrounding flow of diluent may mix in the diluent/sweetener mixing chamber in whole or in part and may be dispensed via the dispensing ports 410 of the target assembly 160. the diluent/sweetener mixture may flow downward through the channels 390 of the target assembly 160 and continue mixing therealong. [0161] one or more macro-ingredients may flow into the macro-ingredient ports 200 of the upper injector ring 120 of the injector ring assembly 110. the macro ingredients may flow through the macro-ingredient inlet chambers 220 and may be dispensed via the macro-ingredient outlet tubes 230 with the angled configuration 240 towards the target assembly 160. having a number of the macro-ingredient outlet tubes 230 used in combination with each of the macro-ingredient inlet chambers 220 allows for good flow of the macro-ingredients therethrough. [0162] likewise, micro-ingredients may flow into the micro-ingredient ports 250 of the upper injector ring 120 of the injector ring assembly 110. the micro-ingredients may flow into the micro-ingredient passage 290 and into the micro-ingredient dispensing chamber 300 via the micro-ingredient dispensing chamber inlet tube 310. the micro- ingredients may pass through the micro-ingredient dispensing chamber 300 and may exit via the micro-ingredient dispensing chamber outlet tube 330 at the angled configuration 240 towards the targeted assembly 160. the diluent, the sweetener, the macro-ingredients, and/or the micro-ingredients all may mix as they flow along the target assembly 160 and fall towards a consumer’s cup or other type of vessel. different beverages may use different combinations of ingredients. [0163] the common dispensing nozzle assembly 100 thus may be used to dispense any number of beverages. for example, a carbonated soft drink may include a flow of carbonated water as a diluent via the diluent port 350 and a flow of a conventional beverage syrup via one of the macro-ingredient ports 200. alternatively, the carbonated soft drink also may include the flow of carbonated water via the diluent port 350, a flow of sweetener via the sweetener port 360, and a number of flows of micro-ingredients via the micro-ingredient ports 250. further, a tea or coffee beverage may be created via a flow of still water as the diluent, a flow of tea concentrate as a macro-ingredient or a micro ingredient, and a flow of a sweetener as a macro-ingredient or a micro-ingredient. any number and combination of different beverages may be produced herein in a fast and efficient manner. [0164] the dispensing nozzle assembly 100 may dispense syrups/concentrates with reconstitution ratios of anywhere from about three (3) to one (1) to about one hundred fifty (150) to one (1) or higher. the number, size, and shape of the various ports and pathways herein may be varied and reconfigured as desired. the dispensing nozzle assembly 100 thus may be used with almost any type of beverage dispenser. for example, the dispensing nozzle assembly 100 may be used with a conventional syrup based dispenser, a micro-ingredient based dispenser, and/or a hybrid or other type of dispenser based upon availability or any type of operational parameters or needs. the dispensing nozzle assembly 100 may be original equipment or part of a retrofit. multiple dispensing nozzles assemblies 100 may be used together herein in different configurations. [0165] the following chart shows how the dispensing nozzle assembly 100 may produce different types of beverages: beverage diluent 350 sweetener 360 macro 230 micro 330 nutritive sweetened on on off 2+ on micro-based non-nutritive on off off 2+ on sweetened micro-based macro-based on off one on off flavored macro- on off one on 1+ on based mid-calorie on on off 3+ on micro-based [0166] fig. 11 shows an alternative embodiment of a micro-ingredient dispensing chamber outlet tube 450. the micro-ingredient dispensing chamber outlet tube 450 may have the angled configuration 240 extending through the dispensing ring 340. the micro ingredient dispensing chamber outlet tube 450 may include an insert 460 therein. the insert 460 may be made out of a stainless steel, a ceramic, or other types of a hydrophilic material in whole or in part. as described above, the micro-ingredient dispensing chamber outlet tubes 450 may be laser drilled through a plastic material of the dispensing ring 340 or otherwise formed therein. the plastic material may be largely hydrophobic. by using different materials and positions therein, the hydrophilic/hydrophobic ratio of the micro ingredient dispensing chamber outlet tubes 450 may be varied. specifically, the hydrophilic material tends to hold the micro-ingredients within the micro-ingredient dispensing chamber outlet tube 450 so as to resist carryover between dispenses. the insert 460 thus may not extend the entire length of the micro-ingredient dispensing chamber outlet tube 450. rather, a length of the plastic material may extend at the exit. other components and other configurations may be used herein. [0167] alternatively as shown in fig. 12, the micro-ingredient dispensing chamber outlet tube 450 may include a surface treatment 470 therein. the surface treatment 470 also may vary hydrophilic properties of the micro-ingredient dispensing chamber outlet tubes 450 in whole or in part. as above, the surface treatment 470 may end before the exit of the micro-ingredient dispensing chamber outlet tube 450 given the hydrophobic properties of the plastic. [0168] to the extent that the dispensing ring 340 is made out of stainless steel or similar types of material, each micro-ingredient dispensing chamber outlet tube 450 may take the form of any number of smaller tubes drilled therethrough. the tubes may have the same or a number of different shapes. the use of a number of smaller holes may fan out the velocity of the micro-ingredient stream so as to slow the stream while creating additional surface tension to prevent dripping. the use of the insert 460, the surface treatment 470, and the angled configuration 240 all may contribute to reduce dripping and carryover. the insert 460, the surface treatment 470, and the angled configuration 240 may be used separately or in combination. other components and other configurations may be used herein. [0169] figs. 13 and 14 show an alternative embodiment of an upper injector ring 500 as may be described herein. in this example, the macro-ingredient outlet tubes 230 may include a number of threads 510 formed therein. the size, shape, angle, and configuration of the threads 510 may vary. the threads 510 act somewhat like rifling in a gun barrel to increase the speed of the flow therein. specifically, the threads 510 are surface instabilities that add a rotational component to the macro-ingredient flow therethrough. this unstable rotation allows the macro-ingredients to mix more easily with the other ingredients so as to reduce thereby brix stratification in the beverage. other components and other configurations may be used herein. [0170] figs. 15 - 17 show further embodiments of a target assembly 160 as may be described herein. fig. 15 shows a target assembly 520 with a number of twisted fins 530 and twisted channels 540 instead of the straight fins 380 and straight channels 390 shown above. in this example, the twist may be about twenty degrees or so. other angles may be used herein. in a manner similar to the rifling in the macro-ingredient outlet tubes 230, the twisted fins 530 and the twisted channels 540 create instability and swirl at the end of the target assembly 520 to promote good mixing of the macro-ingredients and the other ingredients and, hence, reduced brix stratification. the target assembly 520 may be used with or without the threads 510 of the macro-ingredient outlet tubes 230. other components and other configurations may be used herein. [0171] fig. 16 shows a target assembly 550 using the twisted fins 530 and the twisted channels 540 at about the twenty degree twist. in this example, the twisted fins 530 and the twisted channels 540 may include a taper 560. specifically, the taper 560 represents a reduction in diameter from the top to the bottom of the target assembly 550. the nature of the taper 560 may vary. fig. 17 shows a target assembly 570 using the twisted fins 530 and the twisted channels 540 with the taper 560. in this example, the twist may be about forty degrees or so. the angle may range from about fifteen degrees to about forty-five degrees. other angles may be used herein. other variations may include changing the length of the fins and the channels. other components and other configurations may be used herein. [0172] experimentation has shown that the combination of the treads 510 in the macro-ingredient outlet ports 230 and the twisted fins 530 and twisted channels 540 with the twenty degree twist of the target assembly 520 may have the greatest impact to date on reducing brix stratification in macro-ingredients such a certain types of viscous syrups. extensive laboratory testing has shown such improved mixing the amount of brix stratification may vary. such a reduction may bring the resultant beverage into specification such that the flexibility of the overall beverage dispenser is improved. [0173] figs. 18 and 19 show an alternative embodiment of an upper injector ring 600 as may be described herein. in this example, the micro-ingredient dispensing chamber outlet tubes 330 and the macro-ingredient outlet tubes 230 may be in a“showerhead” configuration or a raised bowl 610. the micro-ingredient dispensing chamber outlet tubes 330 may be largely similar to those described above in number and configuration. many more macro-ingredient outlet tubes 230, however, may be used herein. for example, if twelve groups of four macro-ingredient tubes 230 in a line configuration for a total of forty-eight macro-ingredient outlet tubes are shown in fig. 4, twelve groups of eleven macro-ingredient outlet tubes 230 in a four by three by four configuration for a total of 132 macro-ingredient tubes 230 are shown herein. the increased number of macro ingredient tubes 230 provides increased turbulence about the target assembly 160 for improved mixing and, hence, improved brix stratification. the number of macro ingredient outlet tubes 230 may vary. likewise, the size, shape, and configuration of the macro-ingredient outlet tubes 230 may vary. the macro-ingredient outlet tubes 230 may or may not include the threads 510 described above. other components and other configurations may be used herein. [0174] figs. 20-23b show an alternative embodiment of an upper injector ring 620 of a dispensing nozzle assembly 100 as may be described herein. in this example, the micro-ingredient dispensing chamber outlet tubes 330 and the macro-ingredient outlet tubes 230 may be positioned in or about the dispensing ring 340 instead of in the “showerhead” configuration or the raised bowl 610. similar to that described above, the macro-ingredient outlet tubes 230 may be used in many different sizes, shapes, and configurations. figs. 20, 21, and 22a, show a number of the macro-ingredient outlet tubes 230 positioned in a number of two by three configurations 630 (two row of three macro ingredient outlet tubes 230). fig. 22b shows a number of the macro-ingredient outlet tubes 230 positioned in a two by four configuration 640 (two rows of four macro ingredient tubes 230). fig. 22c shows a number of the macro-ingredient outlet tubes 230 positioned in a four-two-four configuration 650 (a top row of four macro-ingredient tubes 230, a middle row of two macro-ingredient tubes 230, and a botom row of four macro ingredient tubes 230). fig. 22d shows a single row of three macro-ingredient outlet tubes 230. many other variations may be used herein. a number of different configurations may be used together herein in the upper injector ring 620. the macro-ingredients may be a conventional syrup stream. [0175] in addition to variations in the number and the position of the macro ingredient outlet tubes 230, the diameter of the macro-ingredient outlet tubes 230 also may vary. although a typical diameter may be about 0.03 inches or about 0.046 inches (about 0.76 millimeters or 1.17 millimeters), the diameter may vary from about 0.66 millimeters or less to about 1.2 millimeters or more. these variation may provide a maximum contact width along the target 160 of about 3 millimeter to about 8 millimeters or more with a total perimeter of all of the macro-ingredient outlet tubes 230 of about 22 millimeters to about 34 millimeters or more. variations in the maximum contact width seem to be the most responsive in reducing overall brix stratification. other components and other configurations may be used herein. macro-ingredient outlet tubes 230 of different diameter may be used together herein in the upper injector ring 620. [0176] another variable considered is the angle of the macro-ingredient outlet tubes 230 through the dispensing ring 230. a converging configuration of the macro ingredient outlet tubes 230 may converging into a single channel 390 along the target 160 so as to mix with only one water stream from the diluent-sweetener dispensing ports 410. a parallel configuration 660 of the macro-ingredient outlet tubes 230 as is shown in fig. 23 a may intercept two or three water streams along two or three of the channels 390 of the target 160. a diverging configuration 670 of the macro-ingredient outlet tubes 230 as is shown in fig 23b may intercept three or more water streams along three or more channels 390. the extent of the diverging angle, however, may be limited to prevent or reduce overspraying. better mixing thus may be provided by the macro-ingredients intercepting more of the water streams. [0177] many different variations of the macro-ingredient outlet tubes 230 may be used herein. by way of example only, preferred combinations may include the two by three configuration 630 or the two by four configuration 640 in the parallel configuration 660 or the diverging configuration 670 so as to maximize the overall width of contact with limited overspraying. brix performance of 1.5 degrees or better may be obtained. these configurations may be combined with the inserts 460, the surface treatments 470, the treads 510, the twisted fins 530, the tapered fins 560, and other variations in any combination. the configurations shown herein are by way of example only. any combination of number, size, angle, or position may be used herein. other components and other configurations may be used herein. [0178] figs. 24 and 25 show a further embodiment of a portion of the dispensing nozzle assembly 100. in this example, at least the exterior of the diluent/sweetener module 150 and the target assembly 160 of the core module assembly 140 may be molded as a single element. the target assembly 160 may include a static mixer 700 positioned about a bottom tip 710 of the fins 380 thereof. the static mixer 700 may include an upper mixing tube portion 720 and a lower mixing tube portion 730. the upper mixing tube portion 720 may have a first diameter 740 sized to encircle the fins 380. the lower mixing tube portion 730 may extend beneath the fins 380 and may have a smaller second diameter 750. a number of baffles 760 may extend from a central hub 770. as is shown in fig. 26, the static mixer 700 also may include a number of mixing fins 780 positioned therein in addition to or in place of the baffles 760. the size, shape, and configuration of the mixing fins 780 may vary. other components and other configurations may be used herein. [0179] the use of the static mixer 700 thus promotes good mixing of the fluids flowing therethrough. traditionally, extended tubes and other types of static devices have been used to promote mixing therein. tubes with an extended length, however, may have issues with the use of the micro-ingredients and the macro-ingredients because portions of the extended tube may not be washed consistently by the diluent. the use of the static mixer 700 herein with the upper mixing tube portion 720 and the lower mixing tube portion 730 with the reduced second diameter 750 thus may be preferred in that the diluent may flow about the outside thereof so as to promote cleaning and reduce carryover. the internal baffles 760 and the lower mixing tube portion 730 with the reduced second diameter 750 promote turbulence and, hence, good mixing while the upper mixing tube portion 720 maintains the swirling fluids therein so as to prevent a misdirected spray. the addition of the mixing fins 780 promotes further swirl and turbulence therein. [0180] figs. 27 and 28 show further embodiments of the static mixer 700. as is shown in fig. 27, the target assembly 160 may have an open center configuration 790. specifically, the channels 390 between the fins 380 may have a slot 800 therein for fluid communication between the fins 380 so as to allow fluid to travel around the target assembly 160. such horizontal movement may achieve more fluid coverage than the initial impingement. as is shown in fig. 28, the target assembly 160 also may have a hollow core 810. the hollow core 810 may allow full mixing without regard to the coverage angle. the hollow core 810 may have a substantially conical shape 820 so as to limit areas of possible entrapment. the open center configuration 790 and the hollow core 810 may be used together or separately. other components and other configurations may be used herein. [0181] fig. 29 shows a further embodiment of the static mixer 700. in this example, the fins 380 of the target assembly 160 may have a tapered configuration 830. as is shown, the tapered configuration 830 has a reduced diameter from the top to the bottom of the target assembly 160. the nature and extent of the tapered configuration 830 may vary. the minimized size and diameter of the tapered configuration 830 may provide reduced carryover between pours. additional drip points/edges also may be used. the tapered configuration 830 also provides good cleaning of the static mixer 700 as the diluent flow over the front surface thereof. other components and other configurations may be used herein. [0182] fig. 30 shows a target assembly 160 with a twisted static mixer 840 as may be described herein. in this example, the fins 380 and the channels 390 of the target assembly 160 may be somewhat shorter than those described above. the twisted static mixer 840 may be positioned beneath the tip 710 of the target assembly 160. the twisted static mixer 840 may include a number of twisted mixing fins 850. the twisted mixing fins 850 may have a reduced diameter as compared to the fins 380 of the target assembly 160. any number of the twisted mixing fins 850 may be used in any size, shape, or configuration. the twisted mixing fins 850 may provide agitation so as to promote good mixing. the smaller diameter of the twisted mixing fins 850 may reduce centrifugal forces from spraying fluid away from the target assembly 160. other components and other configurations may be used herein. [0183] figs. 31-33 show a further embodiment of a dispensing nozzle assembly 100. in this example, a core module assembly 860 may be in the form of the unified core module with at least the exterior of the diluent/sweetener module 150 and the target assembly 160 molded as a single part. the target assembly 160 may include the static mixer 700 in the form of the twisted static mixer 840 with the twisted mixing fins 850. unlike the target assembly 160 of fig. 30, the fins 380 and the channels 390 in this example may have the tapered configuration 830 with a reduced diameter from the top to the bottom of the target assembly 160. the nature and extent of the tapered configuration 830 may vary. a finless gap 870 may extend between the end of the fins 380 and the twisted static mixer 840. the length and diameter of the finless gap 870 may vary. other components and other configurations may be used herein [0184] the diluent/sweetener module 150 may include an upper wall 880 and an internal base 890 with the diluent/sweetener mixing chamber 400 and the diluent/sweetener dispensing ports 410 therein. a flow guide 900 may be positioned within the diluent/sweetener module 150. the flow guide 900 may extend from the diluent port 350 and the sweetener port 360 to the base 890. the flow guide 900 may include a central sweetener path 910 with the umbrella valve 415 therein in communication with the sweetener port 360. the flow guide 900 also may have an upper floor 920 defining a diluent chamber 930 and a lower floor 940 with a number of lower diluent ports 950 formed therein. the size, shape, and configuration of the component and paths described herein may vary. [0185] the upper wall 880 of the diluent/sweetener module 150 may have a number of projections 960 positioned on the interior thereof. the projections 960 may extend from the upper wall 880 to the upper floor 920 of the flow guide 900. the projections 960 may have an upper tapered configuration 970 to assist in the installation of the flow guide 900. the number of projections 960 may vary. the projections 960 and the upper floor 920 of the flow guide 900 may define a number of diluent chamber outlets 980 therethrough. the respective size, shape, and configuration of the projections 960 and the diluent chamber outlets 980 may vary. the diluent chamber outlets 980 may define an open space between the projections 960 of about fifty percent (50%) to about seventy percent (70%) with about sixty-six percent (66%) preferred. other spacings may be used herein. other components and other configurations may be used herein. [0186] in use, diluent enters the core module assembly 860 via the diluent port 350 and the sweetener may enter via the sweetener port 360. the diluent may spread out over the diluent chamber 930 and may flow evenly distributed through the diluent chamber outlets 980, through the flow guide 900, and out via the diluent/sweetener ports 410. the diluent then evenly flows down about the fins 380 and the channels 390 of the target assembly 160. the sweetener, if used, also flows out via the sweetener/diluent ports 410. the micro-ingredients, the macro-ingredients, and/or other fluids from the injector ring assembly 110 may intersect the flows and mix along the target assembly 160 and into a consumer’s cup. [0187] the use of the diluent chamber outlets 980 defined by the projections 960 assist in ensuring an even distribution of the diluent flowing around the target assembly 160, particularly at lower flow rates. given that the diluent port 350 is located off center on one side of the diluent/sweetener module 150 (with the centered sweetener port 360 in the middle, see, e.g., figs 7 and 8), more of the diluent flow tended to exit the diluent/sweetener module 150 along the side of the diluent port 350. such an uneven distribution could promote overspray along the channels 390 with less flow. the size and shape of the diluent chamber 930 and the diluent chamber outlets 980 effectively modify the hydraulic parameters of the flow therethrough to provide an evenly distributed flow about the target assembly 160. such an even flow limits overspray. moreover, the even flow thus may limit carryover between beverages in that the diluent effectively washes the entire target assembly 160 of stray droplets. [0188] the use of the tapered configuration 830 along the length of the twisted static mixer 840 as well as the use of the twisted mixing fins 850 also may limit carryover and overspray while providing good mixing. specifically, the tapered configuration 830 promotes more diluent coverage along the length of the target assembly 160 with the diluent forming a near contiguous stream about the finless gap 870. the twisted mixing fins 850 then provide turbulence within the stream for good mixing. other components and other configurations may be used herein. [0189] it should be apparent that the foregoing relates only to certain embodiments of the present application and the resultant patent. numerous changes and modifications may be made herein by one of ordinary skill in the art without departing from the general spirit and scope of the invention as defined by the following claims and the equivalents thereof. [0190] the following numbered clauses set out further aspects of the invention (which may optionally be combined with other aspects) along with preferred and/or optional features thereof: [0191] clause 1. a dispensing nozzle assembly, comprising: a diluent/sweetener module; the diluent/sweetener module comprising a diluent chamber; the diluent chamber comprising a plurality of diluent chamber outlets defined by a plurality of projections; and a target assembly positioned beneath the diluent/sweetener module. [0192] clause 2. the dispensing nozzle assembly of clause 1, wherein the diluent/sweetener module comprises an off center diluent port in communication with the diluent chamber. [0193] clause 3. the dispensing nozzle assembly of clause 2, wherein the diluent/sweetener module comprises a center sweetener port. [0194] clause 4. the dispensing nozzle assembly of clause 1, wherein the diluent/sweetener module comprises a flow guide in communication with the diluent chamber. [0195] clause 5. the dispensing nozzle assembly of clause 4, wherein the flow guide comprises an upper floor extending between the plurality of projections. [0196] clause 6. the dispensing nozzle assembly of clause 1, wherein the plurality of projections comprises a tapered configuration. [0197] clause 7. the dispensing nozzle assembly of clause 1, wherein the target assembly comprises a static mixer. [0198] clause 8. the dispensing nozzle assembly of clause 7, wherein the static mixer comprises a twisted static mixer with a plurality of twisted mixing fins. [0199] clause 9. the dispensing nozzle assembly of clause 1, wherein the target assembly comprises a tapered configuration. [0200] clause 10. the dispensing nozzle assembly of clause 1, wherein the target assembly comprises a plurality of fins and a plurality of channels in a tapered configuration, a finless gap, and a static mixer. [0201] clause 11. a dispensing nozzle assembly, comprising: a diluent/sweetener module; the diluent/sweetener module comprising a diluent chamber; the diluent chamber comprising a plurality of diluent chamber outlets defined by a plurality of projections; and a target assembly positioned beneath the diluent/sweetener module; the target assembly comprising a tapered configuration and a twisted static mixer. [0202] clause 12. the dispensing nozzle assembly of clause 11, wherein the diluent/sweetener module comprises an off center diluent port in communication with the diluent chamber. [0203] clause 13. the dispensing nozzle assembly of clause 11, wherein the diluent/sweetener module comprises a flow guide in communication with the diluent chamber. [0204] clause 14. the dispensing nozzle assembly of clause 11, wherein the twisted static mixer comprises a plurality of twisted mixing fins. [0205] clause 15. the dispensing nozzle assembly of clause 11, wherein the target assembly comprises a plurality of fins and plurality of channels in the tapered configuration.
|
039-798-319-299-878
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US
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B29C70/52,H01B5/10,H01B9/04,B29B15/12,B29C63/10,B29K101/12,B29K105/08,B29L31/34,H01B1/02,H01B1/24,H01B3/42,H01B3/48,H01B7/00,H01B7/18,H01B9/00,B29C/,H01B/,H01B5/08,H01B7/17,B29B/,B29L/
| 2011-04-12T00:00:00 |
2011
|
[
"B29",
"H01"
] |
electrical transmission cables with composite cores
|
the present invention discloses electrical cables containing a cable core and a plurality of conductive elements surrounding the cable core. the cable core contains at least one composite core, and each composite core contains a rod which contains a plurality of unidirectionally aligned fiber rovings embedded within a thermoplastic polymer matrix, and surrounded by a capping layer.
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1 - 20 . (canceled) 21 . an electrical cable comprising: (a) a cable core comprising at least one composite core, the composite core comprising: (i) at least one rod comprising a plurality of consolidated thermoplastic impregnated rovings, the rovings comprising carbon fibers and a thermoplastic matrix that embeds the carbon fibers, the carbon fibers having a ratio of ultimate tensile strength to mass per unit length of greater than about 1,000 mpa/g/m, wherein the thermoplastic matrix comprises a polyphenylene sulfide, and wherein the rod comprises from about 30 wt. % to about 75 wt. % carbon fibers; and (ii) a capping layer surrounding the at least one rod, wherein the capping layer contains less than 5 wt. % of carbon fibers; and (b) a plurality of conductive elements surrounding the cable core. 22 . the cable of claim 21 , wherein the cable has: a sag, at rated temperature of 180° c., for a 300-meter level span with a nesc light loading, in a range from about 3 m to about 9.5 m; and/or a sag, at rated temperature of 180° c., for a 300-meter level span with a nesc heavy loading, in a range from about 3 m to about 7.5 m. 23 . the cable of claim 21 , wherein the cable has: a 10-year creep value at 15% rbs (rated breaking stress) of less than about 0.2%; and/or a 10-year creep value at 30% rbs (rated breaking stress) of less than about 0.25%. 24 . the cable of claim 21 , wherein the capping layer: has a thickness in a range from about 0.01 mm to about 10 mm; contains less than about 1 wt. % of carbon fibers; and comprises a polyether ether ketone. 25 . the cable of claim 21 , wherein the cable passes an aeolian vibration test at 100 million cycles. 26 . the cable of claim 21 , further comprising a partial or complete layer of a tape or a coating between the cable core and the plurality of conductive elements. 27 . the cable of claim 21 , wherein: the cable core comprises from 2 to 37 composite cores; and the cable comprises up to 84 conductive elements arranged in 2, 3, or 4 layers around the cable core. 28 . the cable of claim 27 , wherein: the conductive elements comprise copper, a copper alloy, aluminum, an aluminum alloy, or any combination thereof; and the conductive elements have a substantially circular cross-sectional shape or a substantially trapezoidal cross-sectional shape. 29 . the cable of claim 27 , wherein the conductive elements comprise aluminum or an aluminum alloy having an iacs electrical conductivity in a range from about 59% to about 65%. 30 . the cable of claim 27 , wherein the cable comprises 7, 19, 26, or 37 conductive elements. 31 . the cable of claim 21 , wherein the cable is a high voltage overhead transmission cable. 32 . the cable of claim 21 , wherein the composite core has: a flexural modulus of from about 15 to about 200 gpa; an ultimate tensile strength of from about 500 mpa to about 3,500 mpa; and an elastic modulus in a range from about 70 gpa to about 300 gpa. 33 . the cable of claim 21 , wherein the composite core has: a percent elongation at break in a range from about 1% to about 2.5%; and/or a linear thermal expansion coefficient in the longitudinal direction in a range from about −0.4 to about 5 ppm per ° c. 34 . the cable of claim 21 , wherein the composite core has a bending radius in a range from about 1 cm to about 50 cm. 35 . the cable of claim 21 , wherein: the rod comprises from 2 to 20 rovings; and each roving comprises from about 1,000 to about 100,000 individual fibers. 36 . the cable of claim 21 , wherein the composite core has a void fraction of about 4% or less. 37 . the cable of claim 21 , wherein the capping layer has a thickness in a range from about 0.01 mm to about 10 mm and contains less than about 1 wt. % of carbon fibers. 38 . the cable of claim 21 , wherein the capping layer contains 0 wt. % of carbon fibers. 39 . the cable of claim 38 , wherein the capping layer comprises a polyether ether ketone. 40 . the cable of claim 38 , wherein the capping layer has a thickness in a range from about 0.02 mm to about 5 mm.
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reference to related applications this application claims the benefit of u.s. provisional application no. 61/474,423, filed on apr. 12, 2011, and relates to u.s. provisional application no. 61/474,458, filed on apr. 12, 2011, both of which are incorporated herein by reference in their entirety. background of the invention composite wire structures are commonly used as transmission lines or cables for transmitting electricity to users. examples of composite transmission wire constructions include, for instance, aluminum conductor steel reinforced (acsr) cable, aluminum conductor steel supported (acss) cable, aluminum conductor composite reinforced (accr) cable, and aluminum conductor composite core (accc) cable. acsr and acss cables include an aluminum outer conducting layer surrounding a steel inner core. the transmission lines or cables are designed not only to efficiently transmit electricity, but also to be strong and temperature resistant, especially when the transmission lines are strung on towers and stretched over long distances. it would be beneficial to produce cables with a composite core that are capable of achieving the desired strength, durability, and temperature performance demanded by applications such as overhead power transmission cables. accordingly, it is to these ends that the present disclosure is directed. summary of the invention this summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. this summary is not intended to identify required or essential features of the claimed subject matter. nor is this summary intended to be used to limit the scope of the claimed subject matter. embodiments of the present invention may provide cables, e.g., electrical transmission cables for the overhead transmission of electricity, which may contain a cable core and conductive elements surrounding the cable core. the cable core may contain at least one composite core (the composite core also may be referred to as a composite strand or polymer composite strand). these core elements may serve as load-bearing members for the electrical transmission cable and, in some embodiments, these core elements may be non-conductive. in accordance with one embodiment of the present invention, a composite core for the electrical cable is disclosed. generally, the cables and cores disclosed herein may extend in a longitudinal direction. the composite core may comprise at least one rod that comprises a continuous fiber component comprising a plurality of consolidated thermoplastic impregnated rovings (the rod also may be referred to as a fiber core). the rovings may contain continuous fibers oriented in the longitudinal direction, and a thermoplastic matrix that embeds the fibers. the fibers may have a ratio of ultimate tensile strength to mass per unit length of greater than about 1,000 megapascals per gram per meter (mpa/g/m). the continuous fibers may constitute from about 25 wt. % to about 80 wt. % of the rod and the thermoplastic matrix may constitute from about 20 wt. % to about 75 wt. % of the rod. a capping layer may surround the rod, and this capping layer may be free of continuous fibers. the composite core may have a minimum flexural modulus of about 10 gigapascals (gpa). in accordance with another embodiment of the present invention, a method for forming a composite core for an electrical transmission cable is disclosed. the method may comprise impregnating a plurality of rovings with a thermoplastic matrix and consolidating the rovings to form a ribbon, wherein the rovings may comprise continuous fibers oriented in the longitudinal direction. the fibers may have a ratio of ultimate tensile strength to mass per unit length of greater than about 1,000 mpa/g/m. the continuous fibers may constitute from about 25 wt. % to about 80 wt. % of the ribbon, and the thermoplastic matrix may constitute from about 20 wt. % to about 75 wt. % of the ribbon. the ribbon may be heated to a temperature at or above the softening temperature (or melting temperature) of the thermoplastic matrix and pulled through at least one forming die to compress and shape the ribbon into a rod. a capping layer may be applied to the rod to form the composite core. in accordance with yet another embodiment of the present invention, a method of making an electrical cable is disclosed. this method may comprise providing a cable core comprising at least one composite core, and surrounding the cable core with a plurality of conductive elements. the composite core may comprise at least one rod comprising a plurality of consolidated thermoplastic impregnated rovings. the rovings may comprise continuous fibers oriented in the longitudinal direction and a thermoplastic matrix that embeds the fibers. the fibers may have a ratio of ultimate tensile strength to mass per unit length of greater than about 1,000 mpa/g/m. typically, the rod may comprise from about 25 wt. % to about 80 wt. % fibers, and from about 20 wt. % to about 75 wt. % thermoplastic matrix. a capping layer may surround the at least one rod, and this capping layer generally may be free of continuous fibers. in these and other embodiments, the composite core may have a flexural modulus of greater than about 10 gpa. both the foregoing summary and the following detailed description provide examples and are explanatory only. accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. further, features or variations may be provided in addition to those set forth herein. for example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description. brief description of the drawings the accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate various aspects and embodiments of the present invention. in the drawings: fig. 1 is a perspective view of one embodiment of a consolidated ribbon for use in the present invention; fig. 2 is a cross-sectional view of another embodiment of a consolidated ribbon for use in the present invention; fig. 3 is a schematic illustration of one embodiment of an impregnation system for use in the present invention; fig. 4 is a cross-sectional view of the impregnation die shown in fig. 3 ; fig. 5 is an exploded view of one embodiment of a manifold assembly and gate passage for an impregnation die that may be employed in the present invention; fig. 6 is a perspective view of one embodiment of a plate at least partially defining an impregnation zone that may be employed in the present invention; fig. 7 is a schematic illustration of one embodiment of a pultrusion system that may be employed in the present invention; fig. 8 is a perspective view of one embodiment of a composite core of the present invention; and fig. 9 is a perspective view of one embodiment of an electrical transmission cable of the present invention; fig. 10 is a perspective view of another embodiment of an electrical transmission cable of the present invention; fig. 11 is a top cross-sectional view of one embodiment of various calibration dies that may be employed in accordance with the present invention; fig. 12 is a side cross-sectional view of one embodiment of a calibration die that may be employed in accordance with the present invention; fig. 13 is a front view of a portion of one embodiment of a calibration die that may be employed in accordance with the present invention; fig. 14 is a front view of one embodiment of forming rollers that may be employed in accordance with the present invention; fig. 15 is a perspective view of the electrical cable of examples 6-7; fig. 16 is a stress-strain diagram for the electrical cable of example 7; and fig. 17 is a perspective view of the electrical cable of constructive example 8. detailed description of the invention the following detailed description refers to the accompanying drawings. wherever possible, the same or similar reference numbers are used in the drawings and the following description to refer to the same or similar elements or features. while aspects and embodiments of the invention may be described, modifications, adaptations, and other implementations are possible. for example, substitutions, additions, or modifications may be made to the elements illustrated in the drawings, and the methods described herein may be modified by substituting, reordering, or adding stages to the disclosed methods. accordingly, the following detailed description and its exemplary embodiments do not limit the scope of the invention. the present invention is directed generally to electrical cables, such as high voltage overhead transmission lines, and to the composite cores contained within these electrical cables. in certain embodiments of the invention, an electrical cable may comprise a cable core comprising at least one composite core (or composite strand), and a plurality of conductive elements surrounding the cable core. composite core the composite core may contain a rod (or fiber core) comprising a continuous fiber component, surrounded by a capping layer. the rod may comprise a plurality of unidirectionally aligned fiber rovings embedded within a thermoplastic polymer matrix. while not wishing to be bound by theory, applicants believe that the degree to which the rovings are impregnated with the thermoplastic polymer matrix may be significantly improved through selective control over the impregnation process, and also through control over the degree of compression imparted to the rovings during formation and shaping of the rod, as well as the calibration of the final rod geometry. such a well impregnated rod may have a very small void fraction, which may lead to excellent strength properties. notably, the desired strength properties may be achieved without the need for different fiber types in the rod. as used herein, the term “roving” generally refers to a bundle or tow of individual fibers. the fibers contained within the roving may be twisted or may be straight. although different fibers may be used in individual or different rovings, it may be beneficial for each of the rovings to contain a single fiber type to minimize any adverse impact of using materials having different thermal expansion coefficients. the continuous fibers employed in the rovings may possess a high degree of tensile strength relative to their mass. for example, the ultimate tensile strength of the fibers typically may be in a range from about 1,000 to about 15,000 megapascals (mpa), in some embodiments from about 2,000 mpa to about 10,000 mpa, and in some embodiments, from about 3,000 mpa to about 6000 mpa. such tensile strengths may be achieved even though the fibers are of a relatively light weight, such as a mass per unit length of from about 0.1 to about 2 grams per meter (g/m), in some embodiments from about 0.4 to about 1.5 g/m. the ratio of tensile strength to mass per unit length thus may be about 1,000 megapascals per gram per meter (mpa/g/m) or greater, in some embodiments about 4,000 mpa/g/m or greater, and in some embodiments, from about 5,500 to about 20,000 mpa/g/m. such high strength fibers may, for instance, be metal fibers, glass fibers (e.g., e-glass, a-glass, c-glass, d-glass, ar-glass, r-glass, s1-glass, s2-glass, etc.), carbon fibers (e.g., amorphous carbon, graphitic carbon, or metal-coated carbon, etc.), boron fibers, ceramic fibers (e.g., alumina or silica), aramid fibers (e.g., kevlar® marketed by e. i. dupont de nemours, wilmington, del.), synthetic organic fibers (e.g., polyamide, polyethylene, paraphenylene, terephthalamide, polyethylene terephthalate and polyphenylene sulfide), and various other natural or synthetic inorganic or organic fibrous materials known for reinforcing thermoplastic and/or thermoset compositions. carbon fibers may be particularly suitable for use as the continuous fibers, which typically have a tensile strength to mass per unit length ratio in the range of from about 5,000 to about 7,000 mpa/g/m. often, the continuous fibers may have a nominal diameter of about 4 to about 35 micrometers (μm), and in some embodiments, from about 5 to about 35 μm. the number of fibers contained in each roving may be constant or may vary from roving to roving. typically, a roving may contain from about 1,000 fibers to about 100,000 individual fibers, and in some embodiments, from about 5,000 to about 50,000 fibers. any of a variety of thermoplastic polymers may be employed to form the thermoplastic matrix in which the continuous fibers are embedded. suitable thermoplastic polymers for use in the present invention may include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (pbt)), polycarbonates, polyam ides (e.g., nylon™) polyether ketones (e.g., polyetherether ketone (peek)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (ppdk)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (pps), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (abs)), and the like, or combinations thereof. generally, the properties of the thermoplastic matrix may be selected to achieve a desired combination of processability and end-use performance of the composite core. for example, the melt viscosity of the thermoplastic matrix generally may be low enough so that the polymer may adequately impregnate the fibers and become shaped into the rod configuration. in this regard, the melt viscosity typically may range from about 25 to about 2,000 pascal-seconds (pa-s), in some embodiments from 50 about 500 pa-s, and in some embodiments, from about 60 to about 200 pa-s, determined at the operating conditions used for the thermoplastic polymer (e.g., about 360° c.). likewise, because the core may be used at high temperatures (e.g., in high voltage transmission cables), a thermoplastic polymer having a relatively high melting temperature may be employed. for example, the melting temperature of such high temperature polymers may be in a range from about 200° c. to about 500° c., in some embodiments from about 225° c. to about 400° c., and in some embodiments, from about 250° c. to about 350° c. in particular embodiments contemplated herein, polyarylene sulfides may be used in the present invention as a high temperature matrix with the desired melt viscosity. polyphenylene sulfide, for example, is a semi-crystalline resin that generally includes repeating monomeric units represented by the following general formula: these monomeric units may constitute at least 80 mole %, and in some embodiments, at least 90 mole %, of the recurring units, in the polymer. it should be understood, however, that the polyphenylene sulfide may contain additional recurring units, such as described in u.s. pat. no. 5,075,381 to gotoh, et al., which is incorporated herein in its entirety by reference thereto for all purposes. when employed, such additional recurring units typically may constitute less than about 20 mole % of the polymer. commercially available high melt viscosity polyphenylene sulfides may include those available from ticona, llc (florence, ky.) under the trade designation fortron®. such polymers may have a melting temperature of about 285° c. (determined according to iso 11357-1,2,3) and a melt viscosity of from about 260 to about 320 pa-s at 310° c. according to the present invention, an extrusion device generally may be employed to impregnate the rovings with the thermoplastic matrix. among other things, the extrusion device may facilitate the application of the thermoplastic polymer to the entire surface of the fibers. the impregnated rovings also may have a very low void fraction, which may increase the resulting strength of the rod. for instance, the void fraction may be about 6% or less, in some embodiments about 4% or less, in some embodiments about 3% or less, in some embodiments about 2% or less, in some embodiments about 1% or less, and in some embodiments, about 0.5% or less. the void fraction may be measured using techniques well known to those skilled in the art. for example, the void fraction may be measured using a “resin burn off” test in which samples are placed in an oven (e.g., at 600° c. for 3 hours) to burn off the resin. the mass of the remaining fibers may then be measured to calculate the weight and volume fractions. such “burn off” testing may be performed in accordance with astm d 2584-08 to determine the weights of the fibers and the thermoplastic matrix, which may then be used to calculate the “void fraction” based on the following equations: v f =100*(ρ t −ρ c )/ρ t where, v f is the void fraction as a percentage; ρ c is the density of the composite as measured using known techniques, such as with a liquid or gas pycnometer (e.g., helium pycnometer); ρ t is the theoretical density of the composite as is determined by the following equation: ρ t =1/[ w f /ρ f +w m /ρ m ] ρ m is the density of the thermoplastic matrix (e.g., at the appropriate crystallinity); ρ f is the density of the fibers; w f is the weight fraction of the fibers; and w m is the weight fraction of the thermoplastic matrix. alternatively, the void fraction may be determined by chemically dissolving the resin in accordance with astm d 3171-09. the “burn off” and “dissolution” methods may be particularly suitable for glass fibers, which are generally resistant to melting and chemical dissolution. in other cases, however, the void fraction may be indirectly calculated based on the densities of the thermoplastic polymer, fibers, and ribbon (or tape) in accordance with astm d 2734-09 (method a), where the densities may be determined by astm d792-08 method a. of course, the void fraction also may be estimated using conventional microscopy equipment, or through the use of computed tomography (ct) scan equipment, such as a metrotom 1500 (2 k×2 k) high resolution detector. referring to fig. 3 , one embodiment of an extrusion device is shown. more particularly, the apparatus may include an extruder 120 containing a screw shaft 124 mounted inside a barrel 122 . a heater 130 (e.g., an electrical resistance heater) may be mounted outside the barrel 122 . during use, a thermoplastic polymer feedstock 127 may be supplied to the extruder 120 through a hopper 126 . the thermoplastic feedstock 127 may be conveyed inside the barrel 122 by the screw shaft 124 and heated by frictional forces inside the barrel 122 and by the heater 130 . upon being heated, the feedstock 127 may exit the barrel 122 through a barrel flange 128 and enter a die flange 132 of an impregnation die 150 . a continuous fiber roving 142 or a plurality of continuous fiber rovings 142 may be supplied from a reel or reels 144 to die 150 . generally, the rovings 142 may be kept apart a certain distance before impregnation, such as at least about 4 mm, and in some embodiments, at least about 5 mm. the feedstock 127 may further be heated inside the die by heaters 133 mounted in or around the die 150 . the die generally may be operated at temperatures that are sufficient to cause melting and impregnation of the thermoplastic polymer. typically, the operation temperatures of the die may be higher than the melt temperature of the thermoplastic polymer, such as at temperatures from about 200° c. to about 450° c. when processed in this manner, the continuous fiber rovings 142 may become embedded in the polymer matrix, which may be a resin 214 ( fig. 4 ) processed from the feedstock 127 . the mixture then may be extruded from the impregnation die 150 to create an extrudate 152 . a pressure sensor 137 ( fig. 3 ) may monitor the pressure near the impregnation die 150 , so that the extruder 120 can be operated to deliver a correct amount of resin 214 for interaction with the fiber rovings 142 . the rate of extrusion may be varied by controlling the rotational speed of the screw shaft 124 and/or feed rate of the feedstock 127 . the extruder 120 may be operated to produce the extrudate 152 (impregnated fiber rovings), which after leaving the impregnation die 150 , may enter an optional pre-shaping or guiding section (not shown), before entering a nip formed between two adjacent rollers 190 . the rollers 190 may help to consolidate the extrudate 152 into the form of a ribbon (or tape), as well as to enhance fiber impregnation and to squeeze out any excess voids. in addition to the rollers 190 , other shaping devices also may be employed, such as a die system. the resulting consolidated ribbon 156 may be pulled by tracks 162 and 164 mounted on rollers. the tracks 162 and 164 also may pull the extrudate 152 from the impregnation die 150 and through the rollers 190 . if desired, the consolidated ribbon 156 may be wound up at a section 171 . generally speaking, the ribbons may be relatively thin and may have a thickness of from about 0.05 to about 1 millimeter (mm), in some embodiments from about 0.1 to about 0.8 mm, and in some embodiments, from about 0.2 to about 0.4 mm. within the impregnation die, it may be beneficial that the rovings 142 are traversed through an impregnation zone 250 to impregnate the rovings with the polymer resin 214 . in the impregnation zone 250 , the polymer resin may be forced generally transversely through the rovings by shear and pressure created in the impregnation zone 250 , which may significantly enhance the degree of impregnation. this may be particularly useful when forming a composite from ribbons of a high fiber content, such as about 35% weight fraction (wf) or more, and in some embodiments, from about 40% wf or more. typically, the die 150 may include a plurality of contact surfaces 252 , such as, for example, at least 2, at least 3, from 4 to 7, from 2 to 20, from 2 to 30, from 2 to 40, from 2 to 50, or more contact surfaces 252 , to create a sufficient degree of penetration and pressure on the rovings 142 . although their particular form may vary, the contact surfaces 252 typically may possess a curvilinear surface, such as a curved lobe, rod, etc. the contact surfaces 252 typically may be made of a metal material. fig. 4 shows a cross-sectional view of an impregnation die 150 . as shown, the impregnation die 150 may include a manifold assembly 220 , a gate passage 270 , and an impregnation zone 250 . the manifold assembly 220 may be provided for flowing the polymer resin 214 therethrough. for example, the manifold assembly 220 may include a channel 222 or a plurality of channels 222 . the resin 214 provided to the impregnation die 150 may flow through the channels 222 . as shown in fig. 5 , some portions of the channels 222 may be curvilinear, and in exemplary embodiments, the channels 222 may have a symmetrical orientation along a central axis 224 . further, in some embodiments, the channels may be a plurality of branched runners 222 , which may include first branched runner group 232 , second group 234 , third group 236 , and, if desired, more branched runner groups. each group may include 2, 3, 4 or more runners 222 branching off from runners 222 in the preceding group, or from an initial channel 222 . the branched runners 222 and the symmetrical orientation thereof may evenly distribute the resin 214 , such that the flow of resin 214 exiting the manifold assembly 220 and coating the rovings 142 may be substantially uniformly distributed on the rovings 142 . beneficially, this may result in generally uniform impregnation of the rovings 142 . further, the manifold assembly 220 may in some embodiments define an outlet region 242 , which generally encompasses at least a downstream portion of the channels or runners 222 from which the resin 214 exits. in some embodiments, at least a portion of the channels or runners 222 disposed in the outlet region 242 may have an increasing area in a flow direction 244 of the resin 214 . the increasing area may permit diffusion and further distribution of the resin 214 as the resin 214 flows through the manifold assembly 220 , which may further result in substantially uniform distribution of the resin 214 on the rovings 142 . as further illustrated in figs. 4 and 5 , after flowing through the manifold assembly 220 , the resin 214 may flow through gate passage 270 . gate passage 270 may be positioned between the manifold assembly 220 and the impregnation zone 250 , and may be configured for flowing the resin 214 from the manifold assembly 220 such that the resin 214 coats the rovings 142 . thus, resin 214 exiting the manifold assembly 220 , such as through outlet region 242 , may enter gate passage 270 and flow therethrough, as shown. upon exiting the manifold assembly 220 and the gate passage 270 of the die 150 as shown in fig. 4 , the resin 214 may contact the rovings 142 being traversed through the die 150 . as discussed above, the resin 214 may substantially uniformly coat the rovings 142 , due to distribution of the resin 214 in the manifold assembly 220 and the gate passage 270 . further, in some embodiments, the resin 214 may impinge on an upper surface of each of the rovings 142 , or on a lower surface of each of the rovings 142 , or on both an upper and lower surface of each of the rovings 142 . initial impingement on the rovings 142 may provide for further impregnation of the rovings 142 with the resin 214 . as shown in fig. 4 , the coated rovings 142 may traverse in run direction 282 through impregnation zone 250 , which is configured to impregnate the rovings 142 with the resin 214 . for example, as shown in figs. 4 and 6 , the rovings 142 may be traversed over contact surfaces 252 in the impregnation zone. impingement of the rovings 142 on the contact surface 252 may create shear and pressure sufficient to impregnate the rovings 142 with the resin 214 , thereby coating the rovings 142 . in some embodiments, as shown in fig. 4 , the impregnation zone 250 may be defined between two spaced apart opposing plates 256 and 258 . first plate 256 may define a first inner surface 257 , while second plate 258 may define a second inner surface 259 . the contact surfaces 252 may be defined on or extend from both the first and second inner surfaces 257 and 259 , or only one of the first and second inner surfaces 257 and 259 . fig. 6 illustrates the second plate 258 and the various contact surfaces thereon that may form at least a portion of the impregnation zone 250 according to these embodiments. in exemplary embodiments, as shown in fig. 4 , the contact surfaces 252 may be defined alternately on the first and second surfaces 257 and 259 such that the rovings alternately impinge on contact surfaces 252 on the first and second surfaces 257 and 259 . thus, the rovings 142 may pass contact surfaces 252 in a waveform, tortuous, or sinusoidal-type pathway, which enhances shear. angle 254 at which the rovings 142 traverse the contact surfaces 252 may be generally high enough to enhance shear, but not so high as to cause excessive forces that will break the fibers. thus, for example, the angle 254 may be in the range between approximately 1° and approximately 30°, and in some embodiments, between approximately 5° and approximately 25°. in alternative embodiments, the impregnation zone 250 may include a plurality of pins (not shown), each pin having a contact surface 252 . the pins may be static, freely rotational, or rotationally driven. in further alternative embodiments, the contact surfaces 252 and impregnation zone 250 may comprise any suitable shapes and/or structures for impregnating the rovings 142 with the resin 214 as desired or required. to further facilitate impregnation of the rovings 142 , they also may be kept under tension while present within the impregnation die. the tension may, for example, range from about 5 to about 300 newtons (n), in some embodiments from about 50 to about 250 n, and in some embodiments, from about 100 to about 200 n, per roving 142 or tow of fibers. as shown in fig. 4 , in some embodiments, a land zone 280 may be positioned downstream of the impregnation zone 250 in run direction 282 of the rovings 142 . the rovings 142 may traverse through the land zone 280 before exiting the die 150 . as further shown in fig. 4 , in some embodiments, a faceplate 290 may adjoin the impregnation zone 250 . faceplate 290 may be generally configured to meter excess resin 214 from the rovings 142 . thus, apertures in the faceplate 290 , through which the rovings 142 traverse, may be sized such that when the rovings 142 are traversed therethrough, the size of the apertures may cause excess resin 214 to be removed from the rovings 142 . the impregnation die shown and described above is but one of various possible configurations that may be employed in the present invention. in alternative embodiments, for example, the rovings may be introduced into a crosshead die that may be positioned at an angle relative to the direction of flow of the polymer melt. as the rovings move through the crosshead die and reach the point where the polymer exits from an extruder barrel, the polymer may be forced into contact with the rovings. examples of such a crosshead die extruder are described, for instance, in u.s. pat. no. 3,993,726 to moyer, u.s. pat. no. 4,588,538 to chung, et al.; u.s. pat. no. 5,277,566 to augustin, et al.; and u.s. pat. no. 5,658,513 to amaike, et al., which are incorporated herein in their entirety by reference thereto for all purposes. it should also be understood that any other extruder design also may be employed, such as a twin screw extruder. still further, other components optionally may be employed to assist in the impregnation of the fibers. for example, a “gas jet” assembly may be employed in certain embodiments to help uniformly spread a roving of individual fibers, which may each contain up to as many as 24,000 fibers, across the entire width of the merged tow. this may help achieve uniform distribution of strength properties. such an assembly may include a supply of compressed air or another gas that may impinge in a generally perpendicular fashion on the moving rovings that pass across the exit ports. the spread rovings then may be introduced into a die for impregnation, such as described above. regardless of the technique employed, the continuous fibers may be oriented in the longitudinal direction (the machine direction “a” of the system of fig. 3 ) to enhance tensile strength. besides fiber orientation, other aspects of the pultrusion process also may be controlled to achieve the desired strength. for example, a relatively high percentage of continuous fibers may be employed in the consolidated ribbon to provide enhanced strength properties. for instance, continuous fibers typically may constitute from about 25 wt. % to about 80 wt. %, in some embodiments from about 30 wt. % to about 75 wt. %, and in some embodiments, from about 35 wt. % to about 60 wt. % of the ribbon. likewise, thermoplastic polymer(s) typically may constitute from about 20 wt. % to about 75 wt. %, in some embodiments from about 25 wt. % to about 70 wt. %, and in some embodiments, from about 40 wt. % to about 65 wt. % of the ribbon. the percentage of the fibers and thermoplastic matrix in the final rod also may be within the ranges noted above. as noted above, the rovings may be consolidated into the form of one or more ribbons before being shaped into the desired rod configuration. when such a ribbon is subsequently compressed, the rovings may become distributed in a generally uniform manner about a longitudinal center of the rod. such a uniform distribution enhances the consistency of the strength properties (e.g., flexural modulus, ultimate tensile strength, etc.) over the entire length of the rod. when employed, the number of consolidated ribbons used to form the rod may vary based on the desired thickness and/or cross-sectional area and strength of the rod, as well as the nature of the ribbons themselves. in most cases, however, the number of ribbons may be from 1 to 20, and in some embodiments, from 2 to 10. the number of rovings employed in each ribbon may likewise vary. typically, however, a ribbon may contain from 2 to 10 rovings, and in some embodiments, from 3 to 5 rovings. to help achieve the symmetric distribution of the rovings in the final rod, it may be beneficial that they are spaced apart approximately the same distance from each other within the ribbon. referring to fig. 1 , for example, one embodiment of a consolidated ribbon 4 is shown that contains three (3) rovings 5 spaced equidistant from each other in the −x direction. in other embodiments, however, it may be desired that the rovings are combined, such that the fibers of the rovings are generally evenly distributed throughout the ribbon 4 . in these embodiments, the rovings may be generally indistinguishable from each other. referring to fig. 2 , for example, one embodiment of a consolidated ribbon 4 is shown that contains rovings that are combined such that the fibers are generally evenly distributed throughout. the specific manner in which the rovings are shaped also may be carefully controlled to ensure that rod may be formed with an adequate degree of compression and strength properties. referring to fig. 7 , for example, one particular embodiment of a system and method for forming a rod is shown. in this embodiment, two ribbons 12 initially may be provided in a wound package on a creel 20 . the creel 20 may be an unreeling creel that includes a frame provided with horizontal spindles 22 , each supporting a package. a pay-out creel also may be employed, particularly if desired to induce a twist into the fibers, such as when using raw fibers in a one-step configuration. it should also be understood that the ribbons also may be formed in-line with the formation of the rod. in one embodiment, for example, the extrudate 152 exiting the impregnation die 150 from fig. 3 may be supplied directly to the system used to form a rod. a tension-regulating device 40 also may be employed to help control the degree of tension in the ribbons 12 . the device 40 may include inlet plate 30 that lies in a vertical plane parallel to the rotating spindles 22 of the creel 20 and/or perpendicular to the incoming ribbons. the tension-regulating device 40 may contain cylindrical bars 41 arranged in a staggered configuration so that the ribbon 12 may pass over and under these bars to define a wave pattern. the height of the bars may be adjusted to modify the amplitude of the wave pattern and control tension. the ribbons 12 may be heated in an oven 45 before entering a consolidation die 50 . heating may be conducted using any known type of oven, such as an infrared oven, a convection oven, etc. during heating, the fibers in the ribbon may be unidirectionally oriented to optimize the exposure to the heat and maintain even heat across the entire ribbon. the temperature to which the ribbons 12 are heated generally may be high enough to soften the thermoplastic polymer to an extent that the ribbons may bond together. however, the temperature may not be so high as to destroy the integrity of the material. the temperature may, for example, range from about 100° c. to about 500° c., in some embodiments from about 200° c. to about 400° c., and in some embodiments, from about 250° c. to about 350° c. in one particular embodiment, for example, polyphenylene sulfide (“pps”) may be used as the polymer, and the ribbons may be heated to or above the melting point of pps, which may be about 285° c. upon being heated, the ribbons 12 may be provided to a consolidation die 50 that may compress them together into a preform 14 , as well as may align and form the initial shape of the rod. as shown generally in fig. 7 , for example, the ribbons 12 may be guided through a flow passage 51 of the die 50 in a direction “a” from an inlet 53 to an outlet 55 . the passage 51 may have any of a variety of shapes and/or sizes to achieve the rod configuration. for example, the channel and rod configuration may be circular, elliptical, parabolic, trapezoidal, rectangular, etc. within the die 50 , the ribbons generally may be maintained at a temperature at or above the melting point of the thermoplastic matrix used in the ribbon to ensure adequate consolidation. the desired heating, compression, and shaping of the ribbons 12 may be accomplished through the use of a die 50 having one or multiple sections. for instance, although not shown in detail herein, the consolidation die 50 may possess multiple sections that function together to compress and shape the ribbons 12 into the desired configuration. for instance, a first section of the passage 51 may be a tapered zone that initially may shape the material as it flows into the die 50 . the tapered zone generally may possess a cross-sectional area that is larger at its inlet than at its outlet. for example, the cross-sectional area of the passage 51 at the inlet of the tapered zone may be about 2% or more, in some embodiments about 5% or more, and in some embodiments, from about 10% to about 20% greater than the cross-sectional area at the outlet of the tapered zone. regardless, the cross-section of the flow passage typically may change gradually and smoothly within the tapered zone so that a balanced flow of the composite material through the die may be maintained. a shaping zone may follow the tapered zone, and may compress the material and provide a generally homogeneous flow therethrough. the shaping zone also may pre-shape the material into an intermediate shape that is similar to that of the rod, but typically of a larger cross-sectional area to allow for expansion of the thermoplastic polymer while heated to minimize the risk of backup within the die 50 . the shaping zone also may include one or more surface features that impart a directional change to the preform. the directional change may force the material to be redistributed, resulting in a more even distribution of the fiber/resin in the final shape. this also may reduce the risk of dead spots in the die that may cause burning of the resin. for example, the cross-sectional area of the passage 51 at a shaping zone may be about 2% or more, in some embodiments about 5% or more, and in some embodiments, from about 10% to about 20% greater than the width of the preform 14 . a die land also may follow the shaping zone to serve as an outlet for the passage 51 . the shaping zone, tapered zone, and/or die land may be heated to a temperature at or above that of the glass transition temperature or melting point of the thermoplastic matrix. if desired, a second die 60 (e.g., a calibration die) also may be employed to compress the preform 14 into the final shape of the rod. when employed, it may be beneficial to allow the preform 14 to cool briefly after exiting the consolidation die 50 and before entering the optional second die 60 . this may allow the consolidated preform 14 to retain its initial shape before progressing further through the system. typically, cooling may reduce the temperature of the exterior of the rod below the melting point temperature of the thermoplastic matrix to minimize and substantially prevent the occurrence of melt fracture on the exterior surface of the rod. the internal section of the rod, however, may remain molten to ensure compression when the rod enters the calibration die body. such cooling may be accomplished by simply exposing the preform 14 to the ambient atmosphere (e.g., room temperature) or through the use of active cooling techniques (e.g., water bath or air cooling) as is known in the art. in one embodiment, for example, air may blown onto the preform 14 (e.g., with an air ring). the cooling between these stages, however, generally may occur over a small period of time to ensure that the preform 14 still may be soft enough to be further shaped. for example, after exiting the consolidation die 50 , the preform 14 may be exposed to the ambient environment for only from about 1 to about 20 seconds, and in some embodiments, from about 2 to about 10 seconds, before entering the second die 60 . within the die 60 , the preform generally may be kept at a temperature below the melting point of the thermoplastic matrix used in the ribbon so that the shape of the rod can be maintained. although referred to above as single dies, it should be understood that the dies 50 and 60 may in fact be formed from multiple individual dies (e.g., face plate dies). thus, in some embodiments, multiple individual dies 60 may be utilized to gradually shape the material into the desired configuration. the dies 60 may be placed in series, and provide for gradual decreases in the dimensions of the material. such gradual decreases may allow for shrinkage during and between the various steps. for example, as shown in figs. 11 through 13 , a first die 60 may include one or more inlets 62 and corresponding outlets 64 , as shown. any number of inlets 62 and corresponding outlets 64 may be included in a die 60 , such as four as shown, or one, two, three, five, six, or more. an inlet 62 in some embodiments may be generally oval or circular shaped. in other embodiments, the inlet 62 may have a curved rectangular shape, i.e., a rectangular shape with curved corners or a rectangular shape with straight longer sidewalls and curved shorter sidewalls. further, an outlet 64 may be generally oval or circular shaped, or may have a curved rectangular shape. in some embodiments wherein an oval shaped inlet is utilized, the inlet 62 may have a major axis length 66 to minor axis length 68 ratio in a range between approximately 3:1 and approximately 5:1. in some embodiments wherein an oval or circular shaped inlet is utilized, the outlet 64 may have a major axis length 66 to minor axis length 68 ratio in a range between approximately 1:1 and approximately 3:1. in embodiments wherein a curved rectangular shape is utilized, the inlet and outlet may have major axis length 66 to minor axis length 66 ratios (aspect ratios) between approximately 2:1 and approximately 7:1, and the outlet 64 ratio may be less than the inlet 62 ratio. in further embodiments, the cross-sectional area of an inlet 62 and the cross-sectional area of a corresponding outlet 64 of the first die 60 may have a ratio in a range between approximately 1.5:1 and 6:1. the first die 60 thus may provide a generally smooth transformation of polymer impregnated fiber material to a shape that is relatively similar to a final shape of the resulting rod, which in exemplary embodiments has a circular or oval shaped cross-section. subsequent dies, such as a second die 60 and third die 60 as shown in fig. 11 , may provide for further gradual decreases and/or changes in the dimensions of the material, such that the shape of the material is converted to a final cross-sectional shape of the rod. these subsequent dies 60 may both shape and cool the material. for example, in some embodiments, each subsequent die 60 may be maintained at a lower temperature than the previous dies. in exemplary embodiments, all dies 60 may be maintained at temperatures that are higher than a softening point temperature for the material. in further exemplary embodiments, dies 60 having relatively long land lengths 69 may be desired, due to, for example, proper cooling and solidification, which may be important in achieving a desired rod shape and size. relatively long land lengths 69 may reduce stresses and provide smooth transformations to desired shapes and sizes, and with minimal void fraction and bow characteristics. in some embodiments, for example, a ratio of land length 69 at an outlet 64 to major axis length 66 at the outlet 64 for a die 60 may be in the range between 0 and approximately 20, such as between approximately 2 and approximately 6. the use of calibration dies 60 according to the present disclosure may provide for gradual changes in material cross-section, as discussed. these gradual changes may in exemplary embodiments ensure that the resulting product, such as a rod or other suitable product, has a generally uniform fiber distribution with relatively minimal void fraction. it should be understood that any suitable number of dies 60 may be utilized to gradually form the material into a profile having any suitable cross-sectional shape, as desired or as required by various end-use applications. in addition to the use of one or more dies, other mechanisms also may be employed to help compress the preform 14 into the shape of a rod. for example, forming rollers 90 , as shown in fig. 14 , may be employed between the consolidation die 50 and the calibration die 60 , between the various calibration dies 60 , and/or after the calibration dies 60 to further compress the preform 14 before it is converted into its final shape. the rollers may have any configuration, such as pinch rollers, overlapping rollers, etc., and may be vertical as shown or horizontal rollers. depending on the roller 90 configuration, the surfaces of the rollers 90 may be machined to impart the dimensions of the final product, such as the rod, core, profile, or other suitable product, to the preform 14 . in an exemplary embodiment, the pressure of the rollers 90 may be adjustable to optimize the quality of the final product. the rollers 90 in exemplary embodiments, such as at least the portions contacting the material, may have generally smooth surfaces. for example, relatively hard, polished surfaces may be beneficial in many embodiments. for example, the surface of the rollers may be formed from a relatively smooth chrome or other suitable material. this may allow the rollers 90 to manipulate the preform 14 without damaging or undesirably altering the preform 14 . for example, such surfaces may prevent the material from sticking to the rollers, and the rollers may impart smooth surfaces onto the materials. in some embodiments, the temperature of the rollers 90 may be controlled. this may be accomplished by heating of the rollers 90 themselves, or by placing the rollers 90 in a temperature controlled environment. further, in some embodiments, surface features 92 may be provided on the rollers 90 . the surface features 92 may guide and/or control the preform 14 in one or more directions as it is passed through the rollers. for example, surface features 92 may be provided to prevent the preform 14 from folding over on itself as it is passed through the rollers 90 . thus, the surface features 92 may guide and control deformation of the preform 14 in the cross-machine direction relative to the machine direction a as well as in the vertical direction relative to the machine direction a. the preform 14 thus may be pushed together in the cross-machine direction, rather than folded over on itself, as it is passed through the rollers 90 in the machine direction a. in some embodiments, tension regulation devices may be provided in communication with the rollers. these devices may be utilized with the rollers to apply tension to the preform 14 in the machine direction, cross-machine direction, and/or vertical direction to further guide and/or control the preform. as indicated above, the resulting rod also may be applied with a capping layer to protect it from environmental conditions and/or to improve wear resistance. referring again to fig. 7 , for example, such a capping layer may be applied via an extruder oriented at any desired angle to introduce a thermoplastic resin into a capping die 72 . to help prevent a galvanic response, it may be beneficial for the capping material to have a dielectric strength of at least about 1 kv per millimeter (kv/mm), in some embodiments at least about 2 kv/mm, in some embodiments from about 3 kv/mm to about 50 kv/mm, and in some embodiments, from about 4 kv/mm to about 30 kv/mm, such as determined in accordance with astm d149-09. suitable thermoplastic polymers for this purpose may include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (pbt)), polycarbonates, polyamides (e.g., nylon™) polyether ketones (e.g., polyetherether ketone (peek)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (ppdk)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (pps), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (abs)), acrylic polymers, polyvinyl chloride (pvc), etc. particularly suitable high dielectric strength capping layer materials may include polyketone (e.g., polyetherether ketone (peek)), polysulfide (e.g., polyarylene sulfide), or a mixture thereof. the capping layer generally may be “free” of continuous fibers. that is, the capping layer may contain “less than about 10 wt. %” of continuous fibers, in some embodiments about 5 wt. % or less of continuous fibers, and in some embodiments, about 1 wt. % or less of continuous fibers (e.g., 0 wt. %). nevertheless, the capping layer may contain other additives for improving the final properties of the composite core. additive materials employed at this stage may include those that are not suitable for incorporating into the continuous fiber material. for instance, it may be beneficial to add pigments to reduce finishing labor, or it may be beneficial to add flame retardant agents to enhance the flame retardancy of the core. because many additive materials may be heat sensitive, an excessive amount of heat may cause them to decompose and produce volatile gases. therefore, if a heat sensitive additive material is extruded with an impregnation resin under high heating conditions, the result may be a complete degradation of the additive material. additive materials may include, for instance, mineral reinforcing agents, lubricants, flame retardants, blowing agents, foaming agents, ultraviolet light resistant agents, thermal stabilizers, pigments, and combinations thereof. suitable mineral reinforcing agents may include, for instance, calcium carbonate, silica, mica, clays, talc, calcium silicate, graphite, calcium silicate, alumina trihydrate, barium ferrite, and combinations thereof. while not shown in detail herein, the capping die 72 may include various features known in the art to help achieve the desired application of the capping layer. for instance, the capping die 72 may include an entrance guide that aligns the incoming rod. the capping die also may include a heating mechanism (e.g., heated plate) that pre-heats the rod before application of the capping layer to help ensure adequate bonding. following capping, the shaped part 15 then may be finally cooled using a cooling system 80 as is known in the art. the cooling system 80 may, for instance, be a sizing system that includes one or more blocks (e.g., aluminum blocks) that may completely encapsulate the composite core while a vacuum pulls the hot shape out against its walls as it cools. a cooling medium may be supplied to the sizer, such as air or water, to solidify the composite core in the correct shape. even if a sizing system is not employed, it may be beneficial to cool the composite core after it exits the capping die (or the consolidation or calibration die, if capping is not applied). cooling may occur using any technique known in the art, such a water tank, cool air stream or air jet, cooling jacket, an internal cooling channel, cooling fluid circulation channels, etc. regardless, the temperature at which the material is cooled may be controlled to achieve certain mechanical properties, part dimensional tolerances, good processing, and an aesthetically pleasing composite. for instance, if the temperature of the cooling station is too high, the material might swell in the tool and interrupt the process. for semi-crystalline materials, too low of a temperature likewise may cause the material to cool down too rapidly and not allow complete crystallization, thereby adversely affecting the mechanical and chemical resistance properties of the composite. multiple cooling die sections with independent temperature control may be utilized to impart a beneficial balance of processing and performance attributes. in one particular embodiment, for example, a water tank may be employed at a temperature of from about 0° c. to about 30° c., in some embodiments from about 1° c. to about 20° c., and in some embodiments, from about 2° c. to about 15° c. if desired, one or more sizing blocks (not shown) also may be employed, such as after capping. such blocks may contain openings that are cut to the exact core shape, graduated from oversized at first to the final core shape. as the composite core passes therethrough, any tendency for it to move or sag may be counteracted, and it may be pushed back (repeatedly) to its correct shape. once sized, the composite core may be cut to the desired length at a cutting station (not shown), such as with a cut-off saw capable of performing cross-sectional cuts, or the composite core may be wound on a reel in a continuous process. the length of rod and/or the composite core may be limited to the length of the fiber tow. as will be appreciated, the temperature of the rod or composite core as it advances through any section of the system of the present invention may be controlled to yield certain manufacturing and final composite properties. any or all of the assembly sections may be temperature controlled utilizing electrical cartridge heaters, circulated fluid cooling, etc., or any other temperature controlling device known to those skilled in the art. referring again to fig. 7 , a pulling device 82 may be positioned downstream from the cooling system 80 to pull the finished composite core 16 through the system for final sizing of the composite. the pulling device 82 may be any device capable of pulling the core through the process system at a desired rate. typical pulling devices may include, for example, caterpillar pullers and reciprocating pullers. one embodiment of the composite core (or composite strand) formed from the method described above is shown in more detail in fig. 8 as element 516 . as illustrated, the composite core 516 may have a substantially circular shape and may include a rod (or fiber core) 514 comprising one or more consolidated ribbons (a continuous fiber component). by “substantially circular,” it is generally meant that the aspect ratio of the core (height divided by the width) is typically from about 1.0 to about 1.5, and in some embodiments, about 1.0. due to the selective control over the process used to impregnate the rovings and form a consolidated ribbon, as well the process for compressing and shaping the ribbon, the composite core may comprise a relatively even distribution of the thermoplastic matrix across along its entire length. this also means that the continuous fibers may be distributed in a generally uniform manner about a longitudinal central axis “l” of the composite core 516 . as shown in fig. 8 , for example, the rod 514 of the composite core 516 may include continuous fibers 526 embedded within a thermoplastic matrix 528 . the fibers 526 may be distributed generally uniformly about the longitudinal axis “l.” it should be understood that only a few fibers are shown in fig. 8 , and that the composite core typically may contain a substantially greater number of uniformly distributed fibers. a capping layer 519 also may extend around the perimeter of the rod 514 and define an external surface of the composite core 516 . the cross-sectional thickness of the rod 514 may be selected strategically to help achieve a particular strength for the composite core. for example, the rod 514 may have a thickness (e.g., diameter) of from about 0.1 to about 40 mm, in some embodiments from about 0.5 to about 30 mm, and in some embodiments, from about 1 to about 10 mm. the thickness of the capping layer 519 may depend on the intended function of the part, but typically may be from about 0.01 to about 10 mm, and in some embodiments, from about 0.02 to about 5 mm. the total cross-sectional thickness, or height, of the composite core 516 also may range from about 0.1 to about 50 mm, in some embodiments from about 0.5 to about 40 mm, and in some embodiments, from about 1 to about 20 mm (e.g., diameter, if a circular cross-section). while the composite core may be substantially continuous in length, the length of the composite core may be limited in practice by the spool onto which it will be wound and stored and/or by the length of the continuous fibers. for example, the length often may range from about 1,000 m to about 5,000 m, although even greater lengths are certainly possible. through control over the various parameters mentioned above, cores having very high strengths may be formed. for example, the composite cores may exhibit a relatively high flexural modulus. the term “flexural modulus” generally refers to the ratio of stress to strain in flexural deformation (units of force per unit area), or the tendency for a material to bend. it is determined from the slope of a stress-strain curve produced by a “three point flexural” test (such as astm d790-10, procedure a, room temperature). for example, the composite core of the present invention may exhibit a flexural modulus of from about 10 gpa or more, in some embodiments from about 12 to about 400 gpa, in some embodiments from about 15 to about 200 gpa, and in some embodiments, from about 20 to about 150 gpa. composite cores used to produce electrical cables consistent with certain embodiments disclosed herein may have ultimate tensile strengths over about 300 mpa, such as, for instance, in a range from about 400 mpa to about 5,000 mpa, or from about 500 mpa to about 3,500 mpa. further, suitable composite cores may have an ultimate tensile strength in a range from about 700 mpa to about 3,000 mpa; alternatively, from about 900 mpa to about 1,800 mpa; or alternatively, from about 1,100 mpa to about 1,500 mpa. the term “ultimate tensile strength” generally refers to the maximum stress that a material can withstand while being stretched or pulled before breaking, and is the maximum stress reached on a stress-strain curve produced by a tensile test (such as astm d3916-08) at room temperature. additionally or alternatively, the composite core may have a tensile modulus of elasticity, or elastic modulus, in a range from about 50 gpa to about 500 gpa, from about 70 gpa to about 400 gpa, from about 70 gpa to about 300 gpa, or from about 70 gpa to about 250 gpa. in certain embodiments, the composite core may have an elastic modulus in a range from about 70 gpa to about 200 gpa; alternatively, from about 70 gpa to about 150 gpa; or alternatively, from about 70 gpa to about 130 gpa. the term “tensile modulus of elasticity” or “elastic modulus” generally refers to the ratio of tensile stress over tensile strain and is the slope of a stress-strain curve produced by a tensile test (such as astm 3916-08) at room temperature. composite cores made according to the present disclosure may further have relatively high flexural fatigue life, and may exhibit relatively high residual strength. flexural fatigue life and residual flexural strength may be determined based on a “three point flexural fatigue” test (such as astm d790, typically at room temperature). for example, the cores of the present invention may exhibit residual flexural strength after one million cycles at 160 newtons (“n”) or 180 n loads of from about 60 kilograms per square inch (“ksi”) to about 115 ksi, in some embodiments from about 70 ksi to about 115 ksi, and in some embodiments from about 95 ksi to about 115 ksi. further, the cores may exhibit relatively minimal reductions in flexural strength. for example, cores having void fractions of about 4% or less, in some embodiments about 3% or less, may exhibit reductions in flexural strength after three point flexural fatigue testing of about 1% (for example, from a maximum pristine flexural strength of about 106 ksi to a maximum residual flexural strength of about 105 ksi). flexural strength may be tested before and after fatigue testing using, for example, a three point flexural test as discussed above. in some embodiments, the composite core may have a density or specific gravity of less than about 2.5 g/cc, less than about 2.2 g/cc, less than about 2 g/cc, or less than about 1.8 g/cc. in other embodiments, the composite core density may be in a range from about 1 g/cc to about 2.5 g/cc; alternatively, from about 1.1 g/cc to about 2.2 g/cc; alternatively, from about 1.1 g/cc to about 2 g/cc; alternatively, from about 1.1 g/cc to about 1.9 g/cc; alternatively, from about 1.2 g/cc to about 1.8 g/cc; or alternatively, from about 1.3 g/cc to about 1.7 g/cc. in some cable applications, such as in overhead transmission lines, the strength to weight ratio of the composite core may be important. the ratio may be quantified by the ratio of the tensile strength of the core material to the density of the core material (in units of mpa/(g/cc)). illustrative and non-limiting strength to weight ratios of composite cores in accordance with embodiments of the present invention may be in a range from about 400 to about 1,300, from about 400 to about 1,200, from about 500 to about 1,100, from about 600 to about 1,100, from about 700 to about 1,100, from about 700 to about 1,000, or from about 750 to about 1,000. again, the ratios are based on the tensile strength in mpa, and the composite core density in g/cc. in some embodiments, the percent elongation at break for the composite core may be less than 4%, less than 3%, or less than 2%, while in other embodiments, the elongation at break may be in a range from about 0.5% to about 2.5%, from about 1% to about 2.5%, or from about 1% to about 2%. the linear thermal expansion coefficient of the composite core may be less than about 5×10 −6 /° c., less than about 4×10 −6 /° c., less than about 3×10 −6 /° c., or less than about 2×10 −6 /° c. (or in units of m/m/° c.). stated another way, the linear thermal expansion coefficient may be, on a ppm basis per ° c., less than about 5, less than about 4, less than about 3, or less than about 2. for instance, the coefficient (ppm/° c.) may be in a range from about −0.4 to about 5; alternatively, from about −0.2 to about 4; alternatively, from about 0.4 to about 4; or alternatively, from about 0.2 to about 2. the temperature range contemplated for this linear thermal expansion coefficient may be generally in the −50° c. to 200° c. range, the 0° c. to 200° c. range, the 0° c. to 175° c. range, or the 25° c. to 150° c. range. the linear thermal expansion coefficient is measured in the longitudinal direction, i.e., along the length of the fibers. the composite core also may exhibit a relatively small “bending radius”, which is the minimum radius that the rod can be bent without damage and is measured to the inside curvature of the composite core or composite strand. a smaller bend radius means that the composite core may be more flexible and may be spooled onto a smaller diameter bobbin. this property also may permit easier substitution of the composite core in cables that currently use metal cores, and allow for the use of tools and installation methods presently in use in conventional overhead transmission cables. the bending radius for the composite core may, in some embodiments, be in a range from about 1 cm to about 60 cm, from about 1 cm to about 50 cm, from about 1 cm to about 50 cm, or from about 2 cm to about 45 cm, as determined at a temperature of about 25° c. the bending radius may be in a range from about 2 cm to about 40 cm, or from about 3 cm to about 40 cm in certain embodiments contemplated herein. in other embodiments, bending radiuses may be achieved that are less than about 40 times the outer diameter of the composite core, in some embodiments from about 1 to about 30 times the outer diameter of the composite core, and in some embodiments, from about 2 to about 25 times the outer diameter of the composite core, determined at a temperature of about 25° c. notably, the strength, physical, and thermal properties of the composite core referenced above also may be maintained over a relatively wide temperature range, such as from about −50° c. to about 300° c., from about 100° c. to about 300° c., from about 110° c. to about 250° c., from about 120° c. to about 200° c., from about 150° c. to about 200° c., or from about 180° c. to about 200° c. the composite core also may have a low void fraction, such as about 6% or less, in some embodiments about 3% or less, in some embodiments about 2% or less, in some embodiments about 1% or less, and in some embodiments, about 0.5% or less. the void fraction may be determined in the manner described above, such as using a “resin burn off” test in accordance with astm d 2584-08 or through the use of computed tomography (ct) scan equipment, such as a metrotom 1500 (2 k×2 k) high resolution detector. in one embodiment, a composite core of the present invention may be characterized by the following properties: an ultimate tensile strength in a range from about 700 mpa to about 3,500 mpa; an elastic modulus from about 70 gpa to about 300 gpa; and a linear thermal expansion coefficient (in units of ppm per ° c.) in a range from about −0.4 to about 5. additionally, the composite core may have a density of less than about 2.5 g/cc and/or a strength to weight ratio (in units of mpa/(g/cc)) in a range from about 500 to about 1,100. further, in certain embodiments, the composite core may have a bending radius in a range from about 1 cm to about 50 cm. still further, the composite core may have a percent elongation at break of less than about 3%. in another embodiment, a composite core of the present invention may be characterized by the following properties: an ultimate tensile strength in a range from about 1,100 mpa to about 1,500 mpa; an elastic modulus in a range about 70 gpa to about 130 gpa; and a linear thermal expansion coefficient (in units of ppm per ° c.) in a range from about 0.2 to about 2. additionally, the composite core may have a density in a range from about 1.2 g/cc to about 1.8 g/cc and/or a strength to weight ratio (in units of mpa/(g/cc)) in a range from about 700 to about 1,100. further, in certain embodiments, the composite core may have a bending radius in a range from about 2 cm to about 40 cm. still further, the composite core may have a percent elongation at break in a range from about 1% to about 2.5%. as will be appreciated, the particular composite core embodiments described above are merely exemplary of the numerous designs that may be within the scope of the present invention. among the various possible composite core designs, it should be understood that additional layers of material may be employed in addition to those described above. in certain embodiments, for example, it may be beneficial to form a multi-component core in which one component comprises a higher strength material and another component comprises from a lower strength material. such multi-component cores may be particularly useful in increasing overall strength without requiring the need for more expensive high strength materials for the entire core. the lower and/or higher strength components may comprise ribbon(s) that contain continuous fibers embedded within a thermoplastic matrix. further, it should be understood that the scope of the present invention is by no means limited to the embodiments described above. for example, the composite cores may contain various other components depending on the desired application and its required properties. the additional components may be formed from a continuous fiber ribbon, such as described herein, as well as other types of materials. in one embodiment, for example, the composite core may contain a layer of discontinuous fibers (e.g., short fibers, long fibers, etc.) to improve its transverse strength. the discontinuous fibers may be oriented so that at least a portion of these fibers may be positioned at an angle relative to the direction in which the continuous fibers extend. electrical cable consistent with embodiments disclosed herein, electrical cables of the present invention, such as high voltage overhead transmission lines, may comprise a cable core comprising at least one composite core, and a plurality of conductive elements surrounding the cable core. the cable core may be a single composite core, incorporating any composite core design and accompanying physical and thermal properties provided above. alternatively, the cable core may comprise two or more composite cores, or composite strands, having either the same or different designs, and either the same or different physical and thermal properties. these two or more composite cores may be assembled parallel to each other (straight), or stranded, e.g., about a central composite core member. accordingly, in some embodiments, an electrical cable may comprise a cable core comprising one composite core surrounded by a plurality of conductive elements, while in other embodiments, an electrical cable may comprise a cable core comprising two or more composite cores, the cable core surrounded by a plurality of conductive elements. for example, the cable core may comprise, for instance, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 composite cores, or more (e.g., 37 composite cores), each of which may incorporate any composite core design and accompanying physical and thermal properties provided above. the composite cores may be arranged, bundled, or oriented in any suitable fashion, as would be recognized by one of skill in the art. for instance, the composite cores can be stranded, such as a cable core comprising 7 stranded composite cores or 19 stranded composite cores. alternatively, the composite cores can be parallel, such as a cable core comprising a bundle of 7 composite cores aligned parallel to each other. the electrical cable may comprise a plurality of conductive elements surrounding the cable core (e.g., a single composite core, a plurality of stranded composite cores). the conductive elements may be of any geometric shape, and may be round/circular wires or trapezoidal wires, among others, and including combinations thereof. the conductive elements may be in one layer, or 2 layers, or 3 layers, or 4 layers, and so forth, around the cable core. the conductive elements may be configured parallel to the cable core, or wrapped helically, or in any other suitable arrangement. any number of conductive elements (e.g., wires) may be used, but a typical number of conductive elements in a cable may be up to 84 conductive elements, and often in a range from 2 to about 50. for instance, in some common conductor arrangements, 7, 19, 26, or 37 wires may be employed. exemplary transmission cable designs with composites cores which may be employed in various embodiments of the present invention are described in u.s. pat. no. 7,211,319 to heil, et al., which is incorporated herein in its entirety by reference thereto for all purposes. referring now to fig. 9 , one embodiment of an electrical cable 420 is shown. as illustrated, the electrical cable 420 may include a plurality of conductive elements 422 (e.g., aluminum or an alloy thereof) radially disposed about a substantially cylindrical cable core 400 , which is illustrated as a single composite core but could be a plurality of stranded composite cores. the conductive elements may be arranged in a single layer or in multiple layers. in the illustrated embodiment, the conductive elements 422 are arranged to form a first concentric layer 426 and a second concentric layer 428 . the shape of the conductive elements 422 also may be varied around the cable core 400 . in the illustrated embodiment, the conductive elements 422 have a generally trapezoidal cross-sectional shape. other shapes also may be employed, such as circular, elliptical, rectangular, square, etc. the conductive elements 422 also may be twisted or wrapped around the cable core 400 in any desired geometrical configuration, such as in a helical manner. referring to fig. 10 , for instance, another embodiment of an electrical transmission cable 420 is shown. as illustrated, the electrical transmission cable 420 may include a plurality of conductive elements 422 (e.g., aluminum or an alloy thereof) radially disposed about a bundle of generally cylindrical composite cores 400 , which may be formed in accordance with the present invention. fig. 10 illustrates six composite cores 400 surrounding a single core 400 , although any suitable number of composite cores 400 in any suitable arrangement is within the scope and spirit of the present disclosure and may be used as the cable core. a capping layer 519 also may extend around the perimeter of and define an external surface of each rod. the conductive elements may be arranged in a single layer or in multiple layers. in the illustrated embodiment, for example, the conductive elements 422 are arranged to form a first concentric layer 426 and a second concentric layer 428 . of course, any number of concentric layers may be employed. the shape of the conductive elements 422 also may be varied to optimize the number of elements that can be disposed about the cable core. in the illustrated embodiment, for example, the conductive elements 422 have a generally trapezoidal cross sectional shape. other shapes also may be employed, such as circular, elliptical, rectangular, square, etc. the conductive elements 422 also may be twisted or wrapped around the cable core containing the bundle of composite cores 400 in any desired geometrical configuration, such as in a helical manner. the cross-sectional area of individual conductive elements may vary considerably, but generally the cross-sectional area of individual elements may be in a range from about 10 to about 50 mm 2 , or from about 15 to about 45 mm 2 . the overall conductor area may range (in kcmil), for instance, from about 167 to about 3500 kcmil, from about 210 to about 2700 kcmil, from about 750 to about 3500 kcmil, or from about 750 to about 3000 kcmil. overall conductor areas of about 795, about 825, about 960, and about 1020 kcmil, often may be employed in many end-uses for electrical cables, such as in overheard power transmission lines. for instance, a common aluminum conductor steel reinforced cable known in the industry is often referred to as the 795 kcmil acsr “drake” conductor cable. the outside diameter of cables in accordance with the present invention is not limited to any particular range. however, typical cable outside diameters may be within a range, for example, of from about 7 to about 50 mm, from about 10 to about 48 mm, from about 20 to about 40 mm, from about 25 to about 35 mm, or from about 28 to about 30 mm. likewise, the cross-sectional area of a composite core in the cable is not limited to any particular range. however, typical cross-sectional areas of the composite core may be within a range from about 20 to about 140 mm 2 , or from about 30 to about 120 mm 2 . the conductive elements may be made from any suitable conductive or metal material, including various alloys. the conductive elements may comprise copper, a copper alloy, aluminum, an aluminum alloy, or combinations thereof. as used herein, the term “aluminum or an aluminum alloy” is meant to collectively refer to grades of aluminum or aluminum alloys having at least 97% aluminum by weight, at least 98% aluminum by weight, or at least 99% aluminum by weight, including pure or substantially pure aluminum. aluminum alloys or grades of aluminum having an iacs electrical conductivity of at least 57%, at least 58%, at least 59%, at least 60%, or at least 61% (e.g., 59% to 65%) may be employed in embodiments disclosed herein, and this is inclusive of any method that could produce such conductivities (e.g., annealing, tempering, etc.). for example, aluminum 1350 alloy may be employed as the aluminum or aluminum alloy in certain embodiments of this invention. aluminum 1350, its composition, and its minimum iacs, are described in astm b233, the disclosure of which is incorporated herein by reference in its entirety. in some applications, such as in overhead transmission lines, the sag of the electrical cable may be an important feature. sag is generally considered to be the distance that a cable departs from a straight line between the end points of a span. the sag across a span of towers may affect the ground clearance, and subsequently, the tower height and/or the number of towers needed. sag generally may increase with the square of the span length, but may be reduced by an increase in tensile strength of the cable and/or a decrease in weight of the cable. electrical cables in some embodiments of the present invention may have a sag (at rated temperature (180° c.), and for a 300-meter level span) with a nesc light loading of from about 3 to about 9.5 m, from about 4.5 to about 9.5 m, from about 5.5 to about 8 m, or from about 6 to about 7.5 m. likewise, with a nesc heavy loading, under similar conditions, the sag may be in a range from about 3 to about 9.5 m, from about 3 to about 7.5 m, from about 4.5 to about 7.5 m, or from about 5 to about 7 m. in some embodiments, the cable also may be characterized as having a stress parameter of about 10 mpa or more, in some embodiments about 15 mpa or more, and in some embodiments, from about 20 to about 50 mpa. the method for determining the stress parameter is described in more detail in u.s. pat. no. 7,093,416 to johnson, et al., which is incorporated herein in its entirety by reference thereto for all purposes. for example, sag and temperature may be measured and plotted as a graph of sag versus temperature. a calculated curve may be fitted to the measured data using an alcoa sag10 graphic method available in a software program from southwire company (carrollton, ga.) under the trade designation sag10 (version 3.0 update 3.10.10). the stress parameter is a fitting parameter in sag10 labeled as the “built-in aluminum stress”, which may be altered to fit other parameters, if a material other than aluminum is used (e.g., an aluminum alloy), and which adjusts the position of the knee-point on the predicted graph and also the amount of sag in the high temperature, post-knee-point regime. a description of the stress parameter also may be provided in the sag10 users manual (version 2.0), incorporated herein by reference in its entirety. in relation to the subject matter disclosed herein, creep is generally considered to be the permanent elongation of a cable under load over a long period of time. the amount of creep of a length of cable may be impacted by the length of time in service, the load on the cable, the tension on the cable, the encountered temperature conditions, amongst other factors. it is contemplated that cables disclosed herein may have 10-year creep values at 15%, 20%, 25%, and/or 30% rbs (rated breaking stress) of less than about 0.25%, less than about 0.2%, or less than about 0.175%. for instance, the 10-year creep value at 15% rbs may be less than about 0.25%; alternatively, less than about 0.2%; alternatively, less than about 0.15%; alternatively, less than about 0.1%; or alternatively, less than about 0.075%. the 10-year creep value at 30% rbs may be less than about 0.25%; alternatively, less than about 0.225%; alternatively, less than about 0.2; or alternatively, less than about 0.175%. these creep values are determined in accordance with the 10-year acsr conductor creep test (aluminum association creep test rev. 1999), incorporated herein by reference in its entirety. electrical cables in accordance with embodiments of this invention may have a maximum operating temperature up to about 300° c., up to about 275° c., or up to about 250° c. certain cables provided herein may have maximum operating temperatures that may be up to about 225° c.; alternatively, up to 200° c.; alternatively, up to 180° c.; or alternatively, up to 175° c. maximum operating temperatures may be in a range from about 100 to about 300° c., from about 100 to about 250° c., from about 110 to about 250° c., from about 120 to about 200° c., or from about 120 to about 180° c., in various embodiments of the present invention. in accordance with some embodiments, it may be beneficial for the electrical cable to have certain fatigue and/or vibrational resistance properties. for instance, the electrical cable may pass (meet or exceed) the aeolian vibration test specified in ieee 1138, incorporated herein by reference, at 100 million cycles. in some embodiments, the electrical cable may comprise a partial or complete layer of a material between the cable core and the conductive elements. for instance, the material may be conductive or non-conductive, and may be a tape that partially or completely wraps/covers the cable core. the material may be configured to hold or secure the individual composite core elements of a cable core together. in some embodiments, the material may comprise a metal or aluminum foil tape, a polymer tape (e.g., a polypropylene tape, a polyester tape, a teflon tape, etc.), a tape with glass-reinforcement, and the like. often, the thickness of the material (e.g., the tape) may be in a range from about 0.025 mm to about 0.25 mm, although the thickness is not limited only to this range. in one embodiment, the tape or other material may be applied so that each subsequent wrap overlaps the previous wrap. in another embodiment, the tape or other material may be applied so that each subsequent wrap leaves a gap between the previous wrap. in yet another embodiment, the tape or other material may be applied so that abuts the previous wrap with no overlap and no gap. in these and other embodiments, the tape or other material may be applied helically around the cable core. in some embodiments, the electrical cable may comprise a partial or complete coating of a material between the cable core and the conductive elements. for instance, the material may be, or may comprise, a polymer. suitable polymers may include, but are not limited to, a polyolefin (e.g., polyethylene and polypropylene homopolymers, copolymers, etc.), a polyester (e.g., polybutylene terephalate (pbt)), a polycarbonate, a polyamide (e.g., nylon™), a polyether ketone (e.g., polyetherether ketone (peek)), a polyetherimide, a polyarylene ketone (e.g., polyphenylene diketone (ppdk)), a liquid crystal polymer, a polyarylene sulfide (e.g., polyphenylene sulfide (pps), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), a fluoropolymer (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), a polyacetal, a polyurethane, a styrenic polymer (e.g., acrylonitrile butadiene styrene (abs)), an acrylic polymer, a polyvinyl chloride polymer (pvc), and the like, including combinations thereof. moreover, the polymer may be an elastomeric polymer. the coating may be conductive or non-conductive, and may contain various additives typically employed in wire and cable applications. the coating may serve, in some embodiments, as a protective coating for the cable core. additionally, the coating may be used in instances where the composite core does not contain a capping layer, and the coating partially or completely covers the rod (or fiber core), for example, as a protective coating for the rod. in circumstances where the cable core comprises two or more composite cores (e.g., composite strands), the coating may partially or completely fill the spaces between the individual core elements. the present invention also encompasses methods of making an electrical cable comprising a cable core and a plurality of conductive elements surrounding the cable core. generally, electrical cables using various cable core configurations and conductor element configurations disclosed herein may be produced by any suitable method known to those of skill in the art. for instance, a rigid-frame strander, which can rotate spools of composite cores or strands to assemble a cable core, may be employed. in some embodiments, the rigid-frame strander may impart one twist per machine revolution into all composite cores or strands, except for the center composite core, which is not twisted. each successive layer over the center composite core may be closed by a round die. after the final layer is applied, the cable core containing the composite cores or strands may be secured with a tape or other material. if tape is employed, it may be applied using a concentric taping machine. the resulting cable core with tape may be taken-up onto a reel. the cable core then may be fed back through the same rigid-frame strander for the application of a plurality of conductive elements around the cable core. consistent with embodiments of the present invention, methods of transmitting electricity are provided herein. one such method of transmitting electricity may comprise (i) installing an electrical cable as disclosed herein, e.g., comprising a cable core and a plurality of conductive elements surrounding the cable core, and (ii) transmitting electricity across the electrical cable. another method of transmitting electricity may comprise (i) providing an electrical cable as disclosed herein, e.g., comprising a cable core and a plurality of conductive elements surrounding the cable core, and (ii) transmitting electricity across the electrical cable. in these and other embodiments, the electrical cable, cable core, and conductive elements may be any electrical cable, cable core, and conductive elements described herein. for instance, the cable core may comprise any composite core described herein, i.e., one or more composite cores or strands. examples the invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this invention. various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. example 1 two (2) continuous fiber ribbons were initially formed using an extrusion system as substantially described above. carbon fiber rovings (toray t700sc, which contained 12,000 carbon filaments having a tensile strength of 4,900 mpa and a mass per unit length of 0.8 g/m) were employed for the continuous fibers with each individual ribbon containing 4 rovings. the thermoplastic polymer used to impregnate the fibers was polyphenylene sulfide (pps) (fortron® pps 205, available from ticona, llc), which has a melting point of about 280° c. each ribbon contained 50 wt. % carbon fibers and 50 wt. % pps. the ribbons had a thickness of about 0.18 mm and a void fraction of less than 1.0%. once formed, the ribbons were then fed to a pultrusion line operating at a speed of 20 ft/min. before shaping, the ribbons were heated within an infrared oven (power setting of 305). the heated ribbons were then supplied to a consolidation die having a circular-shaped channel that received the ribbons and compressed them together while forming the initial shape of the rod. within the die, the ribbons remained at a temperature of about 177° c. upon consolidation, the resulting preform was then briefly cooled with an air ring/tunnel device that supplied ambient air at a pressure of 1 psig. the preform was then passed through a nip formed between two rollers, and then to a calibration die for final shaping. within the calibration die, the preform remained at a temperature of about 140° c. after exiting this die the profile was capped with a polyether ether ketone (peek), which had a melting point of 350° c. the capping layer had an average thickness of about 0.1-0.15 mm. the resulting part was then cooled with an air stream. the resulting composite core had an average outside diameter of about 3.4-3.6 mm, and contained 45 wt. % carbon fibers, 50 wt. % pps, and 5 wt. % capping material. to determine the strength properties of the composite core, three-point flexural testing was performed in accordance with astm d790-10, procedure a. the support and nose radius was 0.25 inch, the support span was 30 mm, the specimen length was 2 in, and the test speed was 2 mm/min. the resulting flexural modulus was about 31 gpa and the flexural strength was about 410 mpa. the density of the part was 1.48 g/cm 3 and the void content was less than about 3%. the bend radius was 3.27 cm. example 2 two (2) continuous fiber ribbons were initially formed using an extrusion system as substantially described above. carbon fiber rovings (toray t700sc) were employed for the continuous fibers with each individual ribbon containing 4 rovings. the thermoplastic polymer used to impregnate the fibers was fortron® pps 205. each ribbon contained 50 wt. % carbon fibers and 50 wt. % pps. the ribbons had a thickness of about 0.18 mm and a void fraction of less than 1.0%. once formed, the ribbons were then fed to a pultrusion line operating at a speed of 20 ft/min. before shaping, the ribbons were heated within an infrared oven (power setting of 305). the heated ribbons were then supplied to a consolidation die having a circular-shaped channel that received the ribbons and compressed them together while forming the initial shape of the rod. within the die, the ribbons remained at a temperature of about 343° c. upon consolidation, the resulting preform was then briefly cooled with an air ring/tunnel device that supplied ambient air at a pressure of 1 psig. the preform was then passed through a nip formed between two rollers, and then to a calibration die for final shaping. within the calibration die, the preform remained at a temperature of about 140° c. after exiting this die the profile was capped with fortron® pps 320, which had a melting point of 280° c. the capping layer had an average thickness of about 0.1-0.15 mm. the resulting part was then cooled with an air stream. the resulting composite core had an average outside diameter of about 3.4-3.6 mm, and contained 45 wt. % carbon fibers, 50 wt. % pps, and 5 wt. % capping material. to determine the strength properties of the composite core, three-point flexural testing was performed in accordance with astm d790-10, procedure a. the support and nose radius was 0.25 inch, the support span was 30 mm, the specimen length was 2 in, and the test speed was 2 mm/min. the resulting flexural modulus was 20.3 gpa and the flexural strength was about 410 mpa. the density of the part was 1.48 g/cm 3 and the void content was less than about 3%. the bend radius was 4.37 cm. example 3 two (2) continuous fiber ribbons were initially formed using an extrusion system as substantially described above. glass fiber rovings (tufrov® 4588 from ppg, which contained e-glass filaments having a tensile strength of 2,599 mpa and a mass per unit length of 0.0044 lb/yd (2.2 g/m) were employed for the continuous fibers with each individual ribbon containing 2 rovings. the thermoplastic polymer used to impregnate the fibers was polyphenylene sulfide (pps) (fortron® 205, available from ticona, llc), which has a melting point of about 280° c. each ribbon contained 56 wt. % glass fibers and 44 wt. % pps. the ribbons had a thickness of about 0.18 mm and a void fraction of less than 1.0%. once formed, the ribbons were then fed to a pultrusion line operating at a speed of 20 ft/min. before shaping, the ribbons were heated within an infrared oven (power setting of 330). the heated ribbons were then supplied to a consolidation die having a circular-shaped channel that received the ribbons and compressed them together while forming the initial shape of the rod. upon consolidation, the resulting preform was then briefly cooled with ambient air. the preform was then passed through a nip formed between two rollers, and then to a calibration die for final shaping. within the calibration die, the preform remained at a temperature of about 275° c. after exiting this die, the profile was capped with fortron® 205. the capping layer had an average thickness of about 0.1-0.15 mm. the resulting part was then cooled with an air stream. the resulting composite core had an average outside diameter of about 3.4-3.6 mm, and contained 50 wt. % glass fibers and 50 wt. % pps. to determine the strength properties of the composite core, three-point flexural testing was performed in accordance with astm d790-10, procedure a. the support and nose radius was 0.25 inch, the support span was 30 mm, the specimen length was 2 in, and the test speed was 2 mm/min. the resulting flexural modulus was about 18 gpa and the flexural strength was about 590 mpa. the void content was about 0%, and the bend radius was 1.87 cm. example 4 two (2) continuous fiber ribbons were initially formed using an extrusion system as substantially described above. glass fiber rovings (tufrov® 4588) were employed for the continuous fibers with each individual ribbon containing 2 rovings. the thermoplastic polymer used to impregnate the fibers was nylon 66 (pa66), which has a melting point of about 250° c. each ribbon contained 60 wt. % glass fibers and 40 wt. % nylon 66. the ribbons had a thickness of about 0.18 mm and a void fraction of less than 1.0%. once formed, the ribbons were then fed to a pultrusion line operating at a speed of 10 ft/min. before shaping, the ribbons were heated within an infrared oven (power setting of 320). the heated ribbons were then supplied to a consolidation die having a circular-shaped channel that received the ribbons and compressed them together while forming the initial shape of the rod. upon consolidation, the resulting preform was then briefly cooled with ambient air. the preform was then passed through a nip formed between two rollers, and then to a calibration die for final shaping. within the calibration die, the preform remained at a temperature of about 170° c. after exiting this die, the profile was capped with nylon 66. the capping layer had an average thickness of about 0.1-0.15 mm. the resulting part was then cooled with an air stream. the resulting composite core had an average outside diameter of about 3.4-3.6 mm, and contained 53 wt. % glass fibers, 40 wt. % nylon 66, and 7 wt. % capping material. to determine the strength properties of the composite core, three-point flexural testing was performed in accordance with astm d790-10, procedure a. the support and nose radius was 0.25 inch, the support span was 30 mm, the specimen length was 2 in, and the test speed was 2 mm/min. the resulting flexural modulus was about 19 gpa and the flexural strength was about 549 mpa. the void content was about 0%, and the bend radius was 2.34 cm. example 5 three (3) batches of eight (8) cores were formed having different void fraction levels. for each rod, two (2) continuous fiber ribbons were initially formed using an extrusion system as substantially described above. carbon fiber rovings (toray t700sc, which contained 12,000 carbon filaments having a tensile strength of 4,900 mpa and a mass per unit length of 0.8 g/m) were employed for the continuous fibers with each individual ribbon containing 4 rovings. the thermoplastic polymer used to impregnate the fibers was polyphenylene sulfide (“pps”) (fortron® pps 205, available from ticona, llc), which had a melting point of about 280° c. each ribbon contained 50 wt. % carbon fibers and 50 wt. % pps. the ribbons had a thickness of about 0.18 mm and a void fraction of less than 1.0%. once formed, the ribbons were then fed to a pultrusion line operating at a speed of 20 ft/min. before shaping, the ribbons were heated within an infrared oven (power setting of 305). the heated ribbons were then supplied to a consolidation die having a circular-shaped channel that received the ribbons and compressed them together while forming the initial shape of the rod. within the die, the ribbons remained at a temperature of about 177° c. upon consolidation, the resulting preform was then briefly cooled with an air ring/tunnel device that supplied ambient air at a pressure of 1 psi. the preform was then passed through a nip formed between two rollers, and then to a calibration die for final shaping. within the calibration die, the preform remained at a temperature of about 140° c. after exiting this die, the profile was capped with a polyether ether ketone (“peek”), which had a melting point of 350° c. the capping layer had a thickness of about 0.1 mm. the resulting composite core was then cooled with an air stream. the resulting composite core had a diameter of about 3.5 mm, and contained 45 wt. % carbon fibers, 50 wt. % pps, and 5 wt. % capping material. a first batch of composite cores had a mean void fraction of 2.78%. a second batch of composite cores had a mean void fraction of 4.06%. a third batch of composite cores had a mean void fraction of 8.74%. void fraction measurements were performed using ct scanning. a metrotom 1500 (2 k×2 k) high resolution detector was used to scan the core specimens. detection was done using an enhanced analysis mode with a low probability threshold. once the specimens were scanned for void fraction, volume graphics software was used to interpret the data from the 3d scans, and calculate the void levels in each specimen. to determine the flexural fatigue life and residual flexural strength of the rods, three-point flexural fatigue testing was performed in accordance with astm d790. the support span was 2.2 in and the specimen length was 3 in. four (4) composite cores from each batch were tested at a loading level of 160 newtons (“n”) and four (4) composite cores from each batch were tested at a loading level of 180 n, respectively, representing about 50% and 55% of the pristine (static) flexural strength of the cores. each specimen was tested to one million cycles at a frequency of 10 hertz (hz). before and after fatigue testing, to determine the respective pristine and residual flexural strength properties of the rods, three-point flexural testing was performed in accordance with astm d790-10, procedure a. the average pristine and residual flexural strengths of each batch at each loading level were recorded. the resulting pristine flexural strength for the third batch was 107 ksi, and the resulting residual flexural strength for the third batch was 75 ksi, thus resulting in a reduction of about 29%. the resulting pristine flexural strength for the second batch was 108 ksi, and the resulting residual flexural strength for the second batch was 72 ksi, thus resulting in a reduction of about 33%. the resulting pristine flexural strength for the first batch was 106 ksi, and the resulting residual flexural strength for the first batch was 105 ksi, thus resulting in a reduction of about 1%. example 6 fig. 15 illustrates the electrical cable 520 produced in example 6. the 26 conductive elements 522 formed a first layer 526 and a second layer 528 . the cable core 500 was a strand of 7 composite cores. a tape 530 between the cable core 500 and the conductive elements 522 partially covered the cable core 500 in a helical arrangement. electrical cable was produced as follows. seven (7) composite cores having a diameter of about 3.5 mm were stranded to form a stranded cable core with a 508-mm lay length. the composite cores were similar to those produced in example 1 above. the cable core was secured with an aluminum foil tape laminated to a fiberglass scrim and a silicone based adhesive. 26 conductor wires were placed above and around the cable core and tape in two layers as shown in fig. 15 . the conductor wires had a diameter of about 4.5 mm, and were fabricated from fully annealed 1350 aluminum. the ultimate tensile strength of the cable was approximately 19,760 psi (136 mpa). example 7 fig. 15 illustrates the electrical cable 520 produced in example 7. the 26 conductive elements 522 formed a first layer 526 and a second layer 528 . the cable core 500 was a strand of 7 composite cores. a tape 530 between the cable core 500 and the conductive elements 522 partially covered the cable core 500 in a helical arrangement. electrical cable was produced as follows. seven (7) composite cores having a diameter of about 3.5 mm were stranded to form a stranded cable core with a 508-mm lay length. the composite cores were similar to those produced in example 1 above. the cable core was secured with an aluminum foil tape laminated to a fiberglass scrim and a silicone based adhesive. 26 conductor wires were placed above and around the cable core and tape in two layers as shown in fig. 15 . the conductor wires had a diameter of about 4.5 mm, and were fabricated from an aluminum alloy containing zirconium (approximately 0.2-0.33% zirconium). fig. 16 illustrates the stress-strain data for the electrical cable of example 7. the electrical cable of example 7 was tested for its fatigue and/or vibrational resistance properties in accordance with the aeolian vibration test specified in ieee 1138. the electrical cable of example 7 passed the aeolian vibration test at 100 million cycles. using mathematical modeling based on overhead transmission cables similar to example 7, the 10-year creep (elongation) values for the electrical cable of example 7 were estimated. the calculated 10-year creep values at 15%, 20%, 25%, and 30% rbs (rated breaking stress) were approximately 0.054%, approximately 0.081%, approximately 0.119%, and approximately 0.163%, respectively. constructive example 8 fig. 17 illustrates an electrical cable 620 that can be produced in constructive example 8. the 26 conductive elements 622 can form a first layer 626 and a second layer 628 . the cable core 600 can be a strand of 7 composite cores. a tape 630 between the cable core 600 and the conductive elements 622 can partially cover the cable core 600 in a helical arrangement. the electrical cable of fig. 17 can be produced as follows. seven (7) composite cores having a diameter of about 3.5 mm can be stranded to form a stranded cable core with a 508-mm lay length. the composite cores can be similar to those produced in example 1 above. the cable core can be secured with an aluminum foil tape laminated to a fiberglass scrim and a silicone based adhesive. 26 conductor wires can be placed above and around the cable core and tape in two layers as shown in fig. 17 . the conductors can be trapezoidal wires having a cross-sectional area of about 15-17 mm 2 , and can be fabricated from annealed 1350 aluminum (or alternatively, an aluminum alloy containing zirconium).
|
040-093-004-957-00X
|
GB
|
[
"GB",
"EP",
"DE",
"US",
"AT"
] |
B02C18/00,B30B9/30,B02C18/22,B02C18/16
| 2005-07-01T00:00:00 |
2005
|
[
"B02",
"B30"
] |
improvements relating to shredders
|
the improvements relate to shredders for paper and the like having a shredding mechanism (12) with an opening through which shredded material passes out of the shredding mechanism (12), a compactor plate (32) located beneath the shredding mechanism (12) and including an opening (34), and a base (22), wherein the shredder (10) has a waste bag support mechanism (24) of which the compactor plate (32) forms a part. the waste bag support mechanism (24) is secured to the underside of the shredding mechanism (12) towards the rear thereof for pivotal movement between an operating position in which an upper part of the waste bag support mechanism (24) is close to the underside of the shredding mechanism (12), and a bag removal position in which the upper part of the waste bag support mechanism (24) is pivoted downwards at its front away from the shredding mechanism (12). the waste bag support mechanism (24) includes extending runners (26) on which the compactor plate (32) is mounted for sliding movement between the operating position located beneath the shredding mechanism (12) in which the opening (34) in the compactor plate (32) is substantially directly beneath the opening through which the shredded material passes, and the bag removal position in which the compactor plate (32) is located forward of the shredding mechanism (12).
|
a shredder (10) for paper and the like having: a shredding mechanism (12) with an opening through which shredded material passes out of the shredding mechanism (12), a compactor plate (32) located beneath the shredding mechanism (12) and including an opening (34) such that during use of the shredder (10) waste passes through the opening (34) and builds up underneath the compactor plate (32), a base (22), and a waste bag support mechanism (24) characterised in that the compactor plate (32) forms a part of the waste bag support mechanism (24), wherein the waste bag support mechanism (24) is secured to the underside of the shredding mechanism (12) towards the rear thereof for pivotal movement between: an operating position in which an upper part of the waste bag support mechanism (24) is close to the underside of the shredding mechanism (12), and a bag removal position in which the upper part of the waste bag support mechanism (24) is pivoted downwards at its front away from the shredding mechanism (12). a shredder (10) according to claim 1 wherein the waste bag support mechanism (24) includes extending runners (26) on which the compactor plate (32) is mounted for sliding movement between: the operating position located beneath the shredding mechanism (12) in which the opening (34) in the compactor plate (32) is substantially directly beneath the opening through which the shredded material passes, and the bag removal position in which the compactor plate (32) is located forward of the shredding mechanism (12). a shredder (10) according to claim 1 or 2 wherein the waste bag support mechanism (24) further includes a waste bag support platform (38) movable between: the operating position in which it is located beneath the shredding mechanism (12) above the base (22) of the shredder (10) with a space between the platform (38) and the base (22) of the shredder (10), and the bag removal position in which it is closer to the base (22) of the shredder (10). a shredder (10) according to anyone of the preceding claims wherein waste bag support mechanism (24) includes means to retain a waste bag (25) for collection of the shredded material after it has passed through the opening (34) in the compactor plate (32). a shredder (10) according to any preceding claim wherein the compactor plate (32) includes a guide (36) to the opening (34) which, when the waste bag support mechanism (24) is in the operating position is located close to the opening in the shredding mechanism (12) through which the shredded material passes out of the shredding mechanism (12). a shredder (10) according to claim 5 as dependent on claim 4 wherein the means to retain a waste bag (25) for collection of the shredded material is provided by the proximity of the guide (36) in the compactor plate (32) to the underside of the shredding mechanism (12).
|
description of invention the invention relates to improvements in shredders, in particular to the manner in which the shredded material is handled in shredders of the kind intended for the shredding of paper and the like, and generally used in offices. shredders have been known for many years, and are used to shred documents such that they are safely disposed of and cannot be readily reconstructed. originally shredders simply cut the paper into long strips, but more recently they have in general also cross cut those strips into short lengths. this has two main advantages, the first is that reconstruction of the documents is made much more difficult, and secondly the waste is less bulky as the long strips tended to act like springs, and do not naturally compact, whereas shorter pieces do not suffer from this problem to the same extent. one problem with shredders is how often the waste container needs to be emptied. the shredding mechanism of most shredders will cut off when the waste in the container builds up underneath the shredding mechanism. in most shredders without any form of compaction mechanism, particularly those which do not cross-cut, this happens often and the user then has to open the container and push the waste material down to compress it before they can continue their shredding. an example shredder device is described in us 529 960 . in some shredders, particularly those which do not cross-cut, the waste may be crinkled as it leaves the shredding mechanism to reduce its springiness, and in these cases the problem should occur less often. however, it is clearly desirable to be able to operate a shredder for as long as possible without having to either compact the waste by hand, or empty the waste container. it is an object of the present invention to address the above described problem. according to the present invention there is provided a shredder for paper and the like as defined in claim 1. preferably the waste bag support mechanism is secured to the underside of the shredding mechanism towards the rear thereof for pivotal movement between an operating position in which an upper part of the waste bag support mechanism is close to the underside of the shredding mechanism, and a bag removal position in which the upper part of the waste bag support mechanism is pivoted downwards at its front away from the shredding mechanism. preferably the waste bag support mechanism includes extending runners on which the compactor plate is mounted for sliding movement between the operating position located beneath the shredding mechanism in which the opening in the compactor plate is substantially directly beneath the opening through which the shredded material passes, and the bag removal position in which the compactor plate is located forward of the shredding mechanism. conveniently the waste bag support mechanism further includes a waste bag support plate movable between the operating position in which it is located beneath the shredding mechanism above the base of the shredder with a space between the platform and the base of the shredder, and the bag removal position in which it is closer to the base of the shredder. the waste bag support mechanism may include means to retain a waste bag for collection of the shredded material after it has passed through the opening in the compactor plate. preferably the compactor plate includes a guide to the opening which, when the waste bag support mechanism is in the operating position is located close to the opening in the shredding mechanism through which the shredded material passes out of the shredding mechanism. the means to retain a waste bag for collection of the shredded material is conveniently provided by the proximity of the guide in the compactor plate to the underside of the shredding mechanism. an example of a shredder according to the invention will now be described, by way of example only, with reference to the accompanying drawings in which: figure 1 is a perspective view of the shredder according to the invention from above and one side, with the cabinet removed to reveal a waste bag support mechanism of the invention, in its bag removal position, figure 2 is a side view of the shredder of figure 1 , with the cabinet shown in chain lines, and the waste bag support mechanism of the invention, in its bag removal position, figure 3 is also a side view of the shredder of figure 1 , with the cabinet shown in chain lines, and the waste bag support mechanism of the invention, in its operating position, and figure 4 is a perspective view of the shredder of figure 1 , from beneath and one side, with the cabinet removed to reveal the waste bag support mechanism of the invention, in its operating position. referring to the figures, a shredder 10 according to the invention will now be described. in conventional manner the shredder 10 includes a shredding mechanism 12, supported on a cabinet 14. the shredding mechanism 12 has an opening 16 for receipt of sheet material, such as paper and light card, to be shredded, leading to a chute 18 down which the material to be shredded passes before it reaches the cutting heads 20 which are powered by an electric motor and drive (not shown). the shredded material is pushed out of the shredding mechanism 12 through an opening in its underside (not shown) by the cutting heads 20. as the manner in which the shredding mechanism operates has no bearing on the present invention it will not be described further. the cabinet 14 has a base 22, three sides and a door (not shown) at the front which can be opened to gain access to the interior of the cabinet 14. located within the cabinet 14 below the shredding mechanism 12 is a waste bag support mechanism 24. the waste bag support mechanism 24 comprises two sets of extending runners 26, one disposed to each side of the shredder 10, and secured to the underside of the shredding mechanism 12 by means of a bracket 28, such that they can pivot, as discussed below about axis a, the maximum angle of pivot being controlled by the existence of a peg 30 on each bracket 28. each set of extending runners 26 in this example comprises first, second and third parts, referenced 26 a , 26 b and 26 c , but shredders according to the invention may include different numbers of runners in the sets. the waste bag support mechanism 24 also includes a compactor plate 32 which includes an opening 34 and a guide 36 in the form of a funnel on the top of the compactor plate 32. the compactor plate 32 is mounted on the sets of runners 26, and in particular on the third runner part 26 c , for sliding and pivotal movement relative to the shredding mechanism 12 as will be discussed below. the waste bag support mechanism 24 further includes a waste bag support platform 38 which is supported below the runners 26 by a pair of uprights 40, one on each side, which are pivotally connected to the first runner 26 a , such that they can hang vertically downwards at all times, whatever the angle of the runners 26 with respect to the shredding mechanism 12. the waste bag support mechanism 24 has two positions, an operating position shown in figure 3 in which the runners 26 are in a retracted condition, and a bag removal position in which the runners 26 are in extended. in the operating position the compactor plate 32 is located beneath the shredder mechanism 12 such that the guide 36 and opening 34 are directly below the opening in the underside of the shredder mechanism 12 and all shredded material passes through the guide 36 and opening 34. in the bag removal position shown in figure 2 the runners 26 have been pivoted downwards and extended by operation of a handle 42 adjacent the compactor plate 32, such that the compactor plate 32 is located forwardly and downwardly of the shredding mechanism 12 and outside of the cabinet 14. when the waste bag support mechanism 24 is in its operating position the bag support plate 38 is located a distance b above the base 22 of the cabinet 14. however, when the waste bag support mechanism 24 is in its bag removal position the bag support plate 38 is located much closer to the base 22 of the cabinet 14, than the distance b. the importance of this will become clear below. the waste bag support mechanism 24 operates as follows. with the waste bag support mechanism 24 in the bag removal position, the open end 25a of a waste bag 25 is fed upwards through the opening 34 in the compactor plate 32, such that the majority of it hangs down below the compactor plate 32, and its bottom (closed) end reaches or is close to the bag support plate 38. the open end is then spread out around the opening 34, and the handle 42 used to push compactor plate 32 inwards such that the runners 26 are moved from their extended condition to their retracted condition, the handle 42 is then lifted to bring the runners 26 up beneath the shredding mechanism 12 and the waste bag support mechanism 24 into its operating position. a locking means (not shown) is provided to maintain the waste bag support mechanism 24 in that position, which can be of any suitable form. the shredder 10 can then be used and all the shredded material will pass through the opening 34 in the compactor plate 32 and into the waste bag 25. the bag 25 is retained simply by the proximity of the compactor plate 32 to the underside of the shredding mechanism 12, and the support provided generally by the bag support mechanism 24. however other provision may be made to retain it in position, as appropriate. the compactor plate 32 operates in known manner to compact the shredded material and to prevent it building up underneath the shredding mechanism 12. that is as the shredding mechanism 12 operates the cutting heads 20 within it push the shredded material out and through the opening 34, the shredded material accumulates in the bag 25 and as it builds up under the compactor plate 32, the plate retains it in the bag 25 and allows more shredded material to be pushed out by the cutting heads 20, through the opening 34 and into the bag 25. thus as the shredded material builds up in the bag 25 it is compacted. this prevents the shredded material under pressure from pushing back up into the shredding mechanism 12 and jamming it. with the bag support plate 38 beneath the bag 25, such that there is a solid surface both above and below, the bag 25 can hold a very large amount of shredded material and quite a pressure can build up. when it is desired to change the waste bag 25, the locking means is released and the handle 42 is moved downwards, pivoting the runners 26 about axis a to the maximum angle permitted by the peg 30. this moves the compactor plate 32 downwards away from the shredding mechanism 12, and thus releases the funnel 36 from adjacent the opening in the shredding mechanism 12, and from any accumulation of shredded material which has built up there. this also moves the bag support plate 38 downwards towards the base 22 of the cabinet 14, such that the space beneath the bag support plate 38 is then much less than the distance b. the handle 42 is then pulled outwards to extend the runners 26 and move the compactor plate 32 forwards and out of the cabinet 14, and the waste bag support mechanism 24 into its bag removal position. the compactor plate 32 is then released from the runners 26 and lifted clear. the top end 25a of the bag 25 is thus drawn through the opening 34, and pulled upwards, which in general causes any loose shredded material on top of the compactor place 32 to be pulled into the bag 25. the bag 25 can then readily be tied for clean and tidy disposal of the waste shredded material. the bag 25 is then replaced with a new bag 25, as shown in figure 2 , and the process repeated as required. the features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof as defined in appended claims.
|
040-502-104-685-042
|
US
|
[
"KR",
"AU",
"WO",
"EA",
"CN",
"CA",
"EP",
"JP",
"AT",
"HU",
"DE",
"IL",
"CZ",
"MX",
"BR",
"HR"
] |
A61K31/65,A61P31/04,C07C237/00,C07B61/00,C07C231/12,C07C237/26,C07C253/30,C07C255/59
| 2000-07-07T00:00:00 |
2000
|
[
"A61",
"C07"
] |
13-substituted methacycline compounds
|
13-substituted methacycline compounds, methods of treating tetracycline compounds, and pharmaceutical compositions containing the 13-substituted methacycline compounds are described.
|
a compound selected from the group consisting of: 13-(3-nitrophenyl) methacycline, 13-(2,3,4,5,6-pentafluorophenyl) methacycline, 5-propionyl-13-(4'-chlorophenyl) methacycline and pharmaceutically acceptable salts thereof. the compound of claim 1, wherein said compound is 13-(3-nitrophenyl) methacycline or a pharmaceutically acceptable salt thereof. the compound of claim 1, wherein said compound is 13-(2,3,4,5,6-pentafluorophenyl) methacycline or a pharmaceutically acceptable salt thereof. the compound of claim 1, wherein said compound is 5-propionyl-13-(4'-chlorophenyl) methacycline or a pharmaceutically acceptable salt thereof. a compound according to any one of claims 1 to 4 for use as a medicament. a compound according to any one of claims 1 to 4 for treating a tetracycline responsive state selected from bacterial infections, cancer, diabetes, diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and throat infections, wound infections and mastitis. the compound of claim 6, wherein said compound is for treating a bacterial infection. the compound of claim 7, wherein said bacterial infection is associated with e. coli , s. aureus , or e. faecalis . a pharmaceutical composition comprising a therapeutically effective amount of a compound of any one of claims 1 to 4 and a pharmaceutically acceptable carrier. a method for synthesizing a compound according to any one of claims 1 to 4 comprising contacting a methacycline compound with a boronic acid. the method of claim 10, wherein a transition metal catalyst is present. use of a compound according to any one of claims 1 to 4 in the manufacture of a medicament for the treatment of a tetracycline responsive state selected from bacterial infections, cancer, diabetes, diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and throat infections, wound infections and mastitis.
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background of the invention the development of the tetracycline antibiotics was the direct result of a systematic screening of soil specimens collected from many parts of the world for evidence of microorganisms capable of producing bacteriocidal and/or bacteriostatic compositions. the first of these novel compounds was introduced in 1948 under the name chlortetracycline. two years later, oxytetracycline became available. the elucidation of the chemical structure of these compounds confirmed their similarity and furnished the analytical basis for the production of a third member of this group in 1952, tetracycline. a new family of tetracycline compounds, without the ring-attached methyl group present in earlier tetracyclines, was prepared in 1957 and became publicly available in 1967; and minocycline was in use by 1972. recently, research efforts have focused on developing new tetracycline antibiotic compositions effective under varying therapeutic conditions and routes of administration. new tetracycline analogues have also been investigated which may prove to be equal to or more effective than the originally introduced tetracycline compounds. examples include u.s. patent nos. 3,957,980 ; 3,674,859 ; 2,980,584 ; 2,990,331 ; 3,062,717 ; 3,557,280 ; 4,018,889 ; 4,024,272 ; 4,126,680 ; 3,454,697 ; and 3,165,531 . these patents are representative of the range of pharmaceutically active tetracycline and tetracycline analogue compositions. historically, soon after their initial development and introduction, the tetracyclines were found to be highly effective pharmacologically against rickettsiae; a number of gram-positive and gram-negative bacteria; and the agents responsible for lymphogranuloma venereum, inclusion conjunctivitis, and psittacosis. hence, tetracyclines became known as "broad spectrum" antibiotics. with the subsequent establishment of their in vitro antimicrobial activity, effectiveness in experimental infections, and pharmacological properties, the tetracyclines as a class rapidly became widely used for therapeutic purposes. however, this widespread use of tetracyclines for both major and minor illnesses and diseases led directly to the emergence of resistance to these antibiotics even among highly susceptible bacterial species both commensal and pathogenic (e.g., pneumococci and salmonella). the rise of tetracycline-resistant organism has resulted in a general decline in use of tetracyclines and tetracycline analogue compositions as antibiotics of choice. wo-a-01/19784 discloses tetracycline derivatives including 13-substituted methacycline compounds. gb-a-1108310 discloses tetracycline compounds which have an acylated amido group summary of the invention: the invention pertains to a compound selected from the group consisting of: 13-(3-nitrophenyl) methacycline, 13-(2,3,4,5,6-pentafluorophenyl) methacycline, 5-propionyl-13-(4'-chlorophenyl) methacycline and pharmaceutically acceptable salts thereof. the compounds may be used as a medicament. the compounds may be used in a method for treating a tetracycline responsive state in a mammal, by administering to a mammal a compound as defined above. the tetracycline response state is selected from bacterial infections, cancer, diabetes, diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and throat infections, wound infections and mastitis. the invention also pertains to pharmaceutical compositions comprising a compound as defined above, and to the use of a compound as defined above in the manufacture of a medicament to treat a tetracycline responsive state selected from bacterial infections, cancer, diabetes, diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and throat infections, wound infections and mastitis. the invention also pertains, at least in part, to a method for synthesisizing the compounds as defined above. the method includes contacting a methacycline compound with a boronic acid (e.g., an aryl boronic acid), under appropriate conditions such that the compound is formed. detailed description of the invention: the invention pertains to a compound selected from the group consisting of: 13-(3-nitrophenyl) methacycline, 13-(2,3,4,5,6-pentafluorophenyl) methacycline, 5-propionyl-13-(4'-chlorophenyl) methacycline and pharmaceutically acceptable salts thereof. in an embodiment the compound is 13-(3-nitrophenyl) methacycline. in an embodiment the compound is 13-(2,3,4,5,6-pentafluorophenyl) methacycline. in an embodiment the compound is 5-propionyl-13-(4'-chlorophenyl) methacycline. the invention also pertains, at least in part, to a method for synthesisizing the compounds as defined above. the method includes contacting a methacycline compound with a boronic acid, under appropriate conditions such that the methacycline compound is formed. the term "methacycline compound" includes compounds which can be used to synthesize the substituted methacycline compounds of the invention. the term "appropriate conditions" includes conditions which allow for the desired reaction to take place. for example, appropriate conditions may comprise a transition metal catalyst (e.g., the boronic acid coupling) or an acid catalyst (tertiary alcohol addition). the appropriate conditions may also comprise an inert atmosphere (e.g., n 2 , ar, etc.) and an acceptable solvent. furthermore, one of skill in the art use literature references to further illuminate the reactions described herein and in the examples (e.g., pure & applied chemistry, (1991) 63:419-22 ; j. org. chem. (1993) 58:2201 ; organic synthesis 68:130 ). the term "transition metal catalyst" includes transition metals and catalysts comprising a transition metal, e.g ., including elements 21 through 29, 39 through 47, 57 through 79, and 89 on. examples of transition metal catalysts include cucl 2 , copper (i) triflate, copper thiophene chloride, palladium (ii) chloride, organopalladium catalysts such as palladium acetate, pd(pph 3 ) 4 , pd(asph 3 ) 4 , pdcl 2 (phcn) 2 , pdcl 2 (ph 3 p) 2 , pd 2 (dba) 3 -chcl 3 ("dba"= dibenzylacetone); and combinations thereof. other transition metal catalysts include those containing metals such as rhodium (e.g. rhodium (ii) acetate and rh 6 (co) 16 ), iron, iridium, chromium, zirconium, and nickel. a skilled artisan will be able to select the appropriate transition metal catalyst to perform the desired reaction, based on the existing literature (see, for example, lipshutz, b.h. org. react. 1992, 41:135 ) the compounds of the invention can be synthesized by methods known in the art and/or as described herein. in scheme 1, a general synthetic scheme for the synthesis of 13-substituted methacycline compounds is shown. in this reaction, methacycline is coupled with a boronic acid in the presence of a transition metal catalyst. furthermore, other aryl coupling reactions known in the art may also be used. as shown in scheme 1, the methacycline is reacted with a phenylboronic acid in the presence of a palladium catalyst such as pd(oac) 2 . the resulting compound can then be purified using techniques known in the art such as preparative hplc and characterized. the synthesis of the compounds of the invention are described in more detail in example 1. 13-substituted methacycline compounds wherein r 6 is an alkyl group can be synthesized using a tertiary alcohol and an acid catalyst as shown in scheme 2. described herein is a method for synthesizing a 13-substituted methacycline compound, (e.g., a 13-alkyl substituted methacycline compound, e.g., a compound of formula (i) wherein r 6 is alkyl). the method includes contacting a methacycline compound with a tertiary alcohol, under appropriate conditions such that a 13-substituted methacycline compound is synthesized. the term "alkyl" includes saturated aliphatic groups, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl), branched-chain alkyl groups (isopropyl, tert-butyl, isobutyl), cycloalkyl (alicyclic) groups (cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl), alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups. the term alkyl further includes alkyl groups, which comprise oxygen, nitrogen, sulfur or phosphorous atoms replacing one or more carbons of the hydrocarbon backbone. a straight chain or branched chain alkyl may have 6 or fewer carbon atoms in its backbone (e.g., c 1 -c 6 for straight chain, c 3 -c 6 for branched chain), and more preferably 4 or fewer. likewise, preferred cycloalkyls have from 3-8 carbon atoms in their ring structure, and more preferably have 5 or 6 carbons in the ring structure. the term c 1 -c 6 includes alkyl groups containing 1 to 6 carbon atoms. moreover, the term alkyl includes both "unsubstituted alkyls" and "substituted alkyls", the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. such substituents can include, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. cycloalkyls can be further substituted, e.g., with the substituents described above. an "alkylaryl" or an "aralkyl" moiety is an alkyl substituted with an aryl (e.g., phenylmethyl (benzyl)). the term "alkyl" also includes the side chains of natural and unnatural amino acids. the term "aryl" includes groups with aromaticity, including 5- and 6-membered single-ring aromatic groups that may include from zero to four heteroatoms as well as multicyclic systems with at least one aromatic ring. examples of aryl groups include benzene, phenyl, pyrrole, furan, thiophene, thiazole, isothiazole, imidazole, triazole, tetrazole, pyrazole, oxazole, isooxazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like. furthermore, the term "aryl" includes multicyclic aryl groups, e.g., tricyclic, bicyclic, e.g., naphthalene, benzoxazole, benzodioxazole, benzothiazole, benzoimidazole, benzothiophene, methylenedioxyphenyl, quinoline, isoquinoline, napthridine, indole, benzofuran, purine, benzofuran, deazapurine, or indolizine. those aryl groups having heteroatoms in the ring structure may also be referred to as "aryl heterocycles", "heterocycles," "heteroaryls" or "heteroaromatics". the aromatic ring can be substituted at one or more ring positions with such substituents as described above, as for example, halogen, hydroxyl, alkoxy, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkylaminocarbonyl, aralkylaminocarbonyl, alkenylaminocarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkenylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. aryl groups can also be fused or bridged with alicyclic or heterocyclic rings which are not aromatic so as to form a multicyclic system (e.g., tetralin, methylenedioxyphenyl) the term "alkenyl" includes unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but that contain at least one double bond. for example, the term "alkenyl" includes straight-chain alkenyl groups (e.g., ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl), branched-chain alkenyl groups, cycloalkenyl (alicyclic) groups (cyclopropenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl), alkyl or alkenyl substituted cycloalkenyl groups, and cycloalkyl or cycloalkenyl substituted alkenyl groups. the term alkenyl further includes alkenyl groups which include oxygen, nitrogen, sulfur or phosphorous atoms replacing one or more carbons of the hydrocarbon backbone. a straight chain or branched chain alkenyl group may have 6 or fewer carbon atoms in its backbone (e.g., c 2 -c 6 for straight chain, c 3 -c 6 for branched chain). likewise, cycloalkenyl groups may have from 3-8 carbon atoms in their ring structure, and more preferably have 5 or 6 carbons in the ring structure. the term c 2 -c 6 includes alkenyl groups containing 2 to 6 carbon atoms. moreover, the term alkenyl includes both "unsubstituted alkenyls" and "substituted alkenyls", the latter of which refers to alkenyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. such substituents can include, for example, alkyl groups, alkynyl groups, halogens, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. the term "alkynyl" includes unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but which contain at least one triple bond. for example, the term "alkynyl" includes straight-chain alkynyl groups (e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl), branched-chain alkynyl groups, and cycloalkyl or cycloalkenyl substituted alkynyl groups. the term alkynyl further includes alkynyl groups which include oxygen, nitrogen, sulfur or phosphorous atoms replacing one or more carbons of the hydrocarbon backbone. a straight chain or branched chain alkynyl group may have 6 or fewer carbon atoms in its backbone (e.g., c 2 -c 6 for straight chain, c 3 -c 6 for branched chain). the term c 2 -c 6 includes alkynyl groups containing 2 to 6 carbon atoms. moreover, the term alkynyl includes both "unsubstituted alkynyls" and "substituted alkynyls", the latter of which refers to alkynyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. such substituents can include, for example, alkyl groups, alkynyl groups, halogens, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. unless the number of carbons is otherwise specified, "lower alkyl" as used herein means an alkyl group, as defined above, but having from one to five carbon atoms in its backbone structure. "lower alkenyl" and "lower alkynyl" have chain lengths of, for example, 2-5 carbon atoms. the term "acyl" includes compounds and moieties which contain the acyl radical (ch 3 co-) or a carbonyl group. the term "substituted acyl" includes acyl groups where one or more of the hydrogen atoms are replaced by for example, alkyl groups, alkynyl groups, halogens, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. the term "acylamino" includes moieties wherein an acyl moiety is bonded to an amino group. for example, the term includes alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido groups. the term "aroyl" includes compounds and moieties with an aryl or heteroaromatic moiety bound to a carbonyl group. examples of aroyl groups include phenylcarboxy, naphthyl carboxy. the terms "alkoxyalkyl", "alkylaminoalkyl" and "thioalkoxyalkyl" include alkyl groups, as described above, which further include oxygen, nitrogen or sulfur atoms replacing one or more carbons of the hydrocarbon backbone, e.g., oxygen, nitrogen or sulfur atoms. the term "alkoxy" includes substituted and unsubstituted alkyl, alkenyl, and alkynyl groups covalently linked to an oxygen atom. examples of alkoxy groups include methoxy, ethoxy, isopropyloxy, propoxy, butoxy, and pentoxy groups. examples of substituted alkoxy groups include halogenated alkoxy groups. the alkoxy groups can be substituted with groups such as alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moieties. examples of halogen substituted alkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy. the term "amine" or "amino" includes compounds where a nitrogen atom is covalently bonded to at least one carbon or heteroatom. the term "alkylamino" includes groups and compounds wherein the nitrogen is bound to at least one additional alkyl group. the term "dialkylamino" includes groups wherein the nitrogen atom is bound to at least two additional alkyl groups. the term "arylamino" and "diarylamino" include groups wherein the nitrogen is bound to at least one or two aryl groups, respectively. the term "alkylarylamino," "alkylaminoaryl" or "arylaminoalkyl" refers to an amino group which is bound to at least one alkyl group and at least one aryl group. the term "alkaminoalkyl" refers to an alkyl, alkenyl, or alkynyl group bound to a nitrogen atom which is also bound to an alkyl group. the term "amide" or "aminocarboxy" includes compounds or moieties which contain a nitrogen atom which is bound to the carbon of a carbonyl or a thiocarbonyl group. the term includes "alkaminocarboxy" groups which include alkyl, alkenyl, or alkynyl groups bound to an amino group bound to a carboxy group. it includes arylaminocarboxy groups which include aryl or heteroaryl moieties bound to an amino group which is bound to the carbon of a carbonyl or thiocarbonyl group. the terms "alkylaminocarboxy," "alkenylaminocarboxy," "alkynylaminocarboxy," and "arylaminocarboxy" include moieties wherein alkyl, alkenyl, alkynyl and aryl moieties, respectively, are bound to a nitrogen atom which is in turn bound to the carbon of a carbonyl group. the term "carbonyl" or "carboxy" includes compounds and moieties which contain a carbon connected with a double bond to an oxygen atom. examples of moieties which contain a carbonyl include aldehydes, ketones, carboxylic acids, amides, esters, anhydrides. the term "thiocarbonyl" or "thiocarboxy" includes compounds and moieties which contain a carbon connected with a double bond to a sulfur atom. the term "ether" includes compounds or moieties which contain an oxygen bonded to two different carbon atoms or heteroatoms. for example, the term includes "alkoxyalkyl" which refers to an alkyl, alkenyl, or alkynyl group covalently bonded to an oxygen atom which is covalently bonded to another alkyl group. the term "ester" includes compounds and moieties which contain a carbon or a heteroatom bound to an oxygen atom which is bonded to the carbon of a carbonyl group. the term "ester" includes alkoxycarboxy groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, etc. the alkyl, alkenyl, or alkynyl groups are as defined above. the term "thioether" includes compounds and moieties which contain a sulfur atom bonded to two different carbon or hetero atoms. examples of thioethers include, but are not limited to alkthioalkyls, alkthioalkenyls, and alkthioalkynyls. the term "alkthioalkyls" include compounds with an alkyl, alkenyl, or alkynyl group bonded to a sulfur atom which is bonded to an alkyl group. similarly, the term "alkthioalkenyls" and alkthioalkynyls" refer to compounds or moieties wherein an alkyl, alkenyl, or alkynyl group is bonded to a sulfur atom which is covalently bonded to an alkynyl group. the term "hydroxy" or "hydroxyl" includes groups with an -oh or -o - . the term "halogen" includes fluorine, bromine, chlorine, iodine. the term "perhalogenated" generally refers to a moiety wherein all hydrogens are replaced by halogen atoms. the terms "polycyclyl" or "polycyclic radical" refer to two or more cyclic rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls) in which two or more carbons are common to two adjoining rings. rings that are joined through non-adjacent atoms are termed "bridged" rings. each of the rings of the polycycle can be substituted with such substituents as described above, as for example, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, aralkylaminocarbonyl, alkenylaminocarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkenylcarbonyl, aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkyl, alkylaryl, or an aromatic or heteroaromatic moiety. the term "heteroatom" includes atoms of any element other than carbon or hydrogen. examples of heteroatoms include nitrogen, oxygen, sulfur and phosphorus. it will be noted that the structure of some of the compounds of this invention includes asymmetric carbon atoms. it is to be understood accordingly that the isomers arising from such asymmetry (e.g., all enantiomers and diastereomers) are included within the scope of this invention, unless indicated otherwise. such isomers can be obtained in substantially pure form by classical separation techniques and by stereochemically controlled synthesis. furthermore, the structures and other compounds and moieties discussed in this application also include all tautomers thereof. prodrugs are compounds which are converted in vivo to active forms (see, e.g ., rb. silverman, 1992, "the organic chemistry of drug design and drug action", academic press, chp. 8 ). prodrugs can be used to alter the biodistribution (e.g., to allow compounds which would not typically enter the reactive site of the protease) or the pharmacokinetics for a particular compound. for example, a hydroxyl group, can be esterified, e.g., with a carboxylic acid group to yield an ester. when the ester is administered to a subject, the ester is cleaved, enzymatically or non-enzymatically, reductively or hydrolytically, to reveal the hydroxyl group. the term "prodrug moiety" includes moieties which can be metabolized in vivo to a hydroxyl group and moieties which may advantageously remain esterified in vivo. preferably, the prodrugs moieties are metabolized in vivo by esterases or by other mechanisms to hydroxyl groups or other advantageous groups. examples of prodrugs and their uses are well known in the art (see, e.g., berge et al. (1977) "pharmaceutical salts", j. pharm. sci. 66:1-19 ). the prodrugs can be prepared in situ during the final isolation and purification of the compounds, or by separately reacting the purified compound in its free acid form or hydroxyl with a suitable esterifying agent. hydroxyl groups can be converted into esters via treatment with a carboxylic acid. examples of prodrug moieties include substituted and unsubstituted, branch or unbranched lower alkyl ester moieties, (e.g., propionoic acid esters), lower alkenyl esters, di-lower alkylamino lower-alkyl esters (e.g., dimethylaminoethyl ester), acylamino lower alkyl esters (e.g., acetyloxymethyl ester), acyloxy lower alkyl esters (e.g., pivaloyloxymethyl ester), aryl esters (phenyl ester), aryl-lower alkyl esters (e.g., benzyl ester), substituted (e.g., with methyl, halo, or methoxy substituents) aryl and aryl-lower alkyl esters, amides, lower-alkyl amides, di-lower alkyl amides, and hydroxy amides. preferred prodrug moieties are propionoic acid esters and acyl esters. the compounds of the invention may be used in a method for treating a tetracycline compound responsive state in a subject, by administering to the subject a methacycline compound of the invention. preferably, an effective amount of the tetracycline compound is administered. table 1 depicts the structures of some of these compounds. table-tabl0001 table 1 a b the language "tetracycline compound responsive state" includes states which can be treated, prevented, or otherwise ameliorated by the administration of a tetracycline compound of the invention. tetracycline compound responsive states include bacterial infections (including those which are resistant to other tetracycline compounds), cancer, diabetes, and other states for which tetracycline compounds have been found to be active (see, for example, u.s. patent nos. 5,789,395 ; 5,834,450 ; and 5,532,227 ). compounds of the invention can be used to prevent or control important mammalian and veterinary diseases such as diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and throat infections, wound infection, mastitis. in addition, methods for treating neoplasms using tetracycline compounds of the invention are also included ( van der bozert et al., cancer res., 48:6686-6690 (1988 )). bacterial infections may be caused by a wide variety of gram positive and gram negative bacteria. the compounds of the invention are useful as antibiotics against organisms which are resistant to other tetracycline compounds. the antibiotic activity of the tetracycline compounds of the invention may be determined using the method discussed in example 2, or by using the in vitro standard broth dilution method described in waitz, j.a., national commission for clinical laboratory standards, document m7-a2, vol. 10, no. 8, pp. 13-20, 2nd edition, villanova, pa (1990 ). the tetracycline compounds may also be used to treat infections traditionally treated with tetracycline compounds such as, for example, rickettsiae; a number of gram-positive and gram-negative bacteria; and the agents responsible for lymphogranuloma venereum, inclusion conjunctivitis, psittacosis. the tetracycline compounds may be used to treat infections of, e.g., k. pneumoniae , salmonella , e. hirae , a. baumanii , b. catarrhalis , h. influenzae , p. aeruginosa , e. faecium , e. coli , s. aureus or e. faecalis . in one embodiment, the tetracycline compound is used to treat a bacterial infection that is resistant to other tetracycline antibiotic compounds. the tetracycline compound of the invention may be administered with a pharmaceutically acceptable carrier. the language "effective amount" of the compound is that amount necessary or sufficient to treat or prevent a tetracycline compound responsive state. the effective amount can vary depending on such factors as the size and weight of the subject, the type of illness, or the particular tetracycline compound. for example, the choice of the tetracycline compound can affect what constitutes an "effective amount". one of ordinary skill in the art would be able to study the aforementioned factors and make the determination regarding the effective amount of the tetracycline compound without undue experimentation. the invention also pertains to compounds of the invention for use in methods of treatment against microorganism infections and associated diseases. the methods include administration of an effective amount of one or more tetracycline compounds to a subject. the subject can be either a plant or, advantageously, an animal, e.g., a mammal, e.g., a human. in the use in such therapeutic methods, one or more tetracycline compounds of the invention may be administered alone to a subject, or more typically a compound of the invention will be administered as part of a pharmaceutical composition in mixture with conventional excipient, i.e., pharmaceutically acceptable organic or inorganic carrier substances suitable for parenteral, oral or other desired administration and which do not deleteriously react with the active compounds and are not deleterious to the recipient thereof. in one embodiment, the pharmaceutical composition comprises a substituted methacycline compound of the invention. table 1 depicts the structures of some of these compounds. the language "pharmaceutically acceptable carrier" includes substances capable of being coadministered with the tetracycline compound(s), and which allow both to perform their intended function, e.g., treat or prevent a tetracycline compound responsive state. suitable pharmaceutically acceptable carriers include but are not limited to water, salt solutions, alcohol, vegetable oils, polyethylene glycols, gelatin, lactose, amylose, magnesium stearate, talc, silicic acid, viscous paraffin, perfume oil, fatty acid monoglycerides and diglycerides, petroethral fatty acid esters, hydroxymethyl-cellulose, polyvinylpyrrolidone. the pharmaceutical preparations can be sterilized and if desired mixed with auxiliary agents, e.g., lubricants, preservatives, stabilizers, wetting agents, emulsifiers, salts for influencing osmotic pressure, buffers, colorings, flavorings and/or aromatic substances which do not deleteriously react with the active compounds of the invention. the tetracycline compounds of the invention that are basic in nature are capable of forming a wide variety of salts with various inorganic and organic acids. the acids that may be used to prepare pharmaceutically acceptable acid addition salts of the tetracycline compounds of the invention that are basic in nature are those that form non-toxic acid addition salts, i.e., salts containing pharmaceutically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate, maleate, gentisinate, fumarate, gluconate, glucaronate, saccharate, formate, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and palmoate [i.e., 1,1'-methylene-bis-(2-hydroxy-3-naphthoate)] salts. although such salts must be pharmaceutically acceptable for administration to a subject, e.g., a mammal, it is often desirable in practice to initially isolate a tetracycline compound of the invention from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent and subsequently convert the latter free base to a pharmaceutically acceptable acid addition salt. the acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent, such as methanol or ethanol. upon careful evaporation of the solvent, the desired solid salt is readily obtained. the preparation of other tetracycline compounds of the invention not specifically described in the foregoing experimental section can be accomplished using combinations of the reactions described above that will be apparent to those skilled in the art. the preparation of other tetracycline compounds of the invention not specifically described in the foregoing experimental section can be accomplished using combinations of the reactions described above that will be apparent to those skilled in the art. the tetracycline compounds of the invention that are acidic in nature are capable of forming a wide variety of base salts. the chemical bases that may be used as reagents to prepare pharmaceutically acceptable base salts of those tetracycline compounds of the invention that are acidic in nature are those that form non-toxic base salts with such compounds. such non-toxic base salts include, but are not limited to those derived from such pharmaceutically acceptable cations such as alkali metal cations (e.g., potassium and sodium) and alkaline earth metal cations (e.g., calcium and magnesium), ammonium or water-soluble amine addition salts such as n-methylglucamine-(meglumine), and the lower alkanolammonium and other base salts of pharmaceutically acceptable organic amines. the pharmaceutically acceptable base addition salts of tetracycline compounds of the invention that are acidic in nature may be formed with pharmaceutically acceptable cations by conventional methods. thus, these salts may be readily prepared by treating the tetracycline compound of the invention with an aqueous solution of the desired pharmaceutically acceptable cation and evaporating the resulting solution to dryness, preferably under reduced pressure. alternatively, a lower alkyl alcohol solution of the tetracycline compound of the invention may be mixed with an alkoxide of the desired metal and the solution subsequently evaporated to dryness. the preparation of other tetracycline compounds of the invention not specifically described in the foregoing experimental section can be accomplished using combinations of the reactions described above that will be apparent to those skilled in the art. the tetracycline compounds of the invention and pharmaceutically acceptable salts thereof can be administered via either the oral, parenteral or topical routes. in general, these compounds are most desirably administered in effective dosages, depending upon the weight and condition of the subject being treated and the particular route of administration chosen. variations may occur depending upon the species of the subject being treated and its individual response to said medicament, as well as on the type of pharmaceutical formulation chosen and the time period and interval at which such administration is carried out. the pharmaceutical compositions of the invention may be administered alone or in combination with other known compositions for treating tetracycline responsive states in a mammal. preferred mammals include pets (e.g., cats, dogs, ferrets), farm animals (cows, sheep, pigs, horses, goats), lab animals (rats, mice, monkeys), and primates (chimpanzees, humans, gorillas). the language "in combination with" a known composition is intended to include simultaneous administration of the composition of the invention and the known composition, administration of the composition of the invention first, followed by the known composition and administration of the known composition first, followed by the composition of the invention. any of the therapeutically composition known in the art for treating tetracycline responsive states can be used in the methods of the invention. the compounds of the invention may be administered alone or in combination with pharmaceutically acceptable carriers or diluents by any of the routes previously mentioned, and the administration may be carried out in single or multiple doses. for example, the novel therapeutic agents of this invention can be administered advantageously in a wide variety of different dosage forms, i.e., they may be combined with various pharmaceutically acceptable inert carriers in the form of tablets, capsules, lozenges, troches, hard candies, powders, sprays, creams, salves, suppositories, jellies, gels, pastes, lotions, ointments, aqueous suspensions, injectable solutions, elixirs, syrups. such carriers include solid diluents or fillers, sterile aqueous media and various non-toxic organic solvents. moreover, oral pharmaceutical compositions can be suitably sweetened and/or flavored. in general, the therapeutically-effective compounds of this invention are present in such dosage forms at concentration levels ranging from about 5.0% to about 70% by weight. for oral administration, tablets containing various excipients such as -microcrystalline cellulose, sodium citrate, calcium carbonate, dicalcium phosphate and glycine may be employed along with various disintegrants such as starch (and preferably corn, potato or tapioca starch), alginic acid and certain complex silicates, together with granulation binders like polyvinylpyrrolidone, sucrose, gelatin and acacia. additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often very useful for tabletting purposes. solid compositions of a similar type may also be employed as fillers in gelatin capsules; preferred materials in this connection also include lactose or milk sugar as well as high molecular weight polyethylene glycols. when aqueous suspensions and/or elixirs are desired for oral administration, the active ingredient may be combined with various sweetening or flavoring agents, coloring matter or dyes, and, if so desired, emulsifying and/or suspending agents as well, together with such diluents as water, ethanol, propylene glycol, glycerin and various like combinations thereof. for parenteral administration (including intraperitoneal, subcutaneous, intravenous, intradermal or intramuscular injection), solutions of a therapeutic compound of the present invention in either sesame or peanut oil or in aqueous propylene glycol may be employed. the aqueous solutions should be suitably buffered (preferably ph greater than 8) if necessary and the liquid diluent first rendered isotonic. these aqueous solutions are suitable for intravenous injection purposes. the oily solutions are suitable for intraarticular, intramuscular and subcutaneous injection purposes. the preparation of all these solutions under sterile conditions is readily accomplished by standard pharmaceutical techniques well known to those skilled in the art. for parenteral application, examples of suitable preparations include solutions, preferably oily or aqueous solutions as well as suspensions, emulsions, or implants, including suppositories. therapeutic compounds may be formulated in sterile form in multiple or single dose formats such as being dispersed in a fluid carrier such as sterile physiological saline or 5% saline dextrose solutions commonly used with injectables. additionally, it is also possible to administer the compounds of the present invention topically when treating inflammatory conditions of the skin. examples of methods of topical administration include transdermal, buccal or sublingual application. for topical applications, therapeutic compounds can be suitably admixed in a pharmacologically inert topical carrier such as a gel, an ointment, a lotion or a cream. such topical carriers include water, glycerol, alcohol, propylene glycol, fatty alcohols, triglycerides, fatty acid esters, or mineral oils. other possible topical carriers are liquid petrolatum, isopropylpalmitate, polyethylene glycol, ethanol 95%, polyoxyethylene monolauriate 5% in water, sodium lauryl sulfate 5% in water. in addition, materials such as anti-oxidants, humectants, viscosity stabilizers also may be added if desired. for enteral application, particularly suitable are tablets, dragees or capsules having talc and/or carbohydrate carrier binder, the carrier preferably being lactose and/or corn starch and/or potato starch. a syrup, elixir can be used wherein a sweetened vehicle is employed. sustained release compositions can be formulated including those wherein the active component is protected with differentially degradable coatings, e.g., by microencapsulation, multiple coatings. in addition to treatment of human subjects, the therapeutic methods in which the compounds of the invention may be used also will have significant veterinary applications, e.g. for treatment of livestock such as cattle, sheep, goats, cows, swine; poultry such as chickens, ducks, geese, turkeys; horses; and pets such as dogs and cats. also, the compounds of the invention may be used to treat non-animal subjects, such as plants. it will be appreciated that the actual preferred amounts of active compounds used in a given therapy will vary according to the specific compound being utilized, the particular compositions formulated, the mode of application, the particular site of administration. optimal administration rates for a given protocol of administration can be readily ascertained by those skilled in the art using conventional dosage determination tests conducted with regard to the foregoing guidelines. in general, compounds of the invention for treatment can be administered to a subject in dosages used in prior tetracycline therapies. see, for example, the physicians' desk reference . for example, a suitable effective dose of one or more compounds of the invention will be in the range of from 0.01 to 100 milligrams per kilogram of body weight of recipient per day, preferably in the range of from 0.1 to 50 milligrams per kilogram body weight of recipient per day, more preferably in the range of 1 to 20 milligrams per kilogram body weight of recipient per day. the desired dose is suitably administered once daily, or several sub-doses, e.g. 2 to 5 sub-doses, are administered at appropriate intervals through the day, or other appropriate schedule. it will also be understood that normal, conventionally known precautions will be taken regarding the administration of tetracyclines generally to ensure their efficacy under normal use circumstances. especially when employed for therapeutic treatment of humans and animals in vivo , the practitioner should take all sensible precautions to avoid conventionally known contradictions and toxic effects. thus, the conventionally recognized adverse reactions of gastrointestinal distress and inflammations, the renal toxicity, hypersensitivity reactions, changes in blood, and impairment of absorption through aluminum, calcium, and magnesium ions should be duly considered in the conventional manner. furthermore, the invention also pertains to the use of a tetracycline compound of formula i, for the preparation of a medicament. the medicament may include a pharmaceutically acceptable carrier and the tetracycline compound is an effective amount, e.g, an effective amount to treat a tetracycline responsive state. in yet another embodiment, the invention also pertains to the use of a tetracycline compound of formula i to treat a tetracycline responsive state, e.g., in a subject, e.g., a mammal, e.g., a human. compounds of the invention may be made as described below, with modifications to the procedure below within the skill of those of ordinary skill in the art. example 1: synthesis of 13- substituted methacycline compounds general procedure for phenyl boronic acid derivitization of methacycline methacycline (1 equiv.), pdcl 2 (.14 equiv.), and cucl 2 (.90 equiv.) were dissolved in 20 ml of meoh and heated under nitrogen atmosphere. after 1 h, the boronic acid (2 equiv.) was added to it and the reaction mixture was heated for another 6-10 h. the reactions were either monitored by tlc, or analytical hplc. reaction mixture was then cooled down to the room temperature and was passed through a bed of celite. evaporation of the solvent gave a yellow-brown solid in most of the examples, which was purified using preparative hplc (ch 3 cn:meoh:h 2 o). evaporation of the solvent from the fractions indicated the right peak for the expected product, gave a yellow solid, which was again dissolved in meoh and purged with hcl gas. after evaporation of meoh, the yellow material was dried under vacuum for several hours. example 2: synthesis of 5-propionyl-13-(4'-chlorophenyl) methacycline 500 mg of 13-4'-cl phenyl methacycline is dissolved in 20ml of anhydrous hf. 3 ml of propionic acid is added and the reaction left for 2 days at room temperature. the hf was removed under a steady stream of n 2 , and the residue triturated with et 2 o to yield a dark yellow solid. the solid was dissolved in meoh, and chromatographed on a divinyl benzene resin using an acetonitrile gradient from 30% to 100% with a primary solvent system of 0.1% formic acid. the corresponding fractions were collected and dried in vacuo to yield the product in overall 42%. the yellow solid was dissolved in meoh and hcl gas bubbled in to produce the product as a yellow solid hcl salt. reference example 3: synthesis of 9,13-di-t-butyl methacycline 1.0 g of methacycline is added to 15 ml of concentrated h 2 so 4 . 5 ml of isobutylene or t-butanol is added and the reaction stirred for 6 hours at room temperature. the reaction is neutralized with na 2 co 3 (8 grams) and 40ml of water, and the aqueous layer extracted 3x with 100ml ofn-butanol. the extracts were combined and dried to yield 69% of product as a light yellow solid. an analytical sample was obtained by the chromatography on divinyl benzene using a gradient of acetonitrile from 30-100% over 30 minutes against a primary solvent of 0.1% formic acid. physical chemical data for 13-substituted methacycline compounds table-tabl0002 rt (min) ms(m+h) 13-(3'-no 2 -phenyl) methacycline 8.55 564.5 13-(2',3,4',5',6'-pentafluorophenyl) methacycline 609.4 5-(propionyl)-13-(4'-chlorophenyl) methacycline example 4: in vitro minimum inhibitory concentration (mic) assay the following assay is used to determine the efficacy of tetracycline compounds against common bacteria. 2 mg of each compound is dissolved in 100 µl of dmso. the solution is then added to cation-adjusted mueller hinton broth (camhb), which results in a final compound concentration of 200 µg per ml. the tetracycline compound solutions are diluted to 50 µl volumes, with a test compound concentration of .098 µg/ml. optical density (od) determinations are made from fresh log-phase broth cultures of the test strains. dilutions are made to achieve a final cell density of 1x10 6 cfu/ml. at od=1, cell densities for different genera should be approximately: table-tabl0003 e coli 1x10 9 cfu/ml s. aureus 5x10 8 cfu/ml enterococcus sp. 2.5x10 9 cfu/ml 50 µl of the cell suspensions are added to each well of microtiter plates. the final cell density should be approximately 5x10 5 cfu/ml. these plates are incubated at 35°c in an ambient air incubator for approximately 18 hr. the plates are read with a microplate reader and are visually inspected when necessary. the mic is defined as the lowest concentration of the tetracycline compound that inhibits growth. compounds of the invention indicate good inhibition of growth.
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040-813-492-346-488
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US
|
[
"KR",
"US",
"WO",
"CN"
] |
C23C16/30,C23C16/455,C23C16/56,H01L21/316,H05H1/24,C23C16/40,C23C16/50,C23C16/505,H01L21/314
| 2003-06-12T00:00:00 |
2003
|
[
"C23",
"H01",
"H05"
] |
stress reduction of sioc low k film by addition of alkylenes to omcts based processes
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a method for depositing a low dielectric constant film having a dielectric constant of about 3.2 or less, preferably about 3.0 or less, includes providing a cyclic organosiloxane and a linear hydrocarbon compound having at least one unsaturated carbon- carbon bond to a substrate surface. in one aspect, the cyclic organosiloxane and the linear hydrocarbon compound are reacted at conditions sufficient to deposit a low dielectric constant film on the semiconductor substrate. preferably, the low dielectric constant film has compressive stress.
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1 . a method for depositing a low dielectric constant film, comprising: delivering a gas mixture consisting essentially of: a cyclic organosiloxane; a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond to a substrate surface; and an inert gas; and applying rf power to the gas mixture at conditions sufficient to deposit a film on the substrate surface, the film having a dielectric constant less than 3.2. 2 . the method of claim 1 , wherein the film has compressive stress. 3 . the method of claim 1 , wherein the cyclic organosiloxane comprises one or more silicon-carbon bonds. 4 . the method of claim 3 , wherein the cyclic organosiloxane is octamethylcyclotetrasiloxane (omcts). 5 . the method of claim 1 , wherein cyclic organosiloxane is selected from the group consisting of 1,3,5,7-tetramethylcyclotetrasiloxane (tmcts), octamethylcyclotetrasiloxane (omcts), 1,3,5,7,9-pentamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane. 6 . the method of claim 1 , wherein the linear hydrocarbon compound comprises one or two carbon-carbon double bonds. 7 . the method of claim 1 , wherein the linear hydrocarbon compound is ethylene. 8 . the method of claim 1 , wherein the linear hydrocarbon compound is selected from the group consisting of ethylene, propylene, isobutylene, acetylene, allylene, ethylacetylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and piperylene. 9 . the method of claim 1 , wherein the gas mixture includes essentially no oxidizing gas. 10 . the method of claim 1 , wherein the inert gas is selected from the group consisting of helium, argon, and combinations thereof. 11 . the method of claim 1 , wherein the applying rf power comprises applying mixed frequency rf power to the gas mixture. 12 . the method of claim 1 , further comprising post-treating the low dielectric constant film with an electron beam. 13 . a method for depositing a low dielectric constant film, comprising: providing a gas mixture comprising: a cyclic organosiloxane; a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond; and one or more oxidizing gases to a substrate surface; and applying rf power to the gas mixture at conditions sufficient to deposit a film on the substrate surface, the film having a dielectric constant less than 3.2 and compressive stress. 14 . the method of claim 13 , wherein the one or more oxidizing gases is selected from the group consisting of oxygen, carbon dioxide, and combinations thereof. 15 . the method of claim 13 , wherein the one or more oxidizing gases comprises oxygen, and the conditions comprise an oxygen flow rate less than a flow rate of the linear hydrocarbon compound. 16 . the method of claim 13 , wherein the applying rf power comprises applying mixed frequency rf power to the gas mixture. 17 . the method of claim 13 , wherein the cyclic organosiloxane is octamethylcyclotetrasiloxane (omcts). 18 . the method of claim 13 , wherein the cyclic organosiloxane is selected from the group consisting of 1,3,5,7-tetramethylcyclotetrasiloxane (tmcts), octamethylcyclotetrasiloxane (omcts), 1,3,5,7,9-pentamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane. 19 . the method of claim 13 , wherein the linear hydrocarbon compound comprises one or two carbon-carbon double bonds. 20 . the method of claim 13 , wherein the linear hydrocarbon compound is ethylene. 21 . the method of claim 13 , wherein the linear hydrocarbon compound is selected from the group consisting of ethylene, propylene, isobutylene, acetylene, allylene, ethylacetylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and piperylene. 22 . the method of claim 13 , wherein the gas mixture further comprises a gas selected from the group consisting of helium, argon, and combinations thereof. 23 . the method of claim 13 , further comprising post-treating the low dielectric constant film with an electron beam. 24 . a method for depositing a low dielectric constant film, comprising: providing a gas mixture comprising: octamethylcyclotetrasiloxane (omcts); and ethylene; and applying rf power to the gas mixture at conditions sufficient to deposit a film on the substrate surface, the film having a dielectric constant less than 3.0 and compressive stress; and post-treating the film with an electron beam. 25 . the method of claim 24 , wherein the gas mixture further comprises one or more oxidizing gases. 26 . the method of claim 25 , wherein the one or more oxidizing gases is selected from the group consisting of oxygen, carbon dioxide, and combinations thereof. 27 . the method of claim 25 , wherein the one or more oxidizing gases comprises oxygen, and the conditions comprise an oxygen flow rate less than a flow rate of the ethylene. 28 . the method of claim 24 , wherein the applying rf power comprises applying mixed frequency rf power to the gas mixture. 29 . the method of claim 24 , wherein the gas mixture further comprises a gas selected from the group consisting of helium, argon, and combinations thereof. 30 . the method of claim 24 , wherein the gas mixture includes essentially no oxidizing gas.
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background of the disclosure 1. field of the invention embodiments of the present invention relate to the fabrication of integrated circuits. more particularly, embodiments of the present invention relate to a process for depositing dielectric layers on a substrate. 2. background of the invention integrated circuit geometries have dramatically decreased in size since such devices were first introduced several decades ago. since then, integrated circuits have generally followed the two year/half-size rule (often called moore's law), which means that the number of devices on a chip doubles every two years. today's fabrication facilities are routinely producing devices having 0.13 m and even 0.1 m feature sizes, and tomorrow's facilities soon will be producing devices having even smaller feature sizes. the continued reduction in device geometries has generated a demand for films having lower dielectric constant (k) values because the capacitive coupling between adjacent metal lines must be reduced to further reduce the size of devices on integrated circuits. in particular, insulators having low dielectric constants, less than about 4.0, are desirable. examples of insulators having low dielectric constants include spin-on glass, such as un-doped silicon glass (usg) or fluorine-doped silicon glass (fsg), silicon dioxide, and polytetrafluoroethylene (ptfe), which are all commercially available. more recently, organosilicon films having k values less than about 3.5 have been developed. rose et al. (u.s. pat. no. 6,068,884) disclosed a method for depositing an insulator by partially fragmenting a cyclic organosilicon compound to form both cyclic and linear structures in the deposited film. however, this method of partially fragmenting cyclic precursors is difficult to control and thus, product consistency is difficult to achieve. furthermore, while organosilicon films having desirable dielectric constants have been developed, many known low dielectric organosilicon films have undesirable physical or mechanical properties, such as high tensile stress. high tensile stress in a film can lead to film bowing or deformation, film cracking, film peeling, or the formation of voids in the film, which can damage or destroy a device that includes the film. there is a need, therefore, for a controllable process for making lower dielectric constant films that have desirable physical or mechanical properties. summary of the invention embodiments of the invention include a method for depositing a low dielectric constant film having a dielectric constant less than 3.2 by delivering a gas mixture including a cyclic organosiloxane, a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond, and at least one noble gas to a substrate surface at conditions sufficient to deposit a film on the substrate surface. in one aspect, the deposited film has compressive stress. in one embodiment, the cyclic organosiloxane is octamethylcyclotetrasiloxane (omcts) and the linear hydrocarbon compound is ethylene. the deposited film may be treated with an electron beam. embodiments of the invention also include delivering a gas mixture including a cyclic organosiloxane, a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond, one or more oxidizing gases, and at least one noble gas to a substrate surface at conditions sufficient to deposit a film on the substrate surface, wherein the film has a dielectric constant less than 3.2 and compressive stress. in one aspect, the deposited film is treated with an electron beam. brief description of the drawings so that the manner in which the above recited features of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. it is to be noted, however, that the description and appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments. fig. 1 is a cross-sectional diagram of an exemplary cvd reactor configured for use according to embodiments described herein. fig. 2 is an electron beam chamber in accordance with an embodiment of the invention. fig. 3 is a fragmentary view of the electron beam chamber in accordance with an embodiment of the invention. fig. 4 illustrates the electron beam chamber with a feedback control circuit in accordance with an embodiment of the invention. detailed description of the preferred embodiments embodiments of the invention provide low stress in low dielectric constant films containing silicon, oxygen, and carbon by providing a cyclic organosiloxane, a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond, and optionally, one or more oxidizing gases at conditions sufficient to deposit a film having a dielectric constant less than 3.2. preferably, the film is deposited at conditions providing a dielectric constant less than 3.0 and compressive stress. a film that has compressive stress has a stress of less than 0 mpa, as measured by a fsm 128l tool, available from frontier semiconductor, san jose, calif. more generally, conditions that provide compressive stress are determined by depositing a conformal film on a flat silicon substrate. if the conformal film bows down after deposition, i.e., the film edge is pulled lower than the film center, the process conditions introduced compressive stress. the cyclic organosiloxane includes compounds having one or more silicon-carbon bonds. commercially available cyclic organosiloxane compounds that include one or more rings having alternating silicon and oxygen atoms with one or two alkyl groups bonded to the silicon atoms may be used. for example, the cyclic organosiloxane may be one of the following compounds: 1,3,5,7-tetramethylcyclotetrasiloxane (tmcts), (sihch ₃ o) ₄ (cyclic) octamethylcyclotetrasiloxane (omcts), (si(ch ₃ ) ₂ o) ₄ (cyclic) 1,3,5,7,9-pentamethylcyclopentasiloxane, (sihch ₃ o) ₅ (cyclic) hexamethylcyclotrisiloxane, (si(ch ₃ ) ₂ o) ₃ (cyclic) decamethylcyclopentasiloxane (si(ch ₃ ) ₂ o) ₅ (cyclic). a blend of two or more of the cyclic organosiloxanes may also be used. the cyclic organosiloxane is mixed with a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond. the unsaturated carbon-carbon bond may be a double bond or a triple bond. the linear hydrocarbon compound may include one or two carbon-carbon double bonds. as defined herein, a linear hydrocarbon compound includes hydrogen and carbon atoms, but does not include oxygen, nitrogen, or fluorine atoms. preferably, the linear hydrocarbon compound includes only carbon and hydrogen atoms. the linear hydrocarbon compound may be an alkene, alkylene, or diene having two to about 20 carbon atoms, such as ethylene, propylene, isobutylene, acetylene, allylene, ethylacetylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and piperylene. in any of the embodiments described herein, the gas mixtures may essentially exclude or may include one or more oxidizing gases selected from oxygen (o ₂ ), ozone (o ₃ ), nitrous oxide (n ₂ o), carbon monoxide (co), carbon dioxide (co ₂ ), water (h ₂ o), and combinations thereof. in one aspect, the oxidizing gas is oxygen gas. in another aspect, the oxidizing gas is oxygen gas and carbon dioxide. in another aspect, the oxidizing gas is ozone. when ozone is used as an oxidizing gas, an ozone generator converts from 6% to 20%, typically about 15%, by weight of the oxygen in a source gas to ozone, with the remainder typically being oxygen. however, the ozone concentration may be increased or decreased based upon the amount of ozone desired and the type of ozone generating equipment used. the one or more oxidizing gases may be added to the reactive gas mixture to increase reactivity and achieve the desired carbon content in the deposited film. during deposition, a blend/mixture of a cyclic organosiloxane and a linear hydrocarbon compound having at least one unsaturated carbon-carbon bond is reacted to form a low k film on the substrate. optionally, one or more oxidizing gases are included in the blend/mixture. one or more carrier gases, such as argon, helium, or combinations thereof may be included in the blend/mixture. the films contain a carbon content between about 5 and about 30 atomic percent (excluding hydrogen atoms), preferably between about 5 and about 20 atomic percent. the carbon content of the deposited films refers to atomic analysis of the film structure which typically does not contain significant amounts of non-bonded hydrocarbons. the carbon contents are represented by the percent of carbon atoms in the deposited film, excluding hydrogen atoms which are difficult to quantify. for example, a film having an average of one silicon atom, one oxygen atom, one carbon atom, and two hydrogen atoms has a carbon content of 20 atomic percent (one carbon atom per five total atoms), or a carbon content of 33 atomic percent excluding hydrogen atoms (one carbon atom per three total atoms). in any of the embodiments described herein, after the low dielectric constant film is deposited, the film may be treated with an electron beam (e-beam) to reduce the dielectric constant of the film. the electron beam treatment typically has a dose between about 50 and about 2000 micro coulombs per square centimeter (c/cm ² ) at about 1 to 20 kiloelectron volts (kev). the e-beam current typically ranges from about 1 ma to about 40 ma, and is preferably about 10 to about 20 ma. the e-beam treatment is typically operated at a temperature between about room-temperature and about 450 c. for about 10 seconds to about 15 minutes. in one aspect, the e-beam treatment conditions include 6 kv, 10-18 ma and 50 c/cm ² at 350 c. for about 15 to about 30 seconds to treat a film having a thickness of about 1 micron. in another aspect, the e-beam treatment conditions include 4.5 kv, 10-18 ma and 50 pc/cm ² at 350 c. for about 15 to about 30 seconds to treat a film having a thickness of about 5000 . argon or hydrogen may be present during the electron beam treatment. although any e-beam device may be used, one exemplary device is the ebk chamber, available from applied materials, inc. treating the low dielectric constant film with an electron beam after the low dielectric constant film is deposited will volatilize at least some of the organic groups in the film which may form voids in the film. alternatively, in another embodiment, after the low dielectric constant film is deposited, the film is post-treated with an annealing process to reduce the dielectric constant of the film. preferably, the film is annealed at a temperature between about 200 c. and about 400 c. for about 2 seconds to about 1 hour, preferably about 30 minutes. a non-reactive gas such as helium, hydrogen, nitrogen, or a mixture thereof is introduced at a rate of 100 to about 10,000 sccm. the chamber pressure is maintained between about 2 torr and about 10 torr. the rf power is about 200 w to about 1,000 w at a frequency of about 13.56 mhz, and the preferable substrate spacing is between about 300 mils and about 800 mils. the film may be deposited using any processing chamber capable of chemical vapor deposition (cvd). for example, fig. 1 shows a vertical, cross-section view of a parallel plate cvd processing chamber 10 . the chamber 10 includes a high vacuum region 15 and a gas distribution manifold 11 having perforated holes for dispersing process gases there-through to a substrate (not shown). the substrate rests on a substrate support plate or susceptor 12 . the susceptor 12 is mounted on a support stem 13 that connects the susceptor 12 to a lift motor 14 . the lift motor 14 raises and lowers the susceptor 12 between a processing position and a lower, substrate-loading position so that the susceptor 12 (and the substrate supported on the upper surface of susceptor 12 ) can be controllably moved between a lower loading/off-loading position and an upper processing position which is closely adjacent to the manifold 11 . an insulator 17 surrounds the susceptor 12 and the substrate when in an upper processing position. gases introduced to the manifold 11 are uniformly distributed radially across the surface of the substrate. a vacuum pump 32 having a throttle valve controls the exhaust rate of gases from the chamber 10 through a manifold 24 . deposition and carrier gases, if needed, flow through gas lines 18 into a mixing system 19 and then to the manifold 11 . generally, each process gas supply line 18 includes (i) safety shut-off valves (not shown) that can be used to automatically or manually shut off the flow of process gas into the chamber, and (ii) mass flow controllers (also not shown) to measure the flow of gas through the gas supply lines 18 . when toxic gases are used in the process, several safety shut-off valves are positioned on each gas supply line 18 in conventional configurations. in one aspect, the cyclic organosiloxane is introduced to the mixing system 19 at a flowrate of about 75 sccm to about 500 sccm. the linear hydrocarbon compound having at least one unsaturated carbon-carbon bond is introduced to the mixing system 19 at a flowrate of about 200 sccm to about 5,000 sccm. the optional oxidizing gas has a flowrate of about 0 sccm to about 200 sccm. the carrier gas has a flowrate of about 100 sccm to about 5,000 sccm. preferably, the cyclic organosilicon compound is octamethylcyclotetrasiloxane, and the linear hydrocarbon compound is ethylene. the deposition process is preferably a plasma enhanced process. in a plasma enhanced process, a controlled plasma is typically formed adjacent the substrate by rf energy applied to the gas distribution manifold 11 using a rf power supply 25 . alternatively, rf power can be provided to the susceptor 12 . the rf power to the deposition chamber may be cycled or pulsed to reduce heating of the substrate and promote greater porosity in the deposited film. the power density of the plasma for a 200 or 300 mm substrate is between about 0.03 w/cm ² and about 3.2 w/cm ² , which corresponds to a rf power level of about 10 w to about 1,000 w for a 200 mm substrate and about 20 w to about 2,250 w for a 300 mm substrate. preferably, the rf power level is between about 200 w and about 1,700 w for a 300 mm substrate. the rf power supply 25 can supply a single frequency rf power between about 0.01 mhz and 300 mhz. preferably, the rf power may be delivered using mixed, simultaneous frequencies to enhance the decomposition of reactive species introduced into the high vacuum region 15 . in one aspect, the mixed frequency is a lower frequency of about 12 khz and a higher frequency of about 13.56 mhz. in another aspect, the lower frequency may range between about 300 hz to about 1,000 khz, and the higher frequency may range between about 5 mhz and about 50 mhz. preferably, the low frequency power level is about 150 w. preferably, the high frequency power level is about 200 w and about 750 w, more preferably, about 200 w to about 400 w. during deposition, the substrate is maintained at a temperature between about 20 c. and about 500 c., preferably between about 100 c. and about 450 c. the deposition pressure is typically between about 1 torr and about 20 torr, preferably between about 4 torr and about 7 torr. the deposition rate is typically between about 3,000 /min and about 15,000 /min. when additional dissociation of the oxidizing gas is desired, an optional microwave chamber 28 can be used to input power from between about 50 watts and about 6,000 watts to the oxidizing gas prior to the gas entering the processing chamber 10 . the additional microwave power can avoid excessive dissociation of the organosilicon compounds prior to reaction with the oxidizing gas. a gas distribution plate (not shown) having separate passages for the organosilicon compound and the oxidizing gas is preferred when microwave power is added to the oxidizing gas. typically, any or all of the chamber lining, distribution manifold 11 , susceptor 12 , and various other reactor hardware is made out of materials such as aluminum or anodized aluminum. an example of such a cvd reactor is described in u.s. pat. no. 5,000,113, entitled a thermal cvd/pecvd reactor and use for thermal chemical vapor deposition of silicon dioxide and in-situ multi-step planarized process, which is incorporated by reference herein. a system controller 34 controls the motor 14 , the gas mixing system 19 , and the rf power supply 25 which are connected therewith by control lines 36 . the system controller 34 controls the activities of the cvd reactor and typically includes a hard disk drive, a floppy disk drive, and a card rack. the card rack contains a single board computer (sbc), analog and digital input/output boards, interface boards, and stepper motor controller boards. the system controller 34 conforms to the versa modular europeans (vme) standard which defines board, card cage, and connector dimensions and types. the vme standard also defines the bus structure having a 16-bit data bus and 24-bit address bus. the system controller 34 operates under the control of a computer program stored on a hard disk drive 38 . the above cvd system description is mainly for illustrative purposes, and other cvd equipment such as electrode cyclotron resonance (ecr) plasma cvd devices, induction-coupled rf high density plasma cvd devices, or the like may be employed. additionally, variations of the above described system such as variations in susceptor design, heater design, location of rf power connections and others are possible. for example, the substrate could be supported and heated by a resistively heated susceptor. once the film is deposited, the substrate may be transferred to an electron beam (e-beam) apparatus for further processing, i.e., curing. the substrate may be transferred with vacuum break or under vacuum, i.e., without any vacuum break. fig. 2 illustrates an e-beam chamber 200 in accordance with an embodiment of the invention. the e-beam chamber 200 includes a vacuum chamber 220 , a large-area cathode 222 , a target plane 230 located in a field-free region 238 , and a grid anode 226 positioned between the target plane 230 and the large-area cathode 222 . the e-beam chamber 200 further includes a high voltage insulator 224 , which isolates the grid anode 226 from the large-area cathode 222 , a cathode cover insulator 228 located outside the vacuum chamber 220 , a variable leak valve 232 for controlling the pressure inside the vacuum chamber 220 , a variable high voltage power supply 229 connected to the large-area cathode 222 , and a variable low voltage power supply 231 connected to the grid anode 226 . in operation, the substrate (not shown) to be exposed with the electron beam is placed on the target plane 230 . the vacuum chamber 220 is pumped from atmospheric pressure to a pressure in the range of about 1 mtorr to about 200 mtorr. the exact pressure is controlled by the variable rate leak valve 232 , which is capable of controlling pressure to about 0.1 mtorr. the electron beam is generally generated at a sufficiently high voltage, which is applied to the large-area cathode 222 by the high voltage power supply 229 . the voltage may range from about 500 volts to about 30,000 volts or higher. the high voltage power supply 229 may be a bertan model 105-30r manufactured by bertan of hickville, n.y., or a spellman model sl30n-1200258 manufactured by spellman high voltage electronics corp., of hauppauge, n.y. the variable low voltage power supply 231 applies a voltage to the grid anode 226 that is positive relative to the voltage applied to the large-area cathode 222 . this voltage is used to control electron emission from the large-area cathode 222 . the variable low voltage power supply 231 may be an acopian model 150pt12 power supply available from acopian of easton, pa. to initiate electron emission, the gas in the field-free region 238 between the grid anode 226 and the target plane 30 must become ionized, which may occur as a result of naturally occurring gamma rays. electron emission may also be artificially initiated inside the vacuum chamber 220 by a high voltage spark gap. once this initial ionization takes place, positive ions 342 (shown in fig. 3 ) are attracted to the grid anode 226 by a slightly negative voltage, i.e., on the order of about 0 to about 200 volts, applied to the grid anode 226 . these positive ions 342 pass into the accelerating field region 236 , disposed between the large-area cathode 222 and the grid anode 226 , and are accelerated towards the large-area cathode 222 as a result of the high voltage applied to the large-area cathode 222 . upon striking the large-area cathode 222 , these high-energy ions produce secondary electrons 344 , which are accelerated back toward the grid anode 226 . some of these electrons 344 , which travel generally perpendicular to the cathode surface, strike the grid anode 226 , but many of these electrons 344 pass through the grid anode 226 and travel to the target plane 230 . the grid anode 226 is preferably positioned at a distance less than the mean free path of the electrons emitted by the large-area cathode 222 , e.g., the grid anode 226 is preferably positioned less than about 4 mm from the large-area cathode 222 . due to the short distance between the grid anode 226 and the large-area cathode 222 , no, or minimal if any, ionization takes place in the accelerating field region 236 between the grid anode 226 and the large-area cathode 222 . in a conventional gas discharge device, the electrons would create further positive ions in the accelerating field region, which would be attracted to the large-area cathode 222 , creating even more electron emission. the discharge could easily avalanche into an unstable high voltage breakdown. however, in accordance with an embodiment of the invention, the ions 342 created outside the grid anode 226 may be controlled (repelled or attracted) by the voltage applied to the grid anode 226 . in other words, the electron emission may be continuously controlled by varying the voltage on the grid anode 226 . alternatively, the electron emission may be controlled by the variable leak valve 232 , which is configured to raise or lower the number of molecules in the ionization region between the target plane 230 and the large-area cathode 222 . the electron emission may be entirely turned off by applying a positive voltage to the grid anode 226 , i.e., when the grid anode voltage exceeds the energy of any of the positive ion species created in the space between the grid anode 226 and target plane 230 . fig. 4 illustrates the e-beam chamber 200 with a feedback control circuit 400 . in some applications it may be desirable to provide a constant beam current at different electron beam energies. for example, it may be desirable to expose or cure the upper layer of the film formed on the substrate, but not the bottom layer. this may be accomplished by lowering the electron beam energy such that most of the electrons are absorbed in the upper layer of the film. subsequent to curing the top layer, it may be desirable to cure the full thickness of the film. this can be done by raising the accelerating voltage of electron beam to penetrate completely through the film. the feedback control circuit 400 is configured to maintain a constant beam current independent of changes in the accelerating voltage. the feedback control circuit 400 includes an integrator 466 . the beam current is sampled via a sense resistor 490 , which is placed between the target plane 230 and the integrator 466 . the beam current may also be sampled at the grid anode 226 as a portion of the beam is intercepted there. two unity gain voltage followers 492 buffer the signal obtained across the sense resistor 490 and feed it to an amplifier 496 with a variable resistor 494 . the output of this amplifier controls the voltage on the grid anode 226 such that an increase in beam current will cause a decrease in bias voltage on the grid anode 226 and a decrease in beam current from the large-area cathode 222 . the gain of the amplifier 496 is adjusted, by means of the variable resistor 494 , so that any change in beam current caused by a change in the accelerating voltage is counteracted by a change in bias voltage, thereby maintaining a constant beam current at the target. alternatively, the output of the amplifier 496 may be connected to a voltage controlled variable rate leak valve 298 to counteract changes in beam current by raising or lowering the pressure in the ionization region 238 . further, a wider range of beam current control may be provided by utilizing feedback signals to both the variable leak valve 298 and the grid anode 226 . other details of the e-beam chamber 200 are described in u.s. pat. no. 5,003,178, entitled large-area uniform electron source, issued to william r. livesay, assigned to electron vision corporation (which is currently owned by the assignee of the present invention) and is incorporated by reference herein to the extent not inconsistent with the invention. examples the following examples illustrate the low dielectric films of the present invention. the films were deposited using a chemical vapor deposition chamber that is part of an integrated processing platform. in particular, the films were deposited using a producer 300 mm system, available from applied materials, inc. of santa clara, calif. example 1 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 6 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 800 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,709 /min, and had a dielectric constant (k) of about 2.99 measured at 0.1 mhz. the film had a compressive stress of 9.23 mpa. example 2 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 800 sccm; and helium, at about 750 sccm; the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 5,052 /min, and had a dielectric constant (k) of about 2.99 measured at 0.1 mhz. the film had a compressive stress of 5.61 mpa. example 3 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 257 sccm; ethylene, at about 800 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,963 /min, and had a dielectric constant (k) of about 2.98 measured at 0.1 mhz. the film had a compressive stress of 1.69 mpa. example 4 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 800 sccm; and helium, at about 1,000 scorn the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 200 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 3,339 /min, and had a dielectric constant (k) of about 2.97 measured at 0.1 mhz. the film had a compressive stress of 19.22 mpa. example 5 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 1,200 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,814 /min, and had a dielectric constant (k) of about 3.07 measured at 0.1 mhz. the film had a compressive stress of 15.02 mpa. example 6 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of 350 c. octamethylcyclotetrasiloxane (omcts), at about 321 sccm; argon, at about 3,000 sccm; ethylene, at about 1,000 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of 750 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the deposited film had a dielectric constant (k) of about 3.15 measured at 0.1 mhz. the film had a compressive stress of 1.76 mpa. comparison example 1 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of 350 c. octamethylcyclotetrasiloxane (omcts), at about 298 sccm; ethylene, at about 800 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,825 /min, and had a dielectric constant (k) of about 2.94 measured at 0.1 mhz. the film had a tensile stress of 3.23 mpa. comparison example 2 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of 350 c. octamethylcyclotetrasiloxane (omcts), at about 340 sccm; ethylene, at about 800 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,472 /min, and had a dielectric constant (k) of about 2.91 measured at 0.1 mhz. the film had a tensile stress of 5.16 mpa. example 7 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 2,400 sccm; oxygen, at about 160 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,479 /min, and had a dielectric constant (k) of about 2.99 measured at 0.1 mhz. the film had a compressive stress of 3.34 mpa. example 8 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 2,800 sccm; oxygen, at about 160 sccm; and helium, at about 1,000 sccm the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,322 /min, and had a dielectric constant (k) of about 3.00 measured at 0.1 mhz. the film had a compressive stress of 5.8 mpa. example 9 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 200 sccm; ethylene, at about 5,000 sccm; and oxygen, at about 100 sccm helium, at about 1,000 sccm the substrate was positioned 450 mils from the gas distribution showerhead. a power level of about 500 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 3,679 /min, and had a dielectric constant (k) of about 3.14 measured at 0.1 mhz. the film had a compressive stress of 82 mpa. example 10 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 200 sccm; ethylene, at about 4,000 sccm; and oxygen, at about 100 sccm helium, at about 1,000 sccm the substrate was positioned 450 mils from the gas distribution showerhead. a power level of about 500 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,011 /min, and had a dielectric constant (k) of about 3.10 measured at 0.1 mhz. the film had a compressive stress of 38 mpa. example 11 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 200 sccm; ethylene, at about 3,200 sccm; and oxygen, at about 100 sccm helium, at about 1,000 sccm the substrate was positioned 450 mils from the gas distribution showerhead. a power level of about 500 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 4,291 /min, and had a dielectric constant (k) of about 3.07 measured at 0.1 mhz. the film had a compressive stress of 27 mpa. example 12 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 200 sccm; ethylene, at about 1,600 sccm; and oxygen, at about 100 sccm helium, at about 1,000 sccm the substrate was positioned 450 mils from the gas distribution showerhead. a power level of about 500 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 5,163 /min, and had a dielectric constant (k) of about 2.96 measured at 0.1 mhz. the film had a compressive stress of 3 mpa. comparison example 3 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 200 sccm; ethylene, at about 800 sccm; and oxygen, at about 100 sccm helium, at about 1,000 sccm the substrate was positioned 450 mils from the gas distribution showerhead. a power level of about 500 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 6,061 /min, and had a dielectric constant (k) of about 2.86 measured at 0.1 mhz. the film had a tensile stress of 8 mpa. comparison example 4 a low dielectric constant film was deposited on a 300 mm substrate from the following reactive gases at a chamber pressure of about 5 torr and substrate temperature of about 350 c. octamethylcyclotetrasiloxane (omcts), at about 215 sccm; ethylene, at about 800 sccm; and oxygen, at about 160 sccm helium, at about 1,000 scorn the substrate was positioned 300 mils from the gas distribution showerhead. a power level of about 400 w at a frequency of 13.56 mhz and a power level of about 150 w at a frequency of 350 khz were applied to the showerhead for plasma enhanced deposition of the film. the film was deposited at a rate of about 5,810 /min, and had a dielectric constant (k) of about 2.93 measured at 0.1 mhz. the film had a tensile stress of 23.46 mpa. examples 1-6 and comparison examples 1 and 2 show the processing conditions that were used to deposit low dielectric constant films from gas mixtures that included omcts, ethylene, and oxygen. the films of examples 1-6 had dielectric constants of less than 3.2 and compressive stress. the films of comparison examples 1 and 2 also had dielectric constants of less than 3.2. however, the films of comparison examples 1 and 2 had tensile stress, rather than compressive stress. as defined herein, a film that has tensile stress is a film that has a stress of greater than 0 mpa, as measured by a fsm 128l tool. it is believed that the lower flow rate of omcts, i.e., 257 scorn or less, used in examples 1-5 than in the comparison examples 1 and 2 may contribute to the compressive stress of the films in examples 1-5. it is believed that the higher flow rate of omcts in example 6 does not result in a film with tensile stress because a higher flowrate of ethylene and a flow of an additional carrier gas, argon, diluted the amount of omcts in the gas mixture of example 6. examples 7-12 and comparison examples 3 and 4 show the processing conditions that were used to deposit low dielectric constant films from gas mixtures that included omcts and ethylene. the films of examples 7-12 had dielectric constants of less than 3.2 and compressive stress. the films of comparison examples 3 and 4 also had dielectric constants of less than 3.2. however, the films of comparison examples 3 and 4 had tensile stress, rather than compressive stress. it is believed that the higher flow rate of ethylene, i.e., greater than about 800 sccm, used in examples 7-12 than in the comparison examples 3 and 4 may contribute to the compressive stress of the films in examples 7-12. while the foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims which follow.
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041-780-081-702-052
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US
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[
"US"
] |
F02B75/02,F02P7/067
| 1991-11-04T00:00:00 |
1991
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[
"F02"
] |
integral magnetic ignition pickup trigger
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a trigger system for the ignition system of an internal combustion engine having a crankcase with a rotatable crankshaft includes an aluminum disk-shaped hub for connection to the crankshaft and rotatable therewith on the end opposite the flywheel of the engine. the hub has at least one weight formed into the hub and offset from its center of gravity for balancing and reducing vibration of the engine during operation. a plurality of magnets or other magnetically responsive elements are provided in openings in a flange extending around the periphery of the hub. a stationary sensor is mounted adjacent the hub for detecting impulses from the magnetically responsive elements as the hub rotates and utilizing the impulses to trigger the ignition system.
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1. a trigger system for the ignition system of an internal combustion engine having a crankcase with a rotatable crankshaft therein, and a flywheel on one end of said crankcase connected to an end of said crankshaft, the trigger system comprising: a nonferromagnetic disk-shaped hub for connection to said crankshaft and rotatable therewith on the end opposite said flywheel, said hub having at least one attached weight offset from its center of gravity for balancing and reducing vibration of said engine during operation, and, integral therewith, a plurality of magnetically responsive elements about the periphery of the hub; and a stationary sensor mounted adjacent said hub for detecting impulses from said magnetically responsive elements as said hub rotates and utilizing said impulses to trigger said ignition system. 2. the trigger system of claim 1 wherein said weight is formed into said hub. 3. the trigger system of claim 1 wherein said hub has a flange along its periphery, and wherein said magnetically responsive elements are disposed on said flange facing away from the center of the hub. 4. the trigger system of claim 1 wherein said hub has openings along its periphery and wherein said magnetically responsive elements are mounted in said openings. 5. the trigger system of claim 1 wherein said hub is composed of a nonferrous metal. 6. the trigger system of claim 1 wherein said magnetically responsive elements are composed of a ferromagnetic metal. 7. the trigger system of claim 1 wherein said magnetically responsive elements comprise magnets. 8. the trigger system of claim 1 wherein said hub is composed of aluminum. 9. an ignition trigger for attachment to a crankshaft of an internal combustion engine on the end opposite a flywheel comprising a nonferromagnetic disk-shaped hub of diameter less than about 8 inches having a central opening for securing said hub to said crankshaft, at least one individual weight attached near the hub periphery for balancing and reducing vibration of said engine during operation, and, integral therewith, a plurality of magnetically responsive elements about said periphery for inducing impulses in a stationary sensor as said hub rotates and triggering an internal combustion engine ignition system. 10. the device of claim 9 wherein said hub is composed of aluminum and has a flange along its periphery, and wherein said magnetically responsive elements are composed of a ferromagnetic metal and are disposed on said flange facing away from the center of the hub. 11. the device of claim 10 wherein said weight is formed into said hub. 12. the device of claim 9 wherein said hub is composed of a nonferrous metal and has a flange along its periphery, and wherein said magnetically responsive elements comprise magnets disposed on said flange facing away from the center of the hub. 13. the device of claim 12 wherein said weight is formed into said hub. 14. the device of claim 9 wherein said hub has openings along its periphery and wherein said magnetically responsive elements are mounted in said openings. 15. the device of claim 14 wherein said hub is composed of aluminum and has a flange along its periphery, and wherein said magnetically responsive elements comprise magnets disposed on said flange facing away from the center of the hub. 16. the device of claim 15 wherein said weight is formed into said hub. 17. the device of claim 16 wherein said hub has four of said magnetically responsive elements. 18. an internal combustion engine having a crankcase with a rotatable crankshaft therein; a flywheel connected to one end of said crankshaft; an ignition system for said engine; and an ignition trigger including a nonferromagnetic disk-shaped hub key-connected to said crankshaft and rotatable therewith on the end opposite said flywheel, said hub having at least one counterbalancing weight attached at a position offset from the center of gravity for balancing and reducing vibration of said engine during operation, said hub further having integral therewith a plurality of magnetically responsive elements about its periphery, and a sensor mounted on said crankcase adjacent said hub for detecting impulses from said magnetically responsive elements as said hub rotates and utilizing said impulses to trigger said ignition system. 19. the device of claim 9 wherein said hub has a flange along its periphery and is composed of a nonferrous metal, and wherein said magnetically responsive elements are composed of a ferromagnetic metal and are disposed on said flange facing away from the center of the hub. 20. the device of claim 19 wherein said weight is formed into said hub, and wherein said hub has openings along its periphery for receiving said magnetically responsive elements.
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background of the invention this invention relates to a trigger for the ignition system of an internal combustion engine and, in particular, to a magnet triggered ignition system for four-stroke engines in racing vehicles. the prior art discloses various magnet triggered ignition systems which utilize magnet-containing rotors which are ultimately connected to and rotate in unison with the crankshaft of an internal combustion engine. for example, williams u.s. pat. no. 3,875,920, kopera u.s. pat. no. 4,106,460, schmiedel u.s. pat. no. 3,518,978 and hino et al. u.s. pat. no. 4,499,888 disclose that the rotors on which the magnets are mounted are located in the distributor. burson u.s. pat. no. 3,554,179 and finch u.s. pat. no. 3,521,611 disclose the magnet-containing rotors as being incorporated into the flywheel of the engine, while erhard u.s. pat. no. 4,428,333 discloses the magnet-containing rotor as being incorporated into the fan of the engine. other prior art patents do not specify any particular location for the magnet-containing rotor. many racing vehicles utilize stock, four-stroke engines which are heavily modified. for instance, these engines may utilize non-stock internal and external components such as crankshafts, cam shafts, etc. where nonstock, non-counterbalanced crankshafts are installed, such vehicles often employ a counterbalancing hub attached to one end of the crankshaft to dynamically balance the engine and reduce vibration. typically, this hub is attached to the crankshaft in place of the pulley which normally drives stock engine accessories such as the water pump, alternator, power steering pump, air conditioner compressor, etc., since such accessories are either not used (because of weight considerations) or are not driven by a belt off the engine (because of power consumption). the use of magnet triggered ignition systems is desirable in racing vehicles since it saves weight and increases performance. it has even been known to bolt a rotor plate containing magnets to the balancer hub in order to trigger a sensor in such ignition systems. however, such rotors have had a tendency to "walk", i.e. to change orientation with respect to the crankshaft under repeated use and abuse so that they must be frequently readjusted to keep proper ignition timing. furthermore, such bolt-on accessories add undesired weight to the engine and car. bearing in mind the problems and deficiencies of the prior art, it is therefore an object of the present invention to provide a magnetic ignition pickup trigger which is particularly suitable for the engines of racing vehicles. it is another object of the present invention to provide an ignition system for racing vehicles which may be easily installed in existing vehicles. it is a further object of the present invention to provide a magnetic ignition pickup trigger which reduces undesirable weight in the racing vehicle. it is yet another object of the present invention to provide a magnetic ignition pickup trigger which retains its proper orientation with respect to the crankshaft and timing after repeated useage. it is a further object of the present invention to provide a magnetic ignition pickup trigger which dynamically balances non-stock racing crankshafts in internal combustion engines. summary of the invention the above and other objects, which will be apparent to those skilled in the art, are achieved in the present invention which provides a trigger system for the ignition system of an internal combustion engine having a crankcase with a rotatable crankshaft therein. the trigger system includes a nonferromagnetic disk-shaped hub, preferably made of aluminum, for connection to the crankshaft and rotatable therewith on the end opposite the flywheel of the engine. the hub has at least one attached counterbalancing weight which is preferably formed into the hub and offset from its center of gravity for balancing and reducing vibration of the engine during operation. a plurality of magnetically responsive elements are provided integrally with and about the periphery of the hub. the hub is preferably keyed to the crankshaft end so that it does not change orientation under repeated use. a stationary sensor is mounted adjacent the hub for detecting impulses from the magnetically responsive elements as the hub rotates and utilizing the impulses to trigger the ignition system. the hub preferably has a flange along its periphery with openings therein, and the magnetically responsive elements are mounted in the openings, facing away from the center of the hub. the magnetically responsive elements may be composed of a ferromagnetic metal and preferably comprise magnets. brief description of the drawings fig. 1 is a side elevational view of a typical racing engine employing the integral magnetic ignition pickup trigger of the present invention. fig. 2 shows the front of the preferred embodiment of the integral magnetic ignition pickup trigger hub of the present invention. fig. 3 shows the rear of the embodiment depicted in fig. 2. fig. 4 is a cross sectional elevational view of the embodiment depicted in figs. 2 and 3, along line 4--4. fig. 5 is a partial side elevational view of the embodiment of figs. 2-4 as seen along line 5--5 in fig. 4. detailed description of the invention reference will be made herein to figs. 1-5 of the drawings which depict the preferred embodiment of the present invention in which like numerals refer to like features of the invention. in fig. 1 there is shown a side, schematic-type elevational view of a typical four-stroke, eight cylinder racing engine 10 which comprises an engine block or crankcase 12 and internally, a racing crankshaft 15. crankshaft 15 rotates along shaft sections 16 within crankcase bearings (not shown) and includes throws 18 having bearing surfaces to which the piston rods and pistons (not shown) are connected. as seen in the typical longitudinal orientation of the engine in rear wheel drive vehicles, crankshaft end 22 extends from the rear 14 of the engine and is connected to flywheel 24 and, ultimately, to the clutch/transmission assembly (not shown). at the opposite, front end 13 of engine 10, crankshaft end 20 is connected to hub 30 which incorporates the integral magnetic ignition pickup trigger of the present invention. hub 30 is positively secured to crankshaft end 20 by bolt 26, and is additionally keyed into the end of the crankshaft so that the hub orientation with respect to the crankshaft remains fixed in use. to signal the proper commencement of the ignition spark, hub 30 incorporates around its periphery magnetically responsive elements, in this case four timing magnets 32 which are integrally mounted into openings in the hub periphery. during rotation, magnets 32 are sequentially detected by stationary sensor 50 which sends the proper pulse or signal to the ignition system, which then sequentially triggers sparkplugs which ignite the fuel-air mixture in the engine cylinders (not shown). sensor 50 may be bolted or otherwise secured by conventional means to the front of the crankcase near the hub periphery. the type of circuitry employed in the sensor and ignition system may be of any type normally employed in magnet triggered ignition systems, such as the specific patents listed in the background section of the specification, the disclosures of which are hereby incorporated by reference. in the preferred embodiment, the signal transmitted over wire 52 constitutes a timing signal which is sent to a distributor 60. the distributor receives the signal and utilizes it to trigger the crank spark which is received from cable 65 and transmitted through distributor shaft 62 to rotor 64 and to the individual sparkplug wires 68 via terminals 66 on the rotor cap. as seen in more detail in figs. 2-5, hub 30 is disk shaped and is preferably machined or otherwise formed from a nonferrous material such as aluminum or other non-magnetic metal alloy. hub 30 has a sleeve 42 having a central bore or opening 46 which is typically from 0.002 to 0.004 in. less in diameter than the end 20 of crankshaft 15 to provide a proper press fit. additionally, a key way 44 permits a key to be used to positively fix the hub 30 to the crankshaft 15 without the possibility of rotation of one relative to the other. the front stepped face 34 of the hub extends outwardly to peripheral face 35 which is formed along the outside of flange 36. uniformly spaced at 90.degree. intervals about the periphery of hub 30 are four (4) one-quarter inch cylindrical magnets 32 which are received within comparable openings to form an integral part of the hub. any desired type of ferromagnetic material may be employed, for example, steel bolts or plugs, which will create impulses of a metallic shadow which can be picked up by sensor 50 as hub 30 rotates. this clean shadow is possible because the outer portion of the hub is entirely made of a nonferrous material such as aluminum which is thus free of magnetic amplification. to prevent a non-counterbalanced, racing-type crankshaft from causing excess vibration, there is provided in or on hub 30 a counterbalancing weight 40 which is shown as a wedge-shaped mass which is formed into the hub on its rear face 38 near the periphery. this counterbalancing weight 40, which is offset from the longitudinal axis or center of gravity of hub 30, is manufactured according to known techniques to provide dynamic balancing of the engine during operation to reduce vibration which results from the crankshaft and other moving components of the engine. the hub is preferably less than about 8 inches in diameter for easy replacement of the existing hub or pulley in the racing engine, and is preferably about 61/2 in. in diameter. the present invention provides particular weight savings because it incorporates into a single, integral unit the functions of the magnetic trigger for the ignition timing and the balancer to reduce engine vibration. thus, the present invention provides a combination integral magnetic pickup trigger/balancer hub which is useful in racing vehicles and which will not change orientation with respect to the crankshaft at high engine rpms. additionally, the combination trigger/balancer hub considerably reduces weight of the engine, compared to separate prior art devices which perform similar functions, and thereby further contributes to enhanced performance. the invention may be optionally used only as a conventional balancer hub, without weight penalty, if it is not desired to use the integral magnets as an ignition trigger. while this invention has been described with reference to specific embodiments, it will be recognized by those skilled in the art that variations are possible without departing from the spirit and scope of the invention, and that it is intended to cover all changes and modifications of the invention disclosed herein for the purposes of illustration which do not constitute departure from the spirit and scope of the invention.
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042-388-103-048-11X
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US
|
[
"US"
] |
C07K1/06,C07K1/12,C07K1/18,C07K1/20,G01N33/68
| 2001-02-21T00:00:00 |
2001
|
[
"C07",
"G01"
] |
peptide esterification
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the invention provides methods and reagents for the esterification of peptides. the methods can be used to (i) enable a peptide in a first sample to be quantified relative to the level of the same peptide in a second sample, (ii) identify peptides in a complex mixtures that are targets for sequencing efforts, and (iii) aid peptide sequence elucidation. methods that promote esterification and the formation of esters that are labeled with stable isotopes are described. these methods are useful for the analysis of low concentration (e.g., sub-femtomole) peptide mixtures.
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1 . a method for preparing a peptide ester, the method comprising: providing an acidified alcohol solution; providing a peptide sample comprising a peptide species; and mixing the acidified alcohol solution and the peptide sample to form a mixture and thereby generate an ester of the peptide species, wherein concentration of the peptide species in the mixture is less than 1 nm. 2 . the method of claim 1 , wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, and isopropanol. 3 . the method of claim 1 , wherein the alcohol is a substituted alcohol selected from the group consisting of aminoethanol, trialkyl ammonium ethanol, biotinylated alcohol, and histidine labeled alcohol. 4 . the method of claim 2 , further comprising adsorption of the peptide species onto a solid phase prior to the mixing step. 5 . the method of claim 4 , wherein the solid phase comprises a hydrophilic chromatography phase. 6 . the method of claim 4 , wherein the solid phase comprises a strong cation exchanger. 7 . the method of claim 1 , wherein the ester is a methyl ester. 8 . the method of claim 1 , further comprising sequencing the peptide species after generation of the ester. 9 . a method for preparing a peptide methyl ester, the method comprising: providing a first solution comprising diazomethane and a solvent, wherein the solvent is miscible in water; and mixing the first solution with a second solution, wherein the second solution is aqueous and comprises a peptide species, to thereby form a methyl ester of the peptide species. 10 . the method of claim 9 , wherein the solvent is selected from the group consisting of methanol, ethanol, isopropanol, acetonitrile, ethanolamine and triethanolamine. 11 . the method of claim 9 , further comprising sequencing the peptide species after formation of the methyl ester. 12 . a method of determining the relative quantity of a peptide species in a mixture of peptides, the method comprising: providing a first sample comprising a first population of the peptide species, wherein the concentration of the peptide species in the first sample is less than 1 nm; esterifying the first population of the peptide species to form a first population of peptide esters; providing a second sample comprising a second population of the peptide species, wherein the concentration of the peptide species in the second sample is less than 1 nm; esterifying the second population of the peptide species with an isotopically enriched reagent to form a second population of isotopically labeled peptide esters; mixing the first population of peptide esters with the second population of isotopically labeled peptide esters to form a mixture; separating the mixture into a plurality of fractions; analyzing a fraction with a mass spectrometer to obtain a first signal for the first population of peptide esters and a second signal for the second population of isotopically labeled peptide esters; and determining the relative quantity of the peptide species in the first sample as compared to the second sample. 13 . the method of claim 12 , wherein the first population of peptide esters comprises peptide methyl esters. 14 . the method of claim 12 , wherein the second population of isotopically labeled peptide esters comprises peptide methyl esters. 15 . the method of claim 12 , wherein the second population of the peptide species is labeled with a stable isotope selected from the group consisting of deuterium, carbon-13, nitrogen-15 and oxygen-18. 16 . the method of claim 12 , wherein the second population of the peptide species is esterified using a solution comprising an alcohol. 17 . the method of claim 12 , wherein the second population of the peptide species is esterified using a solution comprising a substituted alcohol. 18 . the method of claim 12 , wherein the first sample and second sample comprise biological material derived from the same cell type or tissue type. 19 . the method of claim 12 , wherein the first sample and second sample comprise biological material derived from different cell types or tissue types. 20 . the method of claim 12 , wherein the determining step comprises ascertaining the ratio of hydrogen in the first population of peptide esters to deuterium in the second population of isotopically labeled peptide esters. 21 . the method of claim 12 , further comprising sequencing the peptide species after determining the relative quantity of the peptide species. 22 . a method of fractionating peptides, comprising: providing a sample comprising a plurality of different peptides; adsorbing the peptides onto a strong cation exchanger; selectively desorbing a first subset of the peptides by the action of a first mobile phase; adsorbing the first subset of peptides onto a reversed phase hplc column; selectively eluting a second subset the peptides from the reversed phase hplc column by a second mobile phase that develops an increasing acetonitrile concentration gradient; and collecting peptide fractions eluted from the reversed phase hplc column. 23 . the method of claim 22 , wherein the reversed phase hplc column is a micro-hplc column comprising both a reversed phase and a strong cation exchanger stationary phase, and wherein the second mobile phase comprises both an acetonitrile gradient and a ph gradient. 24 . the method of claim 23 , further comprising sequencing a peptide contained in a peptide fraction by mass spectrometry. 25 . a peptide separation system, comprising: a column comprising an ion exchange stationary phase and a reversed phase hplc phase, wherein the ion exchange stationary phase has strong cation exchange characteristics, and wherein the reversed phase hplc has c2, c4, c8, c18 or polymeric characteristics; and a mobile phase gradient comprising an acetonitrile gradient and a ph gradient.
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cross reference to related applications this application claims priority from u.s. provisional application no. 60/270,336, filed feb. 21, 2001, and u.s. provisional application no. 60/284,416, filed apr. 16, 2001. these applications are incorporated herein by reference in their entirety. field of the invention this invention relates generally to peptides, and in particular to methods of esterifying peptides. background of the invention methods of detecting and quantitating mrna levels are widely used in approaches for profiling gene expression. proteome analysis, the analysis of protein expression, is a complementary method for the study of gene expression. as compared to the study of gene expression at the mrna level, proteome analysis provides detailed information about biological systems by focusing directly on the proteins, rather than on the nucleic acids that encode them. isotopic labeling of peptides constitutes one mechanism that can be used for the quantification and sequence identification of individual proteins within complex mixtures (see, e.g., gygi et al. (1999) nature biotechnology 17:994-999 and wo 00/11208). for example, gygi et al. described the synthesis of hydrogen- and deuterium-labeled isotope-coded affinity tag (icat) reagents that are used to alkylate cysteine residues of peptides. icat reagents also contain biotin functionality to permit the use of an avidin column to specifically isolate derivatized peptides, thereby simplifying the peptide mixture for analysis and enabling the detection of proteins that are expressed at low levels. cysteine-containing peptides constitute only a fraction of the peptides in some complex protein mixtures. summary of the invention the methods described herein involve the esterification of a peptide species or a population of peptides. according to these methods, peptides that contain an acidic residue or free acid c-terminus can be derivatized. in addition, peptides can optionally be isotopically labeled. the peptide esterification methods can be used, for example, to determine relative protein quantities and can aid in sequence identification of proteins in complex mixtures. in one aspect, the invention features a method for preparing a peptide ester. the method includes the steps of: providing an acidified alcohol solution; providing a peptide sample comprising a peptide species; and mixing the acidified alcohol solution and the peptide sample to form a mixture and thereby generate an ester of the peptide species, wherein concentration of the peptide species in the mixture is less than 1 nm. the method for preparing a peptide ester can further include a step of adsorption of the peptide species onto a solid phase prior to the mixing step. example solid phases include a hydrophilic chromatography phase and a strong cation exchanger. in one example, the ester is a methyl ester. the method can optionally include a step of detecting the peptide species. for example, the method can further include sequencing the peptide species after generation of the ester. in one embodiment, the method features microchemistry that yields quantitative methylation of low concentrations (e.g., pm to nm levels) of a peptide or peptides. microchemistry refers to a scale of chemistry that permits efficient derivatization of a peptide in a sample of a complex mixture in which the peptide sample, or an individual peptide species, is at a concentration of less than 1 nm. a complex mixture of peptides includes one that has been derived from a cell or a tissue. as used herein, a peptide ester refers to a peptide that has been chemically modified through one or more acidic free residues or free acid c-terminus. the term peptide is used synonymously with protein and polypeptide. in one example, peptides used herein are 2-30 amino acids in length, e.g., naturally processed hla-binding peptides. peptides may be supplied in a variety of forms, e.g., dry such as lyophilized, or in a mixture, e.g., reconstituted in solution. alcohols useful in preparing peptide esters of the invention include methanol, ethanol, propanol, and isopropanol. additionally, the alcohols used in performing the methods of the invention may be substituted with specific functional groups, which effectively change the chemical properties of esterified peptides that are generated by this reaction. examples of useful substituted alcohols include aminoethanol, trialkyl ammonium ethanol, biotinylated alcohol, and histidine labeled alcohol. according to the methods describe herein, peptides may further be adsorbed onto a solid phase. techniques for adsorbing peptides onto solid phase are well known in the art and include the use of hydrophilic chromatography (hilic) phase mechanisms, which use mobile phases (such as an acetonitrile to water gradient), salt or ph gradient to recover peptide esters after they are produced. ion exchange solid phases (e.g., strong or weak cation exchangers and strong or weak anion exchangers) using a salt or ph gradient to elute the peptide esters can also be used for this application. reversed phase resins such as c2, c4, c8, and c18 or the polymeric reversed phase solid phases (e.g., poros r1, r2, and/or r3, and plrp-s type phases) can also be used to adsorb peptides. the term, solid phase, as used herein, is meant to denote any stationary support or matrix system to which the peptides can be adsorbed. for the purposes of this application, the terms solid phase and stationary phase are used interchangeably. examples of solid phases that are useful include hilic (a strong cation exchanger that can use sulfonic acid groups to adsorb water molecules into which the peptides are adsorbed). in one embodiment, the solid phase comprises a strong cation exchanger (scx). further examples of solid phases that are useful include ion exchange resins such as a strong cation exchanger that uses sulfonic acid groups to adsorb the peptides, a weak cation exchanger that uses carboxylic functionality to adsorb the peptides, a strong anion exchanger that uses quaternary amines to adsorb the peptides, and/or a weak anion exchanger that uses secondary or tertiary amines to adsorb peptide. reversed phase resins such as c2, c4, c8, and c18 or the polymeric reversed phase solid phases (e.g., poros r1, r2, and/or r3, and plrp-s type phases) are also useful for adsorbing peptides. in another aspect, the invention features a method for preparing a peptide methyl ester. the method includes the step of: providing a first solution comprising diazomethane and a solvent, wherein the solvent is miscible in water; and mixing the first solution with a second solution, wherein the second solution is aqueous and comprises a peptide species, to thereby form a methyl ester of the peptide species. the term miscible in water refers to solvents that are freely soluble in water (e.g., solvents that have a solubility of 80-100% in water). examples of solvents that are useful for the method include methanol, ethanol, isopropanol, acetonitrile, ethanolamine and triethanolamine. in one embodiment, the method further includes sequencing the peptide species after formation of the methyl ester. in another aspect, the invention features a method of determining the relative quantity of a peptide species in a mixture of peptides. the method includes the steps of: (a) providing a first sample including a first population of the peptide species, wherein the concentration of the peptide species in the first sample is less than 1 nm; (b) esterifying the first population of the peptide species to form a first population of peptide esters; (c) providing a second sample including a second population of the peptide species, wherein the concentration of the peptide species in the second sample is less than 1 nm; (d) esterifying the second population of the peptide species with an isotopically enriched reagent to form a second population of isotopically labeled peptide esters; (e) mixing the first population of peptide esters with the second population of isotopically labeled peptide esters to form a mixture; (f) separating the mixture into a plurality of fractions; (g) analyzing a fraction with a mass spectrometer to obtain a first signal for the first population of peptide esters and a second signal for the second population of isotopically labeled peptide esters; and (h) determining the relative quantity of the peptide species in the first sample as compared to the second sample. in one embodiment, the first population of peptide esters includes peptide methyl esters. in another embodiment, the second population of isotopically labeled peptide esters includes peptide methyl esters. the second population of the peptide species can labeled with a stable isotope such as deuterium, carbon-13, nitrogen-15 and oxygen-18. in one example, the second population of the peptide species is esterified using a solution containing an alcohol. in another example, the second population of the peptide species is esterified using a solution containing a substituted alcohol. in one embodiment, the first sample and second sample contain biological material derived from the same cell type or tissue type. in another embodiment, the first sample and second sample contain biological material derived from different cell types or tissue types. the determining step of the method can include ascertaining the ratio of hydrogen in the first population of peptide esters to deuterium in the second population of isotopically labeled peptide esters. in addition, the method can further include sequencing the peptide species after determining the relative quantity of the peptide species. methods of obtaining a preparation of peptides are well known and include: culturing transformed host cells under culture conditions suitable to express the encoded peptides and purifying the resulting peptides using known purification process, such as gel filtration and ion exchange chromatography. the purification of peptides may also include using an affinity column containing agents that bind to the peptides; one or more column steps over such affinity resins as concanavalin a-agarose, heparin-toyopearl or cibacrom blue 3ga sepharos; one or more steps involving hydrophobic interaction chromatography using such resins as phenyl ether, butyl ether, or propyl ether; and immunoaffinity chromatography. additionally, one or more reversed-phase high performance liquid chromatography (rp-hplc) steps employing hydrophobic rp-hplc media, e.g., silica gel having pendant methyl or other aliphatic groups, can be employed to further purify the peptides. some or all of the foregoing purification steps, in various combinations, can also be employed to provide a substantially homogenous isolated recombinant peptide. alternately, a preparation of peptides may also be produced by known conventional chemical synthesis. methods for constructing peptides by synthetic means are known to those skilled in the art and include solid phase synthesis schemes that employ strategies that build peptides one amino acid residue at a time from the c-terminal end with side chains protected with either 9-fluorenylmethyloxycarbonyl (fmoc) groups, or t-butyloxycarbonyl (t-boc) groups. peptides may be isolated from any sample of interest. samples may be obtained from vertebrate or invertebrate cells, tissues, or organs, or alternately from cells grown in culture under either control or experimental conditions. the choice of a sample of interest will thus depend on the experimental protocol of the investigator and objective of the investigation. therefore, in this aspect of the invention, a comparison of results obtained from a first sample to a second sample can involve a first sample that is from the same cell, tissue or organ type as the second sample. alternately, the comparison can involve a first sample from a different cell, tissue or organ type as the second sample. comparison of a first sample from the same cell, tissue or organ as the second sample might be done to determine the effects of an experimental condition as compared to a control sample, for example, while comparison of a first sample from a different cell, tissue or organ as the second sample might be carried out to determine how different cells, tissues or organs respond to an experimental condition. in one aspect of the invention, peptides can be methylated using the methods described herein. methylation of peptides can be carried out using, for example, alcohols or substituted alcohols, as described herein. a reagent comprising molecules containing methyl groups refers to chemicals having reactive (ch ₃ or ch ₂ ) groups. examples of such reagents include diazomethane, methanol, and methanolic hcl. an isotopically enriched reagent refers to any isotope of a chemical element that is not subject to rapid degradation, e.g., an isotope that has a long half-life. examples of such useful isotopes include deuterium, carbon-13, nitrogen-15 and oxygen-18. a mixture of peptide esters and isotopically labeled peptide esters refers to a solution that contains specific amounts of the first component (e.g., peptide methyl esters) and the second component (e.g., isotopically labeled peptide methyl esters). varying the components of the mixture will depend on the experimental conditions being tested and under the control of the skilled artisan. examples of mixtures that are useful in the invention include 4:1, 3:1, 2:1, 1:1, 0.5:1, 0.3:1, 0.25:1. separating the mixture into fractions refers to any method of fractionating the solution. methods of fractionation of peptide solutions are well known in the art and include reversed phase, ion exchange, hilic, and normal phase chromatography. in one aspect, the invention features the use of peptide esterification in conjunction with deuteroesterification. these methods can be used, for example, to detect peptides, e.g., novel peptides in antigen pulsed cell lines, to quantitate expressed protein tag (ept) levels for application to proteomic studies, and/or to permit peptide sequence elucidation. in another aspect, the invention features a method of fractionating peptides. the method includes the steps of: (a) providing a sample comprising a plurality of different peptides; (b) adsorbing the peptides onto a strong cation exchanger; (c) selectively desorbing a first subset of the peptides by the action of a first mobile phase; (d) adsorbing the first subset of peptides onto a reversed phase hplc column; (e) selectively eluting a second subset the peptides from the reversed phase hplc column by a second mobile phase that develops an increasing acetonitrile concentration gradient; and (f) collecting peptide fractions eluted from the reversed phase hplc column. in one example of this method, the reversed phase hplc column is a micro-hplc column containing both a reversed phase and a strong cation exchanger stationary phase, and the second mobile phase contains both an acetonitrile gradient and a ph gradient. the method can optionally further include sequencing a peptide contained in a peptide fraction by mass spectrometry. in another aspect, the invention features a peptide separation system including: a column containing an ion exchange stationary phase and a reversed phase hplc phase, wherein the ion exchange stationary phase has strong cation exchange characteristics, and wherein the reversed phase hplc has c2, c4, c8, c18 or polymeric characteristics; and a mobile phase gradient containing an acetonitrile gradient and a ph gradient. the peptide separation system can optionally include a mass spectrometer, e.g., an on-line mass spectrometer wherein that receives peptide eluted via the mobile phase gradient. in another aspect, the invention includes a method, e.g., a method described herein, of sequencing peptides in a sample at sub-femtomole levels of sensitivity. one method includes the steps of: (a) isolating a first population of peptides from a first sample; (b) esterifying the first population of peptides with a reagent containing molecules containing alkyl groups to form peptide esters; (c) isolating a second population of peptides from a second sample, wherein the second sample is substantially identical to the first sample; (d) mixing the peptide esters of (b) with the second population of peptides from (c) to form a mixture; (e) separating the mixture into fractions; (f) analyzing the fractions with a mass spectrometer to obtain a first peptide map for the peptide esters and a second peptide map for the second population of peptides; and (g) sequencing a population of peptides in the fractions by comparing the first peptide map obtained for the peptide esters with the second peptide map obtained for the second population of peptides. sub-femtomole levels of sensitivity refers to the analysis of microliter aliquots of peptide mixtures that contain individual components that are at concentrations below 10 ⁹ m (1 nm). it is an advantage of the invention to be able to sequence peptides at such low levels of detection. alkyl group refers to a hydrocarbon, comprised of carbon and hydrogen atoms that may be of various carbon chain lengths and contain various branches of various carbon chain lengths. carbon chain lengths of 1 to 4 and branch chain lengths of 0-4 carbon atoms can be used in the methods described herein. substantially identical is meant to refer to a second sample that has been derived from the same type of cell, tissue or organ of interest as a first sample at the same time and under the same conditions. in this aspect of the invention, peptides can be esterifieded using the methods described herein. a peptide map refers to the pattern of signals that is generated by hplc separation of peptides in another aspect, the invention includes a method of sequencing peptides in a sample at femtomole levels of sensitivity. the method includes the steps of: (a) isolating a first population of peptides from a first sample; (b) esterifying the first population of peptides with a reagent comprising molecules containing alkyl groups to form peptide esters; (c) isolating a second population of peptides from a second sample, wherein the second sample is substantially identical to the first sample; (d) esterifying the second population of peptides with an isotopically enriched reagent comprising molecules containing stable isotopes to form esters that are labeled with a stable isotope; (e) mixing the peptide esters of (b) with the esters that are labeled with a stable isotope of (d) to form a mixture; (f) separating the mixture into fractions; (g) analyzing the fractions with a mass spectrometer to obtain a first peptide map for the peptide esters and a second peptide map for the esters that are labeled with a stable isotope; and (h) sequencing a population of peptides in the fractions by comparing the peptide map obtained for the peptide esters with the second peptide map obtained for the esters that are labeled with a stable isotope. in this aspect of the invention, esterification of peptides can be accomplished with, for example, methods using alcohols or substituted alcohols, as described herein. forming esters that are labeled with stable isotopes can be performed by the methods described herein. also within the invention is a system for fractionating peptides using combined multi-modal hplc separation mechanisms including: (a) a combination of ion exchange chromatography with reversed phase chromatography; (b) an ion exchange stationary phase, wherein the ion exchange stationary phase has strong cation exchange characteristics; (c) a reversed phase hplc stationary phase, wherein the reversed phase hplc stationary phase has c2, c4, c8, c18 or polymeric characteristics; (d) a mobile phase comprising acetonitrile, wherein the mobile phase promotes a mechanism by which peptides are fractionated by their hydrophobic character; and (e) peptide-ester fractions which are collected for analysis by a lc/ms/ms. reversed phase hplc stationary phase that has c2, c4, c8, c18 or polymeric characteristics refers to a solid particle that imparts hydrophobic character to adsorb peptides or a solid particle that has covalently linked to it functional groups that impart hydrophobic character to adsorb peptides. cation exchange properties refers to a solid particle that has anionic character that attracts the positively charged molecules. for the sake of this application, the terms a strong cation exchanger and a strong cation exchanger stationary phase are used interchangeably. the terms refer to a column of particles that adsorb peptides by a cation exchange mechanism. mobile phase refers to a solvent system that promotes analyte desorption from a chromatographic stationary phase. examples of mobile phases useful in the invention include compositions of acetonitrile and water for reversed phase chromatography and hilic separation and aqueous solutions of low to high ph for scx chromatography. in another aspect, the invention includes a method of fractionating peptides, including the steps of: (a) providing a sample of peptides; (b) adsorbing the peptides onto a strong cation exchanger in the presence of a high acetonitrile concentration; (c) selectively desorbing the peptides by the action of mobile phases that develop a gradient of increasing water concentration; (d) fractionating the peptides by the strong cation exchanger; (e) re-adsorbing the peptides onto a reversed phase hplc column; (f) selectively eluting the peptides from the reversed phase hplc column by mobile phases that develop an increasing acetonitrile concentration gradient; and (g) collecting peptide fractions for analysis by a lc/ms/ms. a high acetonitrile concentration is meant to denote concentrations of acetonitrile that are above 70%. examples of high acetonitrile concentrations include 75, 80, 85, 90, 95 and 100%. in another aspect, the invention includes a method of sequencing peptides, including the steps of: (a) fractionating a sample of peptides by a method described herein; (b) adsorbing the peptides onto a micro-hplc column comprising a reversed phase and a strong cation exchanger stationary phase; (c) selectively eluting the peptides from a mixed phase column by the action of mobile phases, wherein the mobile phases develop an increasing ph and an increasing acetonitrile concentration; (d) analyzing the peptides with a mass spectrometer; and (e) sequencing the peptides that are detected by the mass spectrometer by tandem mass spectrometry. in another aspect, the invention includes a method of sequencing peptides, including the steps of: (a) fractionating a sample of peptides by a method described herein; (b) adsorbing the peptides onto a micro-hplc column comprising a strong cation exchanger stationary phase; (c) selectively eluting the peptides from a strong cation exchange phase by the action of mobile phases, wherein the mobile phases develop an increasing ph; (d) re-adsorbing the peptides that were eluted from the strong cation exchange phase onto a reversed phase; (e) separating the peptides using mobile phases that deliver an increasing acetonitrile concentration; (f) analyzing the peptides with a mass spectrometer; and (g) sequencing the peptides that are detected by the mass spectrometer by tandem mass spectrometry. as used herein, the term a mixed phase column refers to a column that is prepared with two or more stationary phases of different chemical properties. the terms mixed phase column and mixed bed column are used interchangeably. tandem spectrometry refers to multiple stages of mass spectrometry (e.g., mass spectrometry-mass spectrometry (ms/ms) refers to isolation of a precursor ion and fragmentation to products). a precursor ion is a signal that is generated by a mass spectrometer, which commonly defines the molecular weight of the analyzed substance. fragmentation products that result from ms/ms studies are signature signals that define the chemical composition of an analyzed substance. unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described below. all publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. in case of conflict, the present application, including definitions, will control. the materials, methods, and examples are illustrative only and not intended to be limiting. other features and advantages of the invention will be apparent from the following detailed description, and from the claims. brief description of the drawings fig. 1 depicts a comparison of maldi-tof-ms data acquired for a native mixture of hla-a1 presented peptides. peptide maps for native and methylated peptides are compared. fig. 2 depicts the quantification of relative peptide concentration (rtpeptide retention time; aapeak area measurement as made by a quantification algorithm supplied by the instrument vendor) fig. 3 demonstrates the effects of isotope labeling of peptide through esterification. this information can be used to determine the amino acid sequence of a peptide. any fragment ion that increases in m/z value by 3 daltons contains an acidic residue. those fragment ions that contain more than one acidic residue increase in m/z by 3 daltons multiplied by the number of acidic residues (there are no such fragment ions displayed in fig. 3 ). the figure depicts a comparison of methylated and deuteromethylated lc/ms/ms spectra for ntdhqtqlly (seq id no: 1) as collected under the peaks shown in fig. 2 . fig. 4 shows a schematic of the lc/ms/ms system in which a scx trapping a phase is decoupled from a reversed phase micro-capillary column. fig. 5 shows a typical flow of work for identifying and quantifying peptides from two complex mixtures of peptides following esterification with standard reagents (one peptide mixture, e.g., from a control cell line), and reagents that are labeled with a stable isotope (a second peptide mixture, e.g., from a stimulated cell line). detailed description peptide esterification methods the invention includes methods for the esterification of a peptide species or a population of peptides. according to these methods, peptides that contain an acidic residue or free acid c-terminus can be derivatized. in one method, an acidified alcohol solution is used for the esterification of a peptide species. the method includes, for example, the use of an acidified alcohol such as methanolic hcl to generate a peptide ester, e.g., a peptide methyl ester. additionally, other alcohols (such as ethanol, propanol, or isopropanol) or substituted alcohols (such as aminoethanol) can be used to generate a reagent for esterification of acidic residues. following the mixing of the acidified alcohol solution with a sample containing the peptide species, the concentration of the peptide species is preferably less than 1 nm. in some examples, the concentration of the peptide species is less than 100 pm, 10 pm, 1 pm, 100 fm, 10 fm, or 1 fm. in a second method, diazomethane is collected in a solvent, preferably a solvent other than diethyl ether. the solvent is preferably miscible in water. the solvent is mixed with a second solution that contains a peptide species, to thereby form a peptide methyl ester of the peptide species. the concentration of the peptide methyl ester of the peptide species is preferably less than 1 nm. in some examples, the concentration of the peptide methyl ester of the peptide species is less than 100 pm, 10 pm, 1 pm, 100 fm, 10 fm, or 1 fm. according to methods described herein, an acidic residue (e.g., aspartic acid or glutamic acid) and/or a carboxy terminal acid group is modified by combination with, e.g., (ch ₂ ) ₂ nh ₂ . hence, an acidic functional group is replaced to effectively change the chemical properties of a peptide. furthermore, converting a singly charged peptide into a doubly charged peptide can aid in peptide sequence elucidation. for example, the ms/ms spectrum of a peptide that is derivatized with aminoethanol is expected to contain both b (n-terminal) and y (c-terminal) sequence ions. other reagents that have specific functionality to aid sequence elucidation and/or peptide isolation can also be used in the methods of this invention. these include reagents that have a quaternary amine in addition to the alcohol group that is required for ester formation with the acidic residues of the peptide. examples include trialkylammonium-substituted alcohols such as trimethyl-ammonium ethanol. additionally, alcohols that have specific functionality, such as biotin or histidine that can be used to isolate and purify peptides can be used. an esterification reaction can be performed on a solid phase using, for example, an acidified alcohol method in conjunction with solid phase such as a hydrophilic chromatography (hilic) phase (e.g., a strong cation exchanger). by this approach, the peptides can be loaded onto the stationary phase in a suitable solvent (e.g., acidified water with or without a solvent such as a polar organic solvent, e.g., acetonitrile or methanol). the acidified alcohol is then passed through the column where the esterification reaction occurs. subsequently, the esterification reagent is washed from the column and the peptides are eluted in a suitable way using either hilic mobile phases (such as an acetonitrile to water gradient), salt or ph gradient. the derivatized peptides can be further fractionated and then analyzed, or analyzed directly. chromatography esterification of a peptide sample together with mixing a second peptide sample increases the complexity of peptide mixtures, e.g., hla-presented peptide mixtures. in addition, peptide signals that were of low abundance in the native peptide spectrum may be detected with increased intensity. this increases the probability of detecting isobaric peptides and overlapping peptide isotope signals. in this regard, enhanced separation may be required. multi-modal separations using combinations of separation techniques can be used. such techniques can include the following chromatographic and electrophoretic modes of separation to increase peptide resolution during fractionation: cation-exchange; anion-exchange; hilic (hydrophilic chromatography); normal and reverse phase; metal ion affinity; hydrophobic interaction chromatography; capillary electrophoresis; and capillary electrochromatography. additionally, further dimensions of separation on-line with a mass spectrometer can be performed. combinations and mixed bed columns are used in the methods described herein to enhance peptide separations and maximize the identification of peptides by lc/ms/ms. one such approach uses a mixed bed column containing a strong cation exchange (scx) and reversed phase with a simple combined acetonitrile/ph gradient to enhance peptide resolution and therefore aid collection of sequence specific data for individual peptides. another approach uses the same combined acetonitrile/ph gradient system with separate columns of strong cation exchange material and reversed phase stationary phase, to enhance peptide resolution and aid peptide sequence identification. in some aspects, the invention features systems and methods for fractionating, separating, and sequencing peptides. peptide and protein samples are isolated from cell lines, tissue samples, or intact organisms. these samples are manipulated in ways known to skilled artisans to generate peptide mixtures. for example, cell receptors may be isolated and treated in such a way as to release the peptides to which they are complexed. alternatively, a protein mixture may be digested either enzymatically or chemically to produce a mixture of peptides. similar peptide mixtures can be generated from stimulated cells, abnormal tissues or treated organisms. however the peptide mixtures may be generated, one of the peptide mixtures can be esterified with standard (non-isotpoic) reagents and the other peptide mixture can be esterified with reagents that contain a stable isotope. subsequently, the esterified and isotope-esterified peptide mixtures are mixed. this combined mixture is substantially more complex than each extract alone, and single mode chromatographic separation is typically inadequate to sufficiently fractionate the peptides to allow maximal component identification. in this aspect of this invention, multi-modal separation strategies for fractionating peptides have been implemented. coupling of one or more chromatographic modes together significantly simplifies peptide mixtures, thereby increasing the ability to identify more components of a complex mixture. many modes of chromatography are known to separate peptides. these include normal and reversed phase in which hydrophobic character is exploited to fractionate individual components of the mixture, hydrophilic interaction chromatography (hilic) in which the hydrophilic character of peptides is exploited to resolve components, and ion exchange chromatography where the ionic character of peptides in different solutions can be used to separate and fractionate these biopolymers. other modes including affinity chromatography, such as immobilized metal chelation chromatography (imac), immunoaffinity chromatography, and size exclusion chromatography are also useful to separate complex mixtures of peptides. however, many peptides of a complex mixture share similar chemical properties, hence, a single mode of chromatography has a limited capacity to completely resolve a mixture of these biopolymers. more appropriate is to use two or more modes of separation in series. for example, coupling ion exchange chromatography with reversed phase chromatography uses both the ionic and hydrophobic characters of the separation techniques to effect the isolation of target peptides. the ion exchange column bins the peptides according to charge, while the reversed phase separation is used to further resolve and simplify collected fractions. peptides can be binned by ion exchange chromatography using the effects of an increasing salt concentration gradient. for cation exchange chromatography, peptides can be displaced from the solid phase by the action of a small cation (such as sodium, potassium, ammonium, etc.) that has a higher affinity for the solid phase than the peptide. the number of charges that reside on a peptide dictates the strength of its interaction with ion exchange supports, with a higher number of charges proportionately increasing the concentration of salt required to elute the peptide from the column. in this way, peptides that are singly charged in solution are separated from those of double charge, which are in turn separated from those of higher charge. alternatively, peptides can be eluted from a cation exchange stationary phase by the action of a ph gradient. peptides have the ability to take on both positive and negative charge, depending upon the solution in which they are dissolved. in acidic solutions, peptides will be positively charged to varying degrees depending upon the chemical nature of the amino acid residues from which they are comprised. these cationic species adsorb to cation exchange resin. as the ph of the solution that is passed through the cation exchange column is increased, the positive charge that resides on the peptides changes so that ultimately the peptides become negatively charged, at which time they are eluted from the column. alternatively, peptides can be separated according to their hydrophobic character by reversed phase chromatography, in which a water to organic solvent (e.g., acetonitrile) gradient is use to selectively separate and elute peptides from the column. hence, coupling the two modes of chromatography (cation exchange with reversed phase) enhances peptide separation. the peptides binned by charge by the cation exchange chromatography are subsequently further resolved using reversed phase chromatography, and eluted from the second column in the order of increasing hydrophobicity. likewise, other modes of chromatography are complementary. for example, hydrophilic chromatography generally separates peptides in accordance with their different hydrophilic character. hence, coupling hilic and reversed phase chromatography enhances the separation of complex peptide mixtures. ultimately, as mentioned above, a further dimension of chromatography on-line with mass spectrometric analysis of the peptide fractions is preferred. here, an orthogonal chromatographic approach is desirable. a reversed phase chromatography that uses an acetonitrile gradient modified to a basic ph (rather than acidic ph) has been found to be a useful orthogonal mode of chromatography to enhance the analysis of peptide fractions that were generated as described above. the application of such alkaline modified reversed phase conditions enhances the resolution of peptide mixtures, and an elution time window of approximately 14 minutes (during which the peptides were eluted from the column) for reversed phase separated peptide fractions. under acidic modified reversed phase conditions this elution time window was at best 2 minutes, with all peptides of the sample eluting over this short duration. furthermore, a mixed bed column that simultaneously encompasses multiple modes of chromatography with a binary solvent gradient to promote increasing character of two chemical properties is desirable for this purpose. in one example, a combined scx, reversed phase column with a gradient that increases ph and organic character of the mobile phase has proved useful for enhancing the separation of peptides on-line with the mass spectrometer and has improved peptide sequencing efforts. in a second example, decoupling the scx phase from the reversed phase column has further enhanced peptide-sequencing efforts by micro-capillary lc/ms/ms. applicability of esterification to proteomics the methods described herein are applicable to the study of peptides and proteins, e.g., peptides and proteins extracted from in vivo and in vitro sources (e.g., blood, cerebrospinal fluid (csf), urine, feces, tissues, or cultured cells). protein biochemistry studies of human and non-human organisms, including plants, fungi, mammals, birds, fish, amphibians, eukaryotic parasites, bacteria, viruses, and other organisms, are all possible uses of the invention. advantages include the ability to measure and identify a wide variety of peptides and proteins, including peptides and proteins that do not contain an amino acid residue that can be alkylated (e.g., do not contain a cysteine residue). other important uses of the invention include mapping the surface and other solvent accessible sites of a protein. for example, reaction of the protein with the methylating reagent prior to digestion can yield information regarding three-dimensional structure of a protein. a specific example is probing the active site of a protein (e.g., a serine protease which has an aspartic acid residue at the active site). this approach could also be used to inhibit an enzyme such as a serine protease. in these methods, complex peptide mixtures can be generated from isolated proteins using specific proteases such as trypsin, chymotrypsin, lysine endopeptidase, endoproteinase lys-c, endoproteinase asp-n, endoproteinase glu-c, or by chemical methods. protein mixtures can be pre-fractionated or taken from total cell lysates or generated by any other known approaches (e.g., chromatography or gel electrophoresis). additionally, the esterification methods can be performed either before or after the enzymatic or chemical digestion. immobilized enzyme columns can also be used to generate peptide fragments from protein samples. the following are examples of the practice of the invention. they are not to be construed as limiting the scope of the invention in any way. examples example 1 methylation of peptides using diazomethane acetonitrile (0.5-3 ml) was added to the outer tube of an aldrich diazomethane generator. diazald (aldrich (steinheim, germany)) (n-methyl-n-nitroso-p-toluenesulfonamide; 0.2-0.5 g) was dissolved in a solution containing diethyl ether (1 ml) and carbitol (2-(2-ethoxyethoxy) ethanol; 1 ml) and placed in the center tube of the generator. the generator was assembled and placed in an ice bath. sodium hydroxide (30% w/v in water; 1.5 ml) was dispensed drop-wise through the rubber septum of the apparatus using a 22-gauge needle to prevent loss of diazomethane around the shank. the rate of addition was less than 1 drop/5 seconds to prevent pressure build-up in the apparatus. the generated diazomethane dissolved in the acetonitrile that was contained in the outer tube of the apparatus (this took on a bright yellow color as the concentration of diazomethane was increased). the apparatus was gently shaken by hand every 10 min to ensure complete reaction. the maximum yield of diazomethane was obtained in 35 -60 min. the generated acetonitrile solution of diazomethane was kept on ice until it was used. the diazomethane-rich acetonitrile solution was added to aqueous peptide solutions. further reagent was added until a yellow color persisted in the sample. at this time the excess reagent was removed and the sample was concentrated to the original volume in a savant speedvac concentrator. example 2 methylation of peptides using deuterodiazomethane deuterodiazomethane was generated in the same manner as diazomethane, with substitution of reagents. diazald-n-methyl-d3 (0.3-0.4 g) was dissolved in anhydrous diethyl ether (1 ml) and carbitol-d (1 ml) and placed in the center tube of the aldrich diazomethane generator. acetonitrile (0.5-3 ml) was placed in the outer tube of this apparatus, and the apparatus was assembled and immersed in an ice bath. sodium deuteroxide (30 wt %, 1.5 ml) was added drop-wise, and the reagents were reacted as described above. the deuterodiazomethane-rich acetonitrile solution was added to aqueous peptide solutions. further reagent was added until a yellow color persisted in the sample. at this time the excess reagent was removed and the sample was concentrated to the original volume in a savant speedvac concentrator. example 3 esterification of peptides by methanolic hcl methanolic hydrochloric acid was prepared by dissolving acetyl chloride in dry methanol. concentration and volume of reagent, time and temperature of reaction were optimized to increase the yield of peptide methyl esters, and ensure quantitative esterification of all acidic functional groups. optimal conditions for peptide esterification were found to be the addition to a completely dry peptide sample of 30-80 l of reagent prepared by dissolving acetyl chloride (120-180 l) in methanol that was dried over anhydrous sodium sulfate (0.8-1.2 ml). a reaction time of 45 minutes at a temperature of 37 c. yielded quantitative methylation of acidic residues of a naturally derived hla-presented peptide mixture. following reaction, the methylated peptide mixture was again reduced to dryness prior to reconstitution in an aqueous solvent (water/acetonitrile/trifluoroacetic acid 95:5:0.04 v/v/v). example 4 esterification of peptides by deuterated methanolic hcl deuterated methanolic hydrochloric acid was prepared by dissolving deuterated acetyl chloride (120-180 l) in d ₄ -methanol (0.8-1.2 ml) that was dried over anhydrous sodium sulfate. peptide samples were taken to complete dryness in a savant speedvac and reacted for 45 minutes at 37 c. with 30-80 l of deuterated reagent. following reaction, the peptide mixture was again reduced to dryness prior to reconstitution in an aqueous solvent (e.g., water/acetonitrile/trifluoroacetic acid 95:5:0.04 v/v/v). example 5 mass spectrometrymatrix assisted laser desorption/ionization time of flight mass spectrometry (maldi-tof-ms) maldi-tof-ms analysis of esterified peptide mixtures was performed by co-crystallizing an aliquot of a sample with a light-absorbing matrix (such as 2,5-dihydrobenzoic acid, dhb; or 4-hydroxy cinnamic acid, -cyano). specifically, an aliquot (0.5-1.0 l) of a matrix solution comprising dhb (5-15 mg/ml) in an aqueous solution (e.g. water/acetonitrile/trifluoroacetic acid 70:30:0.1 v/v/v) was placed onto the instrument (voyager elite xl from perseptive biosystems, framingham, mass.) sample stage and allowed to dry. once the matrix solution had dried, an aliquot (0.5-1.0 l) of sample was applied to the top of the dry matrix spot. when -cyano was used, the procedure for sample preparation was similar except the sample was first applied to the instrument sample stage and dried. then a solution of -cyano at a concentration of (5-15 mg/ml) dissolved in a solution such as water/acetonitrile/trifluoroacetic acid 70:30:0.1 v/v/v was added to the sample spot and dried. spectra were collected by a means known to those skilled in the art (e.g., ions were generated by laser light's hitting the sample, the ions were then accelerated and allowed to drift down a flight tube that facilitates their separation. signals that are detected at the detector are collected on a computer where ion flight times are converted to mass to charge (m/z) values by comparison of sample data with calibrated time to m/z conversion values generated by analysis of known entities). example 6 mass spectrometryliquid chromatography/tandem mass spectrometry (lc/ms/ms) lc/ms/ms is achieved by coupling a separation technique, e.g., reversed phase hplc to an ion trap mass analyzer. however, other mass analyzers such as but not limited to a triple quadrupole instrument, magnetic sector, fourier transform ion cyclotron resonance, quadrupole time-of-flight, or a hybrid of these analyzers could be coupled to on-line hplc separations though an electrospray interface, and used for this application. aliquots (0.5-10 l) of samples were diluted in suitable aqueous solutions (e.g. 5-15 l of an aqueous solution containing acetonitrile and trifluoroacetic acid (tfa). a suitable composition of solvent for this application is water/acetonitrile/trifluoroacetic acid 95:5:0.04 v/v/v. the whole of the resulting mixture is injected on to a miniaturized peptide trap that contains a small bed volume (0.5 l) of hplc stationary phase (such as polymeric support, c2, c4, c8, c18, metal affinity support, ion exchange media or the like) that is used in place of a sample loop in a hplc injector valve. peptides elute from this phase by action of the gradient that flows across it and are further adsorbed and separated on a micro-capillary hplc column (e.g., 20-100 m id. column that is packed with a stationary phase that is suitable for separating peptides such as polymeric support, c2, c4, c8, c18, metal affinity support, ion exchange media). combinations of support material such as ion exchange material (e.g., scx material) followed by reversed phased support (e.g. c2, c4, c8, or c18 material) can also be used for this purpose. peptides are separated and eluted from the column due to the effects of a solvent gradient (such as increasing the concentration of acetonitrile after starting with a predominantly aqueous mobile phase). such mobile phases can be modified with either acids or bases to change peptide separation characteristics. a typical mobile phase gradient can be 5-100% acetonitrile in 15 minutes with both mobile phases modified with formic acid (0.1-0.5% by volume), acetic acid (0.5-2.0% by volume) or tfa (0.01-0.05% by volume). a mixed acid modified mobile phase system (e.g., 0.5% acetic acid and 0.04% tfa) can also be used to modify peptide separation characteristics. alternatively, mobile phases can be modified with bases such as ammonium hydroxide (1-10 mm) to effect different peptide separations. the mass spectrometer can be used in targeted mode, where specific peptide signals are isolated and fragmented, and data dependent mode of operation. in the latter mode, knowledge of sample composition is not required as specific peptide signals are isolated and fragmented when they are more intense than an operator defined threshold. example 7 quantitative methylation of a naturally derived hla presented peptide mixture quantitative methylation entails the reaction of substantially all of the acidic functional groups in all of the peptides of a protein mixture. hence a peptide in a native mixture is converted by reaction to a fully methylated product at the end of the reaction. while methylation is an example described, quantitative deuteromethylation can also be used, since the chemical nature of reactions (e.g., rates and mechanisms) and reaction conditions are the same. deuteromethylation can use isotopically labeled reagents that include deuterium, carbon 13, nitrogen 15 and/or oxygen 18 isotopes. quantitative methylation of a peptide mixture was demonstrated by the following method. an aliquot (10 l) of a reversed phase hplc fraction of hla-a1 presented peptides derived from an immortalized human b-cell line was reduced to dryness and reacted with methanolic hcl as described above. maldi-tof-ms was used to analyze the native peptide mixture and the sample generated after treatment with the optimized methanolic hcl methylation procedure. following reaction, the peptide mixture was again reduced to dryness prior to reconstitution in an aqueous solvent (water/acetonitrile/trifluoroacetic acid 95:5:0.04 v/v/v). samples were prepared for maldi-tof-ms analysis by co-crystallization of each peptide mixture with a solution of 2,5-dihydroxybenzoic acid (dhb) in an aqueous solution (water/acetonitrile/trifluoroacetic acid 70:30:0.1 v/v/v). the results of these analyses ( fig. 1 ) indicated that the procedure yielded quantitative methylation of the acidic groups. all of the peptide signals, except one (m/z 1029.5), detected in the mass spectrum of the native peptides were converted in their entirety to their esterified analogs. this was determined by detection of peptide responses of increased m/z in the spectrum collected after methylation of the sample. there was also no signal due to the native peptides in this mass spectrum. as shown in table 1, these data enabled elucidation of the number of acidic residues (the c-terminus as well as asparagine and glutamine residues) in each peptide. furthermore, there was no appreciable loss of peptide (as determined by comparison of peak responses in the two maldi-tof-ms spectra shown in fig. 1 ). one peptide was observed only after methylation (see table 1). it was concluded that this peptide signal corresponded to deamidation (conversion of glutamine to glutamic acid or asparagines to aspartic acid) in the peptide of mh 1232.6 followed by three sites of methylation. table 1 correlation of detected peptide signals between the native and methylated mald-tof-ms spectra shown in fig. 1 enabled determination of the number of acid residues in hla-a1 presented peptides m/z native m/z methylated number of sites of peptide peptide methylation 1029.5 1029.7 0 1070.5 1098.7 2 1137.6 1165.7 2 1169.8 1211.8 3 1191.5 1219.8 2 1225.7 1239.7 1 1232.6 1260.8 2 1254.6 1278.8 2 1286.3 1314.7 2 1296.6 contaminant 1275.7 deamidation of q to e or n to d plus 3 sites of methylation example 8 peptide quantification by isotope dilution following methylation and deuteromethylation the methods described herein can be used to determine the relative quantity of a peptide in a cell line or sample, e.g., a tissue sample, as compared to the amount of the same peptide in a different cell line or sample. by this approach the methyl ester of a peptide extract from one cell line or tissue sample and the deuteromethyl ester of the other are prepared and mixed prior to peptide isolation, fractionation and analysis. the relative amounts of the methyl and deuteromethyl analogs determine the relative amounts of the native peptide in the cell line or tissue extracts. this has been exemplified as follows. an aliquot (10 l) of a reversed phase hplc fraction of hla-a1 presented peptides derived from an immortalized human b-cell line was reduced to dryness and reacted methanolic hcl as described above. a second aliquot (10 l) of the same hplc fraction of hla-a1 peptides was reduced to dryness and reacted with deuterated methanolic hcl. following reaction, the peptide mixture was again reduced to dryness prior to reconstitution in an aqueous solvent (water/acetonitrile/trifluoroacetic acid 95:5:0.04 v/v/v). the samples were mixed at a rate of two parts of the methylated sample to one part of the deuteromethylated sample and analyzed by targeted lc/ms/ms, isolating the doubly charged precursor ion for doubly methylated peptide (ntdhqtqlly; seq id no: 1) that was derived from rad51, and the doubly charged precursor ion for doubly deuteromethylated analog of the same peptide. area measurements from under peaks observed in the ion chromatograms reconstructed from the six most abundant fragment ions of both peptides (m/z 468, 477, 524, 533, 952, and 1065 for the methylated peptide and m/z 469, 478, 526, 535, 955 and 1068 for the deuteromethylated peptide) were in good agreement with the ratio of the mixed products ( fig. 2 ). specifically, the peak area of the doubly methylated peptide was 4397998, and the peak area measured for the doubly deuteromethylated peptide was 2525643. the ratio of these measurements was 1.74:1, which is in good agreement with the prepared sample (which was prepared at a 2:1, hydrogen: deterium, h:d, ratio). specific peptide sequence information was also derived from the lc/ms/ms data. those fragment ions that contained an acidic residue were readily identified by these data as peaks whose m/z value increased by three daltons in the deuteromethylated peptide spectrum (1.5 daltons for doubly charged fragment ions; fig. 3 ). example 9 esterification for profile comparison maps an analysis can be directed to the identification of a naturally processed and presented hla epitope that is derived from an antigen that is specifically expressed by a cell line by any means known to those skilled in the art (including infection, transfection, and incubation). naturally expressed peptide pools are isolated by any means known to those skilled in the art (methods for isolating pools of naturally expressed peptides have been described, for example, in u.s. pat. no. 09/372,380, herein incorporated by reference). for example, the peptide extract of a control preparation can be deuteromethylated and the peptide extract an antigen pulsed cell line can be methylated. these samples are mixed in their entirety prior to peptide fractionation. fractionated peptides are analyzed by maldi-tof-ms. any peptide signal that does not have an isotopically labeled partner is a target for sequencing by lc/ms/ms. while this specific example describes the use of methylation for hla peptide research, this invention could be used for comparison of any protein maps. example 10 esterification to enable peptide quantification in studies of organism proteomes an analysis can be directed to the investigation of the effects of stimulants or perturbants on a cell population or a patient subject. naturally expressed peptide pools are isolated by any means known to those skilled in the art (methods for isolating pools of naturally expressed peptides have been described for example in u.s. pat. no. 09/372,380, herein incorporated by reference). the peptide pool extracted from a control cell line is methylated, and the peptide pool extracted from a perturbed cell line is deuteromethylated. prior to fractionation, the two esterified peptide pools are mixed in their entirety and fractionated using multi-modal chromatographic techniques. the separation techniques used here are novel combinations of hplc approaches. for example, peptide fractions are generated by strong cation exchange and are further fractionated by reversed phase hplc. alternatively, those peptide fractions generated by strong cation exchange can be further fractionated using hilic, normal phase, anion exchange, metal affinity, hydrophobic interaction chromatography, or by electrophoretic methods (such as capillary electrophoresis and/or capillary electrochromatography). the fractionated peptides are analyzed by maldi-tof-ms. each peptide is detected with an ion signature that is separated by a multiplicity (that is defined by the number of acidic amino acid residues in a peptide along with its c-terminus) of 2 or 3 daltons (depending upon how the methylation is performed). those peptides that exhibit a fractional or elevated d/h ratio are targeted for sequencing. by this approach, all peptides are monitored by maldi-tof-ms, and knowledge of which peptide to monitor is unnecessary. in addition to identifying target peptides to sequence, this method can enable quantification of the relative amount of a peptide expressed by the two cell lines. this isotope dilution approach is self-normalizing since both methylated and deuteromethylated peptides are in the same fraction. this can aid proteomic studies by enabling an accurate assessment of the biochemistry (e.g., as reported by naturally processed peptide pools) that has occurred (or is occurring) in the cells/organisms as samples are harvested. peptide sequencing efforts can also be aided by this approach since the isotopic label will be detected in all fragment ions except those that do not contain an acid residue and/or the c-terminus. additionally, for positive ions, the elimination of the negativity of acidic residue (through esterification) may increase the relative response factor of a peptide. this often enhances sensitivity, which also aids sequence elucidation. example 11 construction of a mixed phase microcapillary column a mixed phase microcapillary column that can be used in the separation systems of the invention contains discrete beds of at least two hplc stationary phases, and has an outlet at one end, which contains a frit. mobile phase flows over the stationary phase towards the outlet. two stationary phases are contained within the column to construct the mixed phase. a skilled artisan can typically make these columns. an empty fused silica micro-electrospray tip (that contains a sintered glass frit at a tapered outlet end) is packed with the stationary phases. first, a slurry of stationary phase 2 (such as a reversed phase resin) in a suitable solvent (such as methanol or isopropanol) is placed into an enclosed device that allows nitrogen pressure to be exerted on top of the slurry to force the slurry into the micro-electrospray tip (e.g., a picotip, new objectives cambridge mass., usa). the tip is monitored under a stereomicroscope, and once the desired length of stationary phase 2 has been packed, the nitrogen pressure is carefully released (so as not to cause a rapid change of pressure in the column which causes the packed bed to loosen and unpack). subsequently, the slurry of stationary phase 2 is replaced with a slurry of stationary phase 1 (e.g., a scx resin) in a suitable solvent (e.g., methanol) and nitrogen pressure is reapplied. again the tip is monitored under a stereomicroscope to view the stationary phase so that nitrogen pressure can be released when the desired length of stationary phase 1 has been packed into the column. desired lengths of each stationary phase are dependent upon the experiment for which the column is to be used. typical lengths of stationary phase 2 are 2 to 6 cm and typical lengths of stationary phase 1 are 0.5 to 3 cm. a typical internal diameter of the micro-electrospray tip is 25 to 75 um. once packed, these columns are washed with methanol and then a 50:50 v/v mixture of the mobile phases that are used for chromatographic separation of peptides (e.g., mixtures of acetonitrile and water modified with ammonium hydroxide). further washing with one or two gradient s from water to acetonitrile modified with ammonium hydroxide and separation of a test peptide mixture (comprising 2 to 12 synthetic peptides) is performed before the column can be used for separation and analysis of peptide mixtures of interest. example 12 decoupled scx/micro-capillary reversed phase lc/ms/ms fig. 4 depicts a decoupled scx/micro-capillary reversed phase lc/ms/ms system. a microcapillary trap of scx material was in place of the sample loop of the autosampler. peptide mixtures were loaded in acidic solution, after which the scx trap was switched into the flow stream of a high ph aqueous phase mobile. increasing ph eluted peptides from the scx phase, and a gradient delay of the reversed phase solvents ensures that the acetonitrile content of the mobile phases remains low to ensure that peptides of the mixture are refocused on the reversed phase material of the microcapillary analytical column. this approach promotes a high chromatographic performance of the automated microcapillary lc/ms/ms system, and enhanced the approach for sequencing peptides that were extremely hydrophilic. furthermore, a high level of acetonitrile did not disrupt peptide adsorption on the scx phase. therefore, this approach enabled direct analysis of peptides that were fractionated by reversed phase chromatograph. this minimized sample manipulations and prevented analyte losses. for the decoupled scx/reversed phase lc/ms/ms approach, high tfa concentration used to achieve highest peptide resolution for off-line reversed phase peptide fractionation was also advantageous, as this reagent promoted peptide adsorption on the scx phase. example 13 identifying and quantifying peptides fig. 5 depicts a flow chart demonstrating an example of a workflow used in quantifying and/or sequencing peptides as described herein. a first peptide mixture is esterified with standard reagents. a second peptide mixture is esterified with isotopically labeled reagents. the samples are mixed in their entirety. following mixing, the sample is fractionated using a first dimension chromatography and then further fractionated using a second dimension chromatography. the fractions that are generated are analyzed by lc/ms using a third dimension chromatography, preferably a mixed stationary phase column. peptide samples may either be quantified or sequenced from this analysis. example 14 construction of a kit for use in identifying and quantifying peptides a kit may be used for quantifying and/or sequencing peptides as described herein. the kit can contain components that are used towards this end. components of a kit can include: microchemistry reagents (e.g., reagents that permit the generation of peptide esters according to the methods of the invention); chromatography columns (e.g., 1 mm150 mm stainless steel tube packed with a stationary phase that has containing frits at either end of the tubing); a standard peptide (e.g. a synthetic test peptide); a mobile phase (e.g., mixtures containing acetonitrile and water and modified with either an organic acid of an ammonium salt; typical examples include but are not limited to water/acetonitrile/trifluoro acetic acid in various compositions e.g., 95:5:0.1 v/v/v or 5:95:0.1 v/v/v; a mixed bed column (e.g., as described in example 11)); and/or buffers to enable chromatography (e.g. water/acetonitrile/ammonium hydroxide in various compositions e.g., 95:5:0.1 v/v/v or 5:95:0.1 v/v/v). the kit may optionally include a set of instructions that instructs a user to use the components of the kit to carry out a method described herein, e.g., to effect the quantification or sequencing of a peptide or peptides. other embodiments while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. other aspects, advantages, and modifications are within the scope of the following claims.
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043-616-360-834-160
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JP
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[
"US"
] |
H01L33/00,H01L33/20,H01L33/32,H01L33/38,H01L33/62
| 2009-10-19T00:00:00 |
2009
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[
"H01"
] |
rod-like light-emitting device, method of manufacturing rod-like light-emitting device, backlight, illuminating device, and display device
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to facilitate electrode connections and achieve a high light emitting efficiency, a rod-like light-emitting device includes a semiconductor core of a first conductivity type having a rod shape, and a semiconductor layer of a second conductivity type formed to cover the semiconductor core. the outer peripheral surface of part of the semiconductor core is exposed.
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1. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape, the rod shape having a length and a circumference; a semiconductor layer of a second conductivity type covering the semiconductor core so as to form a pn junction between the semiconductor core and the semiconductor layer coaxially with respect to the semiconductor core; and a transparent electrode formed so as to cover substantially a whole of the semiconductor layer, wherein the semiconductor core comprises an n-type semiconductor and the semiconductor layer comprises a p-type semiconductor, wherein an outer peripheral surface of a part of the semiconductor core is exposed along the entire circumference of the rod shape, the exposed part having a part of the length of the rod shape, and wherein the rod-like light-emitting device has a diameter within a range of from 10 nm to 5 μm, inclusive, and a length within a range of from 100 nm to 200 μm, inclusive. 2. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape; a cap layer covering only one of two longitudinal ends of the rod shape of the semiconductor core; and a semiconductor layer of a second conductivity type covering an outer peripheral surface of a portion of the semiconductor core other than an exposed portion, the exposed portion of the semiconductor core being a portion opposite from a portion covered with the cap layer of the semiconductor core, wherein the cap layer is made of a material having a higher electric resistance than the semiconductor layer. 3. the rod-like light-emitting device according to claim 2 , wherein a conductive layer having a lower resistance than the semiconductor layer is formed to cover the semiconductor layer. 4. a light-emitting apparatus comprising: at least one rod-like light-emitting device according to claim 2 ; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the semiconductor layer at the other end of the semiconductor core on which the cap layer is provided is connected to another one of the electrodes on the substrate. 5. a light-emitting apparatus comprising: at least one rod-like light-emitting device according to claim 3 ; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the conductive layer on the other side of the semiconductor core on which the cap layer is provided is connected to another one of the electrodes on the substrate. 6. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape; and a semiconductor layer of a second conductivity type covering an outer peripheral surface of a portion of the semiconductor core other than an exposed portion, the exposed portion of the semiconductor core being one end portion of the semiconductor core, wherein a step portion is provided between an outer peripheral surface of the exposed portion not covered with the semiconductor layer of the semiconductor core and an outer peripheral surface of a covered portion covered with the semiconductor layer of the semiconductor core. 7. the rod-like light-emitting device according to claim 6 , further comprising a conductive layer formed to cover the semiconductor layer and made of a material having a lower electric resistance than the semiconductor layer. 8. a light-emitting apparatus comprising: at least one rod-like light-emitting device according to claim 6 ; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the semiconductor layer at the other end of the semiconductor core is connected to another one of the electrodes on the substrate. 9. a light-emitting apparatus comprising: at least one rod-like light-emitting device according to claim 7 ; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the conductive layer on the other side of the semiconductor core is connected to another one of the electrodes on the substrate. 10. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape; a semiconductor layer of a second conductivity type covering one of two ends of the semiconductor core; an insulator covering an outer peripheral surface, not covered with the semiconductor layer, of the semiconductor core; and an underlying layer of the first conductivity type adjoining the other end of the semiconductor core, wherein an end surface of the underlying layer axially opposite from the semiconductor core and a peripheral surface of the underlying layer are exposed. 11. a light-emitting apparatus comprising: a rod-like light-emitting device including a semiconductor core of a first conductivity type having a rod shape, the rod shape having a length and a circumference, a semiconductor layer of a second conductivity type formed to cover the semiconductor core so as to form a pn junction between the semiconductor core and the semiconductor layer coaxially with respect to the semiconductor core, and a transparent electrode formed so as to cover substantially a whole of the semiconductor layer, wherein the semiconductor core comprises an n-type semiconductor and the semiconductor layer comprises a p-type semiconductor, an outer peripheral surface of a part of the semiconductor core is exposed along the entire circumference of the rod shape, the exposed part having a part of the length of the rod shape, and the rod-like light-emitting device has a diameter within a range of from 10 nm to 5 μm, inclusive, and a length within a range of from 100 nm to 200 μm, inclusive; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate. 12. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape, the rod shape having a length and a circumference; a semiconductor layer of a second conductivity type covering the semiconductor core so as to form a pn junction between the semiconductor core and the semiconductor layer coaxially with respect to the semiconductor core; and a transparent electrode formed so as to cover substantially a whole of the semiconductor layer, wherein the semiconductor core comprises an n-type semiconductor and the semiconductor layer comprises a p-type semiconductor, wherein the semiconductor core has, along the length of the rod shape, a first portion having an outer peripheral surface which is entirely covered with the semiconductor layer of the second conductivity type along the entire circumference of the rod shape, and a second portion having an outer peripheral surface which is at least partially exposed along at least part of the circumference of the rod shape without being covered with the semiconductor layer of the second conductivity type, and wherein the rod-like light-emitting device has a diameter within a range of from 10 nm to 5 μm, inclusive, and a length within a range of from 100 nm to 200 μm, inclusive. 13. a rod-like light-emitting device comprising: a semiconductor core of a first conductivity type having a rod shape, the rod shape having a length and a circumference; and a semiconductor layer of a second conductivity type covering the semiconductor core, wherein an outer peripheral surface of a part of the semiconductor core is exposed along the entire circumference of the rod shape, the exposed part having a part of the length of the rod shape, wherein an outer peripheral surface of one of two longitudinal end portions of the semiconductor core is exposed, and wherein an end surface of the other of the two longitudinal end portions of the semiconductor core is covered with the semiconductor layer. 14. the rod-like light-emitting device according to claim 13 , a thickness of the semiconductor layer in a longitudinal, or axial direction of the rod shape at a part covering the end surface of the other of the two longitudinal end portions of the semiconductor core is larger than a thickness thereof in a radial direction of the rod shape at a part covering the outer peripheral surface of the semiconductor core. 15. an illuminating device including the rod-like light-emitting device according to claim 1 . 16. a display device including the rod-like light-emitting device according to claim 1 .
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technical field this invention relates to a rod-like light-emitting device, a method of manufacturing the rod-like light-emitting device, a backlight, an illuminating device and a display device. background of the invention conventionally, there has been a light-emitting device in a rod-like structure having a size of the order of nanometers in which a rod-like core portion made of a compound semiconductor and a cylindrical shell portion made of a compound semiconductor surrounding the core portion form a heterostructure (see, for example, jp-a-2008-235443). in the light-emitting device, the core portion itself serves as an active layer, and electrons and holes injected from the outer peripheral surface recombine in the core portion to emit light. in the case where using a manufacturing method similar to that for the above light-emitting device, a rod-like light-emitting device is manufactured that has a core portion made of an n-type semiconductor and a shell portion made of a p-type semiconductor and in which electrons and holes recombine at a pn junction between the outer peripheral surface of the core portion and the inner peripheral surface of the shell portion to emit light, the core portion is exposed only on its both end surfaces, and therefore there arises a problem in that connecting the core portion and an electrode is difficult. there has been a method of manufacturing a rod-like light-emitting device. in the method, after a flat first polarity layer is formed on a substrate, a plurality of light-emitting nanoscale rods, which corresponds to the active layer to emit light, are formed on the first polarity layer, and further a second polarity layer wrapping around each of the rods is formed (see, for example, jp-a-2006-332650). in this rod-like light-emitting device, light is emitted from the plurality of rods serving as the active layer. however, the above rod-like light-emitting device is used together with the substrate on which the plurality of nanoscale rods are provided, and is subjected to the constraints of the substrate when incorporated into an illuminating device or a display device. therefore, the rod-like light-emitting device has a problem in that there is less freedom in installing into an apparatus. furthermore, a light-emitting apparatus including the above rod-like light-emitting device has a problem in that the light-extraction efficiency decreases because, under the condition in which the plurality of rods erect on a substrate, most light is emitted laterally to be absorbed into the adjacent rods. in the above rod-like light-emitting device, the plurality of rods erect on the substrate, and therefore there is a problem in that the heat dissipation efficiency is poor. summary of the invention technical problem accordingly, an object of this invention is to provide a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and that has a high light emitting efficiency, and a method of manufacturing such a rod-like light-emitting device. another object of this invention is to provide a backlight, an illuminating device and a display device in which their thicknesses and weights can be reduced, and high light emitting efficiencies and low power consumption are achieved, by using the above rod-like light-emitting devices. another object of this invention is to provide a method of manufacturing a rod-like light-emitting device that has great freedom in installing into an apparatus and is microscopic, and a method of manufacturing a display device including the rod-like light-emitting device. another object of this invention is to provide a light-emitting apparatus having a high light-extraction efficiency and good heat dissipation. another object of this invention is to provide a backlight, an illuminating device and a display device in which high light emitting efficiencies, good heat dissipation and low power consumption are achieved by using the above light-emitting devices. solution to problem a rod-like light-emitting device according to a first aspect of the present invention comprises: a semiconductor core of a first conductivity type having a rod shape; and a semiconductor layer of a second conductivity type covering the semiconductor core, wherein an outer peripheral surface of a part of the semiconductor core is exposed. according to this configuration, the semiconductor layer of a second conductivity type is formed to cover the semiconductor core of the first conductivity type having a rod shape and to expose the outer peripheral surface of part of the semiconductor core. the formation of the semiconductor layer enables an exposed portion of the semiconductor core to be connected to one electrode and enables the other electrode to be connected to a portion covering the semiconductor core of the semiconductor layer even in the case of a microscopic rod-like light-emitting device with a size of the order of micrometers or in the order of nanometers. in the rod-like light-emitting device, with one electrode connected to the exposed portion of the semiconductor core and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes so that electrons and holes recombine at a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. as a result, light is emitted from the pn junction. in the rod-like light-emitting device, light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer. this results in expansion of the light emitting region, and therefore the light emitting efficiency is high. accordingly, it is possible to implement a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and that has a high light emitting efficiency. the rod-like light-emitting device is not integral with the substrate, which allows great freedom in installing into an apparatus. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. in one embodiment, an outer peripheral surface of one of two ends of the semiconductor core is exposed. in one embodiment, an end surface of the other end of the semiconductor core is covered with the semiconductor layer. in one embodiment, the semiconductor layer has a thickness in an axial direction of a portion covering the end surface of the other end of the semiconductor core larger than a thickness in a radial direction of a portion covering the outer peripheral surface of the semiconductor core. in one embodiment, the outer peripheral surface of an exposed region of the semiconductor core is coincident or substantially coincident with an extension of an outermost peripheral surface of a region of the semiconductor core where the semiconductor core is covered with the semiconductor layer. in one embodiment, the rod-like light-emitting device has a quantum well layer formed between the semiconductor core and the semiconductor layer. in one embodiment, an outer peripheral surface of one of two ends of the semiconductor core is exposed, and an end surface of the other end of the semiconductor core is covered with the semiconductor layer. also, the rod-like light-emitting device comprises a quantum well layer formed between the semiconductor core and the semiconductor layer, and the quantum well layer has a thickness in an axial direction of a portion covering the end surface of the other end of the semiconductor core larger than a thickness in a radial direction of a portion covering an outer peripheral surface of the semiconductor core. in one embodiment, the rod-like light-emitting device has a transparent electrode covering the semiconductor layer. in one embodiment, the semiconductor core is made of an n-type semiconductor, the semiconductor layer is made of a p-type semiconductor, and the transparent electrode is formed to cover the whole or nearly whole of the semiconductor layer. a method of manufacturing a rod-like light-emitting device according to a second aspect of the invention comprises steps of: forming a catalyst metal island layer on a substrate of a first conductivity type; forming a semiconductor core of the first conductivity type having a rod shape on the substrate by crystal growth of a semiconductor of the first conductivity type from an interface between the catalyst metal island layer and the substrate; forming a semiconductor layer of a second conductivity type covering a surface of the semiconductor core by performing, under a condition where the catalyst metal island layer is held at a tip of the semiconductor core, crystal growth from an outer peripheral surface of the semiconductor core and an interface between the catalyst metal island layer and the semiconductor core; exposing a substrate-side portion of the outer peripheral surface of the semiconductor core; and separating from the substrate the semiconductor core including the exposed portion exposed in the step of exposing. the term “substrate of a first conductivity type” as used herein may be a substrate made of a semiconductor of the first conductivity type, and may also be a substrate in which a semiconductor film of the first conductivity type is formed on the surface of an underlying substrate. with the configuration mentioned above, the catalyst metal island layer is formed on the substrate of the first conductivity type. then, on the substrate on which the catalyst metal island layer is formed, the semiconductor core of the first conductivity type shaped like a rod is formed by crystal growth of a semiconductor of the first conductivity type from an interface between the catalyst metal island layer and the substrate. thereafter, under the condition where the catalyst metal island layer held at a tip of the semiconductor core, a semiconductor layer of the second conductivity type that covers the surface of the semiconductor core is formed by crystal growth from the outer peripheral surface of the semiconductor core and an interface between the catalyst metal island layer and the semiconductor core. at this point, crystal growth from the interface between the catalyst metal layer and the semiconductor core is promoted rather than crystal growth from the outer peripheral surface of the semiconductor core. as a result, in the semiconductor layer, the thickness in the axial direction of a portion covering the end surface of the other end of the semiconductor core is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core. next, the outer peripheral surface on the substrate side of the semiconductor core is exposed, and then the semiconductor core including the exposed portion is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or using a cutting tool. in the rod-like light-emitting device separated from the substrate in such a way, with one electrode connected to the exposed portion of the semiconductor core, and with the other electrode connected to the semiconductor layer, an electric current is caused to flow between the electrodes, so that electrons and holes recombine in a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. thus, light is emitted from the pn junction. the semiconductor layer of the second conductivity type is formed to cover the surface of the semiconductor core under the condition where the catalyst metal island layer is held at a tip of the semiconductor core, without removing the catalyst metal island layer. due to the catalyst metal layer, crystal growth is promoted. this makes it possible to easily form the semiconductor layer in which the thickness in the axial direction of a portion that covers the end surface of the other end of the semiconductor core is larger than the thickness in the radial direction of a portion that covers the outer peripheral surface of the semiconductor core. in this way, a microscopic rod-like light-emitting device having great freedom in installing in an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. a method of manufacturing a rod-like light-emitting device according to a third aspect of the invention comprises steps of: forming a catalyst metal island layer on a substrate of a first conductivity type; forming a semiconductor core of the first conductivity type having a rod shape on the substrate by crystal growth of a semiconductor of the first conductivity type from an interface between the catalyst metal island layer and the substrate; forming a quantum well layer covering a surface of the semiconductor core by performing, under a condition where the catalyst metal island layer is held at a tip of the semiconductor core, crystal growth from an outer peripheral surface of the semiconductor core and an interface between the catalyst metal island layer and the semiconductor core; forming a semiconductor layer of a second conductivity type covering a surface of the quantum well layer; exposing a substrate-side portion of the outer peripheral surface of the semiconductor core; and separating from the substrate the semiconductor core including the exposed portion exposed in the step of exposing. with the configuration mentioned above, the catalyst metal island layer is formed on the substrate of the first conductivity type. then, on the substrate on which the catalyst metal island layer is formed, the semiconductor core of the first conductivity type shaped like a rod is formed by crystal growth of a semiconductor of the first conductivity type from an interface between the catalyst metal island layer and the substrate. thereafter, under the condition where the catalyst metal island layer held at a tip of the semiconductor core, a quantum well layer that covers the surface of the semiconductor core is formed by crystal growth from the outer peripheral surface of the semiconductor core and from an interface between the catalyst metal island layer and the semiconductor core. at this point, crystal growth from the interface between the catalyst metal layer and the semiconductor core is promoted rather than crystal growth from the outer peripheral surface of the semiconductor core. as a result, in the semiconductor layer, the thickness in the axial direction of a portion covering the end surface of the other end of the semiconductor core is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core. next, the semiconductor layer of the second conductivity type covering the surface of the quantum well layer is formed to expose the outer peripheral surface on the substrate side of the semiconductor core. the outer peripheral surface on the substrate side of the semiconductor core is exposed, and then the semiconductor core including the exposed portion is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or using a cutting tool. in the rod-like light-emitting device separated from the substrate in such a way, with one electrode connected to the exposed portion of the semiconductor core, and with the other electrode connected to the semiconductor layer, an electric current is caused to flow between the electrodes, so that electrons and holes recombine in a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. thus, light is emitted from the pn junction. the quantum well layer is formed to cover the surface of the semiconductor core under the condition where the catalyst metal island layer is held at a tip of the semiconductor core, without removing the catalyst metal island layer. due to the catalyst metal layer, crystal growth is promoted. this makes it possible to easily form the quantum well layer in which the thickness in the axial direction of a portion that covers the end surface of the other end of the semiconductor core is larger than the thickness in the radial direction of a portion that covers the outer peripheral surface of the semiconductor core. in this way, a microscopic rod-like light-emitting device having great freedom in installing in an apparatus can be manufactured by the manufacturing method according to the third aspect of the invention. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. a rod-like light-emitting device according to a fourth aspect of the invention comprises: a semiconductor core of a first conductivity type having a rod shape; a cap layer covering an end surface of one of two ends of the semiconductor core; and a semiconductor layer of a second conductivity type covering an outer peripheral surface of a portion of the semiconductor core other than an exposed portion, the exposed portion of the semiconductor core being a portion opposite from a portion covered with the cap layer of the semiconductor core, wherein the cap layer is made of a material having a higher electric resistance than the semiconductor layer. according to the above configuration, the end surface of one end of the semiconductor core of the first conductivity type shaped like a rod is covered with the cap layer, and the outer peripheral surface of a portion other than an exposed portion of the semiconductor core is covered with the semiconductor layer of the second conductivity type such that a portion opposite to the portion of the semiconductor core covered with the cap layer is not covered, so that the exposed portion is provided. therefore, even with the microscopic rod-like light-emitting device having a size of the order of micrometers or the order of nanometers, it becomes possible to connect the exposed portion of the semiconductor core to one electrode and to connect the other electrode to the portion of the semiconductor layer that covers the semiconductor core. in the rod-like light-emitting device, with one electrode connected to an exposed portion of the semiconductor core and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes so that electrons and holes recombine in an interface (pn junction) between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. as a result, light is emitted from the interface (pn junction) between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. in the rod-like light-emitting device, light is emitted from the whole side surface of the semiconductor core covered with the semiconductor layer. the light emitting region therefore becomes larger, which results in a high light emitting efficiency. note that a quantum well layer may be provided between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. moreover, one end surface of the semiconductor core is covered with the cap layer made of a material having an electric resistance larger than the semiconductor layer. this, on the one hand, prevents a current from flowing between the electrode connected on the cap layer side of the semiconductor core and the semiconductor core through the cap layer, and on the other hand, allows a current to flow between the electrode and the outer peripheral surface side of the semiconductor core through the semiconductor layer having a lower resistance than the cap layer. this eliminates or reduces current concentration to the end surface on the side having the cap layer thereon of the semiconductor core is provided. as a result, without concentration of light emission to the end surface of the semiconductor core, the efficiency of extracting light from the side surface of the semiconductor core is improved. accordingly, it is possible to implement a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and that has a high light emitting efficiency. the rod-like light-emitting device is not integral with the substrate, which allows great freedom in installing into an apparatus. in one embodiment, the outer peripheral surface of the semiconductor core except for the exposed portion and an outer peripheral surface of the cap layer are covered with the semiconductor layer that is continuous. in one embodiment, the cap layer is made of an insulating material. in one embodiment, the cap layer is made of an intrinsic semiconductor. in one embodiment, the cap layer is made of a semiconductor of the first conductivity type. in one embodiment, the cap layer is made of a semiconductor of the second conductivity type. in one embodiment, a quantum well layer is provided between the end surface of the semiconductor core and the cap layer. in one embodiment, a quantum well layer is provided between the outer peripheral surface of the semiconductor core and the semiconductor layer. in one embodiment, the outer peripheral surface of the semiconductor core except for the exposed portion and the outer peripheral surface of the cap layer are covered with the quantum well layer that is continuous. in one embodiment, a conductive layer having a lower electric resistance than the semiconductor layer is formed to cover the semiconductor layer. in one embodiment, a first electrode is connected to the exposed portion at the one end of the semiconductor core, and a second electrode is connected to the semiconductor layer at the other end of the semiconductor core on which the cap layer is provided. in one embodiment, a first electrode is connected to the exposed portion at the one end of the semiconductor core, and a second electrode is connected to at least the conductive layer of the semiconductor layer and the conductive layer on the other side of the semiconductor core on which the cap layer is provided. in one embodiment, the semiconductor core has a diameter of 500 nm or more and 100 μm or less. a light-emitting apparatus according to a fifth aspect of the invention comprises: a rod-like light-emitting device of any of the above-mentioned types; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the semiconductor layer at the other end of the semiconductor core on which the cap layer is provided is connected to another one of the electrodes on the substrate. with the above configuration, with a rod-like light-emitting device mounted on a substrate in such a manner that the longitudinal direction of the device is parallel to the mounting surface of the substrate, the outer peripheral surface of the semiconductor layer is in contact with the mounting surface of the substrate. therefore, heat generated in the rod-like light-emitting device can be dissipated with a good efficiency from the semiconductor layer to the substrate. accordingly, it is possible to implement a light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. in the above light-emitting apparatus, the rod-like light-emitting device is arranged to lie on its side on the substrate. this allows the whole thickness of the rod-like light-emitting device including the substrate to be decreased. in the above light-emitting apparatus, using the microscopic rod-like light-emitting device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. a light-emitting apparatus according to a sixth aspect of the invention comprises: at least one rod-like light-emitting device in which a conductive layer having a lower electric resistance than the semiconductor layer is formed to cover the semiconductor layer; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the conductive layer on the other side of the semiconductor core on which the cap layer is provided is connected to another one of the electrodes on the substrate. with the above configuration, with a rod-like light-emitting device mounted on a substrate in such a manner that the longitudinal direction of the device is parallel to the mounting surface of the substrate, the outer peripheral surface of the conductive layer is in contact with the mounting surface of the substrate. therefore, heat generated in the rod-like light-emitting device can be dissipated with a good efficiency from the conductive layer to the substrate. accordingly, it is possible to implement a light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. in the above light-emitting apparatus, the rod-like light-emitting device is arranged to lie on its side on the substrate. this allows the whole thickness of the rod-like light-emitting device including the substrate to be decreased. in the above light-emitting apparatus, using the microscopic rod-like light-emitting device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. in one embodiment, the light-emitting apparatus further has a second conductive layer formed on a substrate-side portion of the said conductive layer and having a lower electric resistance than the semiconductor layer. in one embodiment, the light-emitting apparatus has a metal portion formed between the electrodes on the substrate and below the rod-like light-emitting device. in one embodiment, there are a plurality of the rod-like light-emitting devices which each are associated with respective ones of metal portions formed on the substrate, and the metal portions associated with adjacent ones of the rod-like light-emitting devices are electrically insulated from each other. a method of manufacturing a light-emitting apparatus according to a seventh aspect of the invention is a manufacturing method for a light-emitting apparatus including at least one rod-like light-emitting device of any of the above-mentioned types, and the method comprises steps of: producing an insulating substrate formed with an alignment region having as a unit at least two electrodes to which independent voltages are respectively to be applied; applying a liquid containing the rod-like light-emitting device in nanometer order size or micrometer order size onto the insulating substrate; and applying the independent voltages respectively to the at least two electrodes to align the rod-like light-emitting device at a position defined by the at least two electrodes. with the above configuration, the insulating substrate where an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided is produced, and a liquid containing the rod-like light-emitting devices with the size of the order of nanometers or of the order of micrometers is applied onto the insulating substrate. thereafter, independent voltages are respectively applied to the at least two electrodes to align the microscopic rod-like light-emitting devices at positions defined by the at least two electrodes. thus, the above rod-like light-emitting devices can be easily aligned on the predetermined insulating substrate. in the above method of manufacturing a light-emitting apparatus, using only microscopic rod-like light-emitting devices makes it possible to decrease the amount of semiconductors used, and to manufacture a light-emitting apparatus whose thickness and weight can be reduced. in the above rod-like light-emitting device, light is emitted from the whole side surface of the semiconductor core covered with the semiconductor layer, and therefore the light emitting region becomes larger. this makes it possible to implement a light-emitting apparatus that has a high light emitting efficiency and achieves low power consumption. a rod-like light-emitting device according to an eighth aspect of the invention comprises: a semiconductor core of a first conductivity type having a rod shape; and a semiconductor layer of a second conductivity type covering an outer peripheral surface of a portion of the semiconductor core other than an exposed portion, the exposed portion of the semiconductor core being one end portion of the semiconductor core, wherein a step portion is provided between an outer peripheral surface of the exposed portion not covered with the semiconductor layer of the semiconductor core and an outer peripheral surface of a covered portion covered with the semiconductor layer of the semiconductor core. with the above configuration, the outer peripheral surface of a portion other than an exposed portion of the semiconductor core is covered with the semiconductor layer of the second conductivity type such that a portion opposite to the portion covered with the cap layer of the semiconductor core is not covered, so that the exposed portion is provided. therefore, even with the microscopic rod-like light-emitting device having a size of the order of micrometers or the order of nanometers, it becomes possible to connect the exposed portion of the semiconductor core to one electrode and to connect the other electrode to the portion of the semiconductor layer that covers the semiconductor core. in the rod-like light-emitting device, with one electrode connected to an exposed portion of the semiconductor core and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes so that electrons and holes recombine in an interface (pn junction) between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. as a result, light is emitted from the interface (pn junction) between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. in the rod-like light-emitting device, light is emitted from the whole side surface of the semiconductor core covered with the semiconductor layer. the light emitting region therefore becomes larger, which results in a high light emitting efficiency. note that a quantum well layer may be provided between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. accordingly, it is possible to implement a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and that has a high light emitting efficiency. the rod-like light-emitting device is not integral with the substrate, which allows great freedom in installing into an apparatus. moreover, a step portion, i.e., a level difference, is provided between the outer peripheral surface of the exposed portion not covered with the semiconductor layer of the semiconductor core, and the outer peripheral surface of a covered portion covered with the semiconductor layer of the semiconductor core. therefore, compared to a case in which the outer peripheral surface of an exposed portion of a semiconductor core is coincident or flush with the outer peripheral surface of a covered portion such that there exists no step, the position of the end surface of the semiconductor layer is determined depending on the step portion formed at the boundary between the exposed portion of the semiconductor core and the semiconductor layer. this can eliminate or reduce variations of the boundary position during manufacturing. here, the exposed portion of the semiconductor core may have a smaller diameter or a larger diameter than the covered portion. the step portion allows the distance between the outer peripheral surface of exposed portion of the semiconductor core and the semiconductor layer to be increased. therefore, when an electrode is connected to the exposed portion of the semiconductor core, short-circuiting and occurrence of a leakage current between the electrode and the semiconductor layer can be eliminated or reduced. light is easily extracted to the outside from the step portion formed at the boundary between the outer peripheral surface of the exposed portion of the semiconductor core and the outer peripheral surface of the covered portion, and therefore the light-extraction efficiency is improved. moreover, in cases where the exposed portion of the semiconductor core has a larger diameter than the covered portion, a large contact surface with the electrode connected to the exposed portion of the semiconductor core can be taken. therefore, the contact resistance can be decreased. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and to implement a light emitting apparatus, a backlight, an illuminating device, and a display device that have high light emitting efficiencies and low power consumption. in one embodiment, a perimeter of a cross section of the exposed portion perpendicular to a longitudinal direction of the semiconductor core is shorter than a perimeter of a cross section of the covered portion perpendicular to the longitudinal direction of the semiconductor core. in one embodiment, the cross section of the covered portion perpendicular to the longitudinal direction of the semiconductor core is polygonal. in one embodiment, a shape of the cross section of the exposed portion perpendicular to the longitudinal direction of the semiconductor core differs from a shape of the cross section of the covered portion perpendicular to the longitudinal direction of the semiconductor core. in one embodiment, the cross section of the exposed portion perpendicular to the longitudinal direction of the semiconductor core is nearly circular. in one embodiment, the rod-like light-emitting device has an insulating layer formed to cover the step portion of the semiconductor core and a step portion-side end surface of the semiconductor layer and also to cover a step portion-side portion of the exposed portion of the semiconductor core. in one embodiment, the rod-like light-emitting device has a conductive layer formed to cover the semiconductor layer and made of a material having a lower electric resistance than the semiconductor layer. in one embodiment, the rod-like light-emitting device has a quantum well layer formed between the semiconductor core and the semiconductor layer. in one embodiment, the rod-like light-emitting device has a cap layer formed to cover an end surface opposite to the exposed portion of the semiconductor core, the cap layer being made of a material having a higher electric resistance than the semiconductor layer. in one embodiment, the semiconductor core has a diameter of 500 nm or more and 100 μm or less. a light-emitting apparatus according to a ninth aspect of the invention comprises: a rod-like light-emitting device of any of the above-mentioned types; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the semiconductor layer at the other end of the semiconductor core is connected to another one of the electrodes on the substrate. with the above configuration, with a rod-like light-emitting device mounted on a substrate in such a manner that the longitudinal direction of the device is parallel to the mounting surface of the substrate, the outer peripheral surface of the semiconductor layer is in contact with the mounting surface of the substrate. therefore, heat generated in the rod-like light-emitting device can be dissipated with a good efficiency from the semiconductor layer to the substrate. accordingly, it is possible to implement a light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. in the above light-emitting apparatus, the rod-like light-emitting device is arranged to lie on its side on the substrate. this allows the whole thickness of the rod-like light-emitting device including the substrate to be decreased. in the above light-emitting apparatus, using the microscopic rod-like light-emitting device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. a light-emitting apparatus according to a tenth aspect of the invention comprises: a rod-like light-emitting device of any of the above-mentioned types; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate, wherein electrodes are formed, with a predetermined spacing therebetween, on the substrate, and wherein the exposed portion at the one end of the semiconductor core of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the conductive layer on the other side of the semiconductor core is connected to another one of the electrodes on the substrate. with the above configuration, with a rod-like light-emitting device mounted on a substrate in such a manner that the longitudinal direction of the device is parallel to the mounting surface of the substrate, the outer peripheral surface of the conductive layer is in contact with the mounting surface of the substrate. therefore, heat generated in the rod-like light-emitting device can be dissipated with a good efficiency from the conductive layer to the substrate. accordingly, it is possible to implement a light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. in the above light-emitting apparatus, the rod-like light-emitting device is arranged to lie on its side on the substrate. this allows the whole thickness of the rod-like light-emitting device including the substrate to be decreased. in the above light-emitting apparatus, using the microscopic rod-like light-emitting device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. in one embodiment, the light-emitting apparatus has a second conductive layer formed on a substrate-side portion of the said conductive layer and made of a material having a lower electric resistance than the semiconductor layer. in one embodiment, the light-emitting apparatus has a metal portion formed between the electrodes on the substrate and below the rod-like light-emitting device. in one embodiment, there are a plurality of the rod-like light-emitting devices which each are associated with respective ones of metal portions formed on the substrate, and the metal portions associated with adjacent ones of the rod-like light-emitting devices are electrically insulated from each other. a method according to an eleventh aspect of the invention is a manufacturing method for a light-emitting apparatus including a rod-like light-emitting device of any of the above-mentioned types, and the method comprises steps of: producing an insulating substrate formed with an alignment region having as a unit at least two electrodes to which independent voltages are respectively to be applied; applying a liquid containing the rod-like light-emitting device in nanometer order size or micrometer order size onto the insulating substrate; and applying the independent voltages respectively to the at least two electrodes to align the rod-like light-emitting device at a position defined by the at least two electrodes. with the above configuration, the insulating substrate where an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided is produced, and a liquid containing one or more rod-like light-emitting devices with the size of the order of nanometers or of the order of micrometers is applied onto the insulating substrate. thereafter, independent voltages are respectively applied to the at least two electrodes to align the microscopic rod-like light-emitting devices at positions defined by the at least two electrodes. thus, the above rod-like light-emitting devices can be easily aligned on the predetermined insulating substrate. in the above method of manufacturing a light-emitting apparatus, using only microscopic rod-like light-emitting devices makes it possible to decrease the amount of semiconductors used, and to manufacture a light-emitting apparatus whose thickness and weight can be reduced. in the above rod-like light-emitting device, light is emitted from the whole side surface of the semiconductor core covered with the semiconductor layer, and therefore the light emitting region becomes larger. this makes it possible to implement a light-emitting apparatus that has a high light emitting efficiency and achieves low power consumption. a backlight according to a twelfth aspect of the invention comprises a rod-like light-emitting device according to any one of the first, fourth, and eighth aspects of the invention. with the above configuration, use of the above rod-like light-emitting devices makes it possible to implement a backlight whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. an illuminating device according to a thirteenth aspect of the invention comprises a rod-like light-emitting device according to any one of the first, fourth, and eighth aspects of the invention. with the above configuration, use of the above rod-like light-emitting devices makes it possible to implement an illuminating device whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. a display device according to a fourteenth aspect of the invention comprises a rod-like light-emitting device according to any one of the first, fourth, and eighth aspects of the invention. with the above configuration, use of the above rod-like light-emitting devices makes it possible to implement a display device whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. a method of manufacturing a rod-like light-emitting device according to a fifteenth aspect of the invention, comprising: a semiconductor core forming step of forming a rod-shaped semiconductor core of a first conductivity type on a substrate; a semiconductor layer forming step of forming a cylindrical semiconductor layer of a second conductivity type to cover a surface of the semiconductor core; a separating step of separating from the substrate the semiconductor core having the cylindrical semiconductor layer of the second conductivity type formed in the semiconductor layer forming step; and an exposing step of, after the semiconductor layer forming step and before the separating step, or after the separating step, exposing part of an outer peripheral surface of the semiconductor core. according to the above configuration, the semiconductor core of the first conductivity type having a rod shape is formed on the substrate, and then the semiconductor layer of the second conductivity type having a cylindrical shape is formed to cover the surface of the semiconductor core. here, the end surface of the semiconductor core opposite to the substrate may be covered with the semiconductor layer or may be exposed. next, part of the outer peripheral surface of the semiconductor core is exposed, and then the semiconductor core including the exposed portion is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or by the use of a cutting tool. alternatively, the semiconductor core having the semiconductor layer is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or by the use of a cutting tool, and then part of the outer peripheral surface of the semiconductor core is exposed. in the rod-like light-emitting device separated from the substrate in such a way, with one electrode connected to the exposed portion of the semiconductor core, and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes, so that electrons and holes recombine in a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. thus, light is emitted from the pn junction. in this way, a microscopic rod-like light-emitting device having great freedom in installing into an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. in one embodiment, in the semiconductor layer forming step, the cylindrical semiconductor layer of the second conductivity type to cover the surface of the semiconductor core is formed under a condition where part of the outer peripheral surface of the semiconductor core is covered with a substance which inhibits forming of the semiconductor layer of the second conductivity type. and, in the exposing step, the substance of inhibiting forming of the semiconductor layer of the second conductivity type is removed to expose part of the outer peripheral surface of the semiconductor core. in one embodiment, the substrate is made of a semiconductor of the first conductivity type. and, after the semiconductor layer forming step and before the separating step, the exposing step removes, by an etching process, the semiconductor layer of the second conductivity type in a region other than a part covering the surface of the semiconductor core, and an upper part of the substrate corresponding to the region, to thereby expose part of the outer peripheral surface of the semiconductor core. in one embodiment, under a condition where the semiconductor core having the semiconductor layer of the second conductivity type and separated from the substrate in the separating step is aligned at a preset position on an insulating substrate, the exposing step exposes part of the outer peripheral surface of the semiconductor core having the semiconductor layer of the second conductivity type. in one embodiment, in the exposing step, a substrate-side portion of the outer peripheral surface of the semiconductor core is exposed, and in the semiconductor layer forming step, an end surface of the semiconductor core opposite from the substrate is covered with the semiconductor layer. in one embodiment, in the separating step, the semiconductor core covered with the semiconductor layer is separated from the substrate using ultrasonic waves. in one embodiment, in the separating step, the semiconductor core is mechanically separated from the substrate using a cutting tool. in one embodiment, the semiconductor core and the semiconductor layer are made of semiconductors whose base materials are gan, and in the exposing step, dry etching is used. in one embodiment, in the exposing step, the outer peripheral surface of the semiconductor core is exposed so as to be continuous with and flush with an outer peripheral surface of the semiconductor layer. in one embodiment, in the exposing step, the outer peripheral surface of a region covered with the semiconductor layer of the semiconductor core and the outer peripheral surface of an exposed region of the semiconductor core are continuous with each other. a method of manufacturing a display device according to a sixteenth aspect of the invention is a manufacturing method for a display device including a rod-like light-emitting device which is manufactured by any one of the above rod-like light-emitting device manufacturing methods, and the method comprises steps of: producing an insulating substrate formed with an alignment region having as a unit at least two electrodes to which independent voltages are respectively to be applied; applying a liquid containing the rod-like light-emitting device in nanometer order size or micrometer order size onto the insulating substrate; and applying the independent voltages respectively to the at least two electrodes to align the rod-like light-emitting device at a position defined by the at least two electrodes. with the above configuration, the insulating substrate where an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided is produced, and a liquid containing the rod-like light-emitting devices with the size of the order of nanometers or of the order of micrometers is applied onto the insulating substrate. thereafter, independent voltages are respectively applied to the at least two electrodes to align the microscopic rod-like light-emitting devices at positions defined by the at least two electrodes. thus, the above rod-like light-emitting devices can be easily aligned on the predetermined insulating substrate. in the above method of manufacturing a light-emitting apparatus, using only microscopic rod-like light-emitting devices makes it possible to decrease the amount of semiconductors used, and to manufacture a display device whose thickness and weight can be reduced. in the above rod-like light-emitting device, light is emitted from the whole side surface of the semiconductor core covered with the semiconductor layer, and therefore the light emitting region becomes larger. this makes it possible to implement a display device that has a high light emitting efficiency and achieves low power consumption. a method of manufacturing a rod-like light-emitting device according to a seventeenth aspect of the invention comprises steps of: forming on a substrate an insulator having a through-hole; forming a semiconductor core of a first conductivity type having a rod shape on a surface of the substrate in a position coincident with the through-hole such that the semiconductor core protrudes from the through-hole; forming a semiconductor core of a first conductivity type having a rod shape on a surface of the substrate in a position coincident with the through-hole such that the semiconductor core protrudes from the through-hole; forming a semiconductor layer of a second conductivity type to cover the semiconductor core protruding from the through-hole; etching the insulator such that part of the insulator remains on at least part of an outer peripheral surface not covered with the semiconductor layer of the semiconductor core, said at least part of the outer peripheral surface not covered with the semiconductor layer being a portion near an outer peripheral surface covered with the semiconductor layer of the semiconductor core; and separating from the substrate a rod-like light-emitting device having the semiconductor core, the semiconductor layer, and the part of the insulator remaining on the substrate in the insulator etching step. here, the term “first conductivity type” means p-type or n-type. also, the “second conductivity type” means n-type in cases where the first conductivity type is p-type whereas the second conductivity type means p-type in cases where the first conductivity type is n-type. according to the above configuration, the insulator having a through-hole is formed on the substrate, and then the semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the through-hole, on the surface of the substrate exposed from the through-hole. next, the semiconductor layer of the second conductivity type is formed to cover the semiconductor core protruding from the through-hole, and the insulator is etched so as to cause part of the insulator to remain on at least a portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core, of the outer peripheral surface not covered with the semiconductor layer of the semiconductor core. thus, one end portion (opposite from the substrate) of the semiconductor core can be covered with the semiconductor layer of the second conductivity type whereas at least the above portion of the other end portion (substrate side) of the semiconductor core can be covered with part of the insulator. next, the rod-like light-emitting device having the semiconductor core, the semiconductor layer, and the part of the insulator remaining on the substrate is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or by the use of a cutting tool. in this way, separating the rod-like light-emitting device from the substrate allows great freedom in installing into an apparatus of the rod-like light-emitting device. therefore, a microscopic rod-like light-emitting device that has great freedom in installing into an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to, for example, a device that has such dimensions that the diameter is within the range of from 10 nm to 5 μm, inclusive, and the length is within the range of from 100 nm to 200 μm, inclusive, and preferably a device that has such dimensions that the diameter is within the range of from 100 nm to 2 μm, inclusive, and the length is within the range of from 1 μm to 50 μm, inclusive. on the surface of the substrate in a position coincident with the through-hole mentioned above, the semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the through-hole. this enables the thickness of the semiconductor core to be uniform. the substrate is separated from the rod-like light-emitting device and therefore need not be used at the time of light emission of the rod-like light-emitting device. accordingly, substrate options that are available at the time of light emission of the rod-like light-emitting device are expanded. this can increase the freedom in selecting the form of the apparatus in which the rod-like light-emitting device is to be mounted. there is a portion of the semiconductor core that is easily broken upon the above-described separation from the substrate at the boundary (undesired position) between a region covered with the semiconductor layer of the second conductivity type and a region not covered with the semiconductor layer of the second conductivity type. this portion is reinforced with the insulator that remains on the semiconductor core. therefore, the rod-like light-emitting device can be easily split at a desired portion, that is, the root of the semiconductor core. accordingly, even in cases where a plurality of rod-like light-emitting devices mentioned above are manufactured, the lengths of the plurality of rod-like light-emitting devices can be made uniform. the substrate that has been used for forming the rod-like light-emitting device can be reused for manufacturing a rod-like light-emitting device after the previous rod-like light-emitting device is separated from the substrate. this can reduce the manufacturing cost. the above rod-like light-emitting device is microscopic, and therefore the amount of semiconductors used can be decreased. therefore, it becomes possible to reduce the thickness and weight of an apparatus in which the rod-like light-emitting devices is to be mounted. this allows loads to the environment to be reduced. in the above-described manufacturing method, of all the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, at least a portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core can be covered with the insulator. with an electrode on a first conductivity side connected to a portion not covered with the insulator of the semiconductor core, and with an electrode on a second conductivity side connected to the semiconductor layer, a current is caused to flow between the electrodes, so that the rod-like light-emitting device emits light. the above-described manufacturing method allows one side, i.e., one end portion, of the semiconductor core to be covered with the semiconductor layer of the second conductivity type. this can expand the light emitting region to increase the amount of emitted light and to raise the light emitting efficiency. with the above-described manufacturing method, of all the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, at least the portion near the outer peripheral surface covered with the semiconductor layer of the one end of the semiconductor core can be covered with the insulator. therefore, the electrode on the first conductivity side can be prevented from being short-circuited to the electrode on the second conductivity side. a method of manufacturing a rod-like light-emitting device according to an eighteenth aspect of the invention comprises steps of: forming on a substrate an underlying layer made of a semiconductor of a first conductivity type; forming on the underlying layer an insulator having a through-hole; forming a semiconductor core of the first conductivity type having a rod shape on a surface of the underlying layer in a position coincident with the through-hole such that the semiconductor core protrudes from the through-hole; forming a semiconductor layer of a second conductivity type to cover the semiconductor core protruding from the through-hole; etching the insulator and the underlying layer such that part of the insulator remains on at least part of an outer peripheral surface not covered with the semiconductor layer of the semiconductor core, said at least part of the outer peripheral surface not covered with the semiconductor layer being a portion near an outer peripheral surface covered with the semiconductor layer of the semiconductor core, and such that part of the underlying layer adjacent to a substrate-side end surface of the semiconductor core remains; and separating from the substrate a rod-like light-emitting device having the semiconductor core, the semiconductor layer, the part of the insulator remaining on the substrate in the etching step, and the part of the underlying layer remaining on the substrate in the etching step. here, the term “first conductivity type” means p-type or n-type. also, the “second conductivity type” means n-type in cases where the first conductivity type is p-type whereas the second conductivity type means p-type in cases where the first conductivity type is n-type. according to the above configuration, the underlying layer made of the semiconductor of the first conductivity type is formed on the substrate, and further the insulator having the through-hole is formed on the underlying layer. then, the semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the through-hole on the surface of the underlying layer exposed from the through-hole. next, the semiconductor layer of the second conductivity type is formed to cover the semiconductor core protruding from the through-hole, and the insulator and the underlying layer are etched so that part of the insulator remains and part of the underlying layer adjacent to an end on the substrate side of the semiconductor core remains on at least a portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core, of the outer peripheral surface not covered with the semiconductor layer of the semiconductor core. thus, one side (opposite to the substrate side) of the semiconductor core can be covered with the semiconductor layer of the second conductivity type whereas at least the above portion on the other side (substrate side) of the semiconductor core can be covered with part of the insulator. part of the outer peripheral surface of the underlying layer can be exposed. next, the rod-like light-emitting device having the semiconductor core, the semiconductor layer, the part of the insulator remaining on the substrate, and the part of the underlying layer remaining on the substrate is separated from the substrate by vibrating the substrate by means of ultrasonic waves, or by the use of a cutting tool. thus, the end surface (end surface in contact with the substrate) in the axial direction opposite to the semiconductor core side of the underlying layer can be exposed. in this way, separating the rod-like light-emitting device from the substrate allows great freedom in installing into an apparatus of the rod-like light-emitting device. therefore, a microscopic rod-like light-emitting device that has great freedom in installing into an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” refers to, for example, a device that has such dimensions that the diameter is within the range of from 10 nm to 5 μm, inclusive, and the length is within the range of from 100 nm to 200 μm, inclusive, and preferably a device that has such dimensions that the diameter is within the range of from 100 nm to 2 μm, inclusive, and the length is within the range of from 1 μm to 50 μm, inclusive. on the surface of the substrate in a position coincident with the through-hole mentioned above, the semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the through-hole. this enables the thickness of the semiconductor core to be uniform. the substrate is separated from the rod-like light-emitting device and therefore need not be used at the time of light emission of the rod-like light-emitting device. accordingly, substrate options that are available at the time of light emission of the rod-like light-emitting device are expanded. this can increase the freedom in selecting the form of the apparatus in which the rod-like light-emitting device is to be mounted. there is a portion of the semiconductor core that is easily broken upon the above-described separation from the substrate at the boundary (undesired position) between a region covered with the semiconductor layer of the second conductivity type and a region not covered with the semiconductor layer of the second conductivity type. this portion is reinforced with the insulator that remains on the semiconductor core. therefore, the rod-like light-emitting device can be easily split at a desired portion, that is, the root of the semiconductor core. accordingly, even in cases where a plurality of rod-like light-emitting devices mentioned above are manufactured, the lengths of the plurality of rod-like light-emitting devices can be made uniform. the substrate that has been used for forming the rod-like light-emitting device can be reused for manufacturing a rod-like light-emitting device after the previous rod-like light-emitting device is separated from the substrate. this can reduce the manufacturing cost. the above rod-like light-emitting device is microscopic, and therefore the amount of semiconductors used can be decreased. therefore, it becomes possible to reduce the thickness and weight of an apparatus in which the rod-like light-emitting devices is to be mounted. this allows loads to the environment to be reduced. with the above-described manufacturing method, the end surface in the axial direction opposite to the semiconductor core side of the underlying layer can be exposed, and the peripheral surface of the underlying layer can be exposed. with an electrode on the first conductivity side connected to at least one of the end surface and the peripheral surface, and with an electrode on the second conductivity side connected to the semiconductor layer, a current is caused to flow between the electrodes, so that the rod-like light-emitting device emits light. the above-described manufacturing method allows one side, i.e., one end portion, of the semiconductor core to be covered with the semiconductor layer of the second conductivity type. this can expand the light emitting region to increase the amount of emitted light and to raise the light emitting efficiency. with the above-described manufacturing method, of all the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, at least the portion near the outer peripheral surface covered with the semiconductor layer of the one end of the semiconductor core can be covered with the insulator. therefore, the electrode on the first conductivity side can be prevented from being short-circuited to the electrode on the second conductivity side. in one embodiment, the method further comprises a step of forming a quantum well layer between the semiconductor core and the semiconductor layer. a rod-like light-emitting device according to a nineteenth aspect of the invention comprises: a semiconductor core of a first conductivity type having a rod shape; a semiconductor layer of a second conductivity type covering one of two ends of the semiconductor core; and an insulator covering at least a portion near an outer peripheral surface covered with the semiconductor layer of the semiconductor core, of an outer peripheral surface not covered with the semiconductor layer of the semiconductor core. here, the term “first conductivity type” means p-type or n-type. also, the “second conductivity type” means n-type in cases where the first conductivity type is p-type whereas the second conductivity type means p-type in cases where the first conductivity type is n-type. according to the above configuration, the rod-like light-emitting device can be manufactured by a method of manufacturing a rod-like light-emitting device according to the present invention because the rod-like light-emitting device has the semiconductor core of the first conductivity type having the rod shape, the semiconductor layer of the second conductivity type covering one side, namely one end, of the semiconductor core, and the insulator covering the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, at least the portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core. with an electrode on the first conductivity side connected to an end portion of the semiconductor core not covered with the insulator, and an electrode on the second conductivity side connected to the semiconductor layer, a current is caused to flow between the electrodes, so that the rod-like light-emitting device emits light. at this point, one side, or end, of the semiconductor core is covered with the semiconductor layer of the second conductivity type, and therefore the light emitting region becomes larger. accordingly, the amount of emitted light can be increased, and the light emitting efficiency can be raised. even in cases where the rod-like light-emitting device is microscopic, at least an axially end surface of the other end of the semiconductor core is exposed. an electrode on the first conductivity side can be easily connected to this end surface. the device includes an insulator that covers at least the portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core, of the outer peripheral surface not covered with the semiconductor layer of the semiconductor core. as a result, the electrode on the first conductivity side becomes less likely to be short-circuited to the electrode on the second conductivity side, which facilitates formation of the electrode on the first conductivity side and the electrode on the second conductivity side. “the rod-like light-emitting device is microscopic” means that the device has such dimensions that, for example, the diameter is within the range of from 10 nm to 5 μm, inclusive, and the length is within the range of from 100 nm to 200 μm, inclusive, and preferably, the device has such dimensions that the diameter is within the range of from 100 nm to 2 μm, inclusive, and the length is within the range of from 1 μm to 50 μm, inclusive. a rod-like light-emitting device according to a twentieth aspect of the invention comprises: a semiconductor core of a first conductivity type having a rod shape; a semiconductor layer of a second conductivity type covering one of two ends of the semiconductor core; an insulator covering at least a portion near an outer peripheral surface covered with the semiconductor layer of the semiconductor core, of an outer peripheral surface not covered with the semiconductor layer of the semiconductor core; and an underlying layer of the first conductivity type adjoining the other end of the semiconductor core, wherein an end surface of the underlying layer axially opposite from the semiconductor core and a peripheral surface of the underlying layer are exposed. here, the term “first conductivity type” means p-type or n-type. also, the “second conductivity type” means n-type in cases where the first conductivity type is p-type whereas the second conductivity type means p-type in cases where the first conductivity type is n-type. according to the above configuration, the rod-like light-emitting device can be manufactured by a method of manufacturing a rod-like light-emitting device according to the invention because the rod-like light-emitting device has a semiconductor core of the first conductivity type having a rod shape, a semiconductor layer of the second conductivity type covering one end, or side, of the semiconductor core, an insulator covering at least a portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core, of all the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, and an underlying layer of the first conductivity type adjoining the other end of the semiconductor core, and an end surface of the underlying layer axially opposite from the semiconductor core and a peripheral surface of the underlying layer are exposed. for example, with an electrode on the first conductivity side connected to at least one of the end surface axially opposite to the semiconductor core of the underlying layer and the peripheral surface of the underlying layer, and with the electrode on the second conductivity side connected to the semiconductor layer, a current is caused to flow between the electrodes, so that the rod-like light-emitting device emits light. at this point, one side of the semiconductor core is covered with the semiconductor layer of the second conductivity type, and therefore the light emitting region becomes larger. accordingly, the amount of emitted light can be increased, and the light emitting efficiency can be raised. even in cases where the rod-like light-emitting device is microscopic, the end surface in the axial direction opposite to the semiconductor core of the underlying layer is exposed, and the peripheral surface of the underlying layer is exposed. therefore, an electrode on the first conductivity side can be easily connected to at least one of the end surface in the axial direction and the peripheral surface. the insulator that covers at least the portion near the outer peripheral surface covered with the semiconductor layer of the semiconductor core, of the outer peripheral surface not covered with the semiconductor layer of the semiconductor core, is included. as a result, the electrode on the first conductivity side becomes less likely to be short-circuited to the electrode on the second conductivity side, which facilitates formation of the electrode on the first conductivity side and the electrode on the second conductivity side. here, the “rod-like light-emitting device being microscopic” means that, for example, the rod-like light-emitting device has such dimensions that the diameter is within the range of from 10 nm to 5 μm and the length is within the range of from 100 nm to 200 μm, and more preferably the device have such dimensions that the diameter is within the range of from 100 nm to 2 μm and the length is within the range of from 1 μm to 50 μm. a backlight according to a twenty-first aspect of the present invention comprises a rod-like light-emitting device according to the nineteenth or twentieth aspect of the invention. according to the above configuration, due to the inclusion of the above rod-like light-emitting device, a backlight that has a high light emitting efficiency and achieves low power consumption can be implemented. an illuminating device according to a twenty-second aspect of the present invention comprises a rod-like light-emitting device according to the nineteenth or twentieth aspect of the invention. according to the above configuration, due to the inclusion of the above rod-like light-emitting device, an illuminating device that has a high light emitting efficiency and achieves low power consumption can be implemented. a display device according to a twenty-third aspect of the present invention comprises a rod-like light-emitting device according to the nineteenth or twentieth aspect of the invention. according to the above configuration, due to the inclusion of the above rod-like light-emitting device, a display device that has a high light emitting efficiency and achieves low power consumption can be implemented. a light-emitting apparatus according to a twenty-fourth aspect of the invention comprises: a rod-like light-emitting device including a semiconductor core of a first conductivity type having a rod shape, and a semiconductor layer of a second conductivity type formed to cover the semiconductor core, with an outer peripheral surface of part of the semiconductor core being exposed; and a substrate on which the rod-like light-emitting device is mounted such that a longitudinal direction of the rod-like light-emitting device is parallel to a mounting surface of the substrate. according to the above configuration, the rod-like light-emitting device that includes the semiconductor core of the first conductivity type having the rod shape, and the semiconductor layer of the second conductivity type formed to cover the semiconductor core, and in which the outer peripheral surface of part of the semiconductor core is exposed, is mounted on the substrate such that the longitudinal direction of the rod-like light-emitting device is parallel to the mounting surface of the substrate. in this rod-like light-emitting device, with one electrode connected to the exposed portion of the semiconductor core, and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes, so that electrons and holes recombine in a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. as a result, light is emitted from the pn junction, that is, the whole periphery of the semiconductor core. thus, the rod-like light-emitting device has an expanded light emitting region, and therefore has a high light emitting efficiency. with the rod-like light-emitting device mounted on the substrate such that the longitudinal direction of the rod-like light-emitting device is parallel to the mounting surface of the substrate, the outer peripheral surface of the semiconductor layer is in contact with the mounting surface of the substrate. therefore, heat generated in the rod-like light-emitting device can be dissipated with a good efficiency from the semiconductor layer to the substrate. accordingly, it is possible to implement a light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. in the above light-emitting apparatus, the rod-like light-emitting device is arranged to lie on its side on the substrate. this allows the whole thickness of the rod-like light-emitting device including the substrate to be decreased. in the above light-emitting apparatus, using the microscopic rod-like light-emitting device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. in one embodiment, an outer peripheral surface of one of two ends of the semiconductor core is exposed. in one embodiment, an end surface of the other end of the semiconductor core is covered with the semiconductor layer. in one embodiment, an outer peripheral surface of an exposed region of the semiconductor core is coincident or substantially coincident with an extension of an outermost peripheral surface of a region of the semiconductor core where the semiconductor core is covered with the semiconductor layer. in one embodiment, an outer peripheral surface of a region covered with the semiconductor layer of the semiconductor core is continuous with an outer peripheral surface of an exposed region of the semiconductor core. in one embodiment, the rod-like light-emitting device has a quantum well layer formed between the semiconductor core and the semiconductor layer. in one embodiment, the rod-like light-emitting device has a transparent electrode covering the semiconductor layer. in one embodiment, the rod-like light-emitting device has a metal layer on a substrate-side portion of the transparent electrode. in one embodiment, the rod-like light-emitting device has an exposed portion in which an outer peripheral surface of one of two ends is exposed, and electrodes are formed, with a predetermined spacing therebetween, on the substrate. the exposed portion at the one end of the rod-like light-emitting device is connected to one of the electrodes on the substrate, and the semiconductor layer at the other end of the rod-like light-emitting device is connected to another one of the electrodes on the substrate, and a metal portion is formed between the electrodes and below the rod-like light-emitting device on the substrate. a backlight according to a twenty-fifth aspect of the invention comprises a light-emitting apparatus according to the twenty-fourth aspect of the invention. according to the above configuration, use of the light-emitting apparatus makes it possible to implement a backlight with a high light emitting efficiency, low power consumption, and a good heat dissipation. use of the microscopic rod-like light-emitting devices for the light-emitting apparatus enables the amount of semiconductors used to be decreased to achieve reduction of the thickness and weight of the apparatus. an illuminating device according to a twenty-sixth aspect of the invention comprises the light-emitting apparatus according to the twenty-fourth aspect of the invention. according to the above configuration, use of the light-emitting apparatus makes it possible to implement an illuminating device with a high light emitting efficiency, low power consumption, and a good heat dissipation. use of the microscopic rod-like light-emitting devices for the light-emitting apparatus enables the amount of semiconductors used to be decreased to achieve reduction of the thickness and weight of the apparatus. a display device according to a twenty-seventh aspect of the invention comprises the light-emitting apparatus according to the twenty-fourth aspect of the invention. according to the above configuration, use of the light-emitting apparatus makes it possible to implement a display device with a high light emitting efficiency, low power consumption, and a good heat dissipation. use of the microscopic rod-like light-emitting devices for the light-emitting apparatus enables the amount of semiconductors used to be decreased to achieve reduction of the thickness and weight of the apparatus. brief description of drawings the present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not intended to limit the present invention, and wherein: fig. 1 is a perspective view of a rod-like light-emitting device of embodiment 1 of this invention; fig. 2 is a perspective view of a rod-like light-emitting device of embodiment 2 of this invention; fig. 3 is a perspective view of a rod-like light-emitting device of embodiment 3 of this invention; fig. 4 is a perspective view of a rod-like light-emitting device of embodiment 4 of this invention; fig. 5 is a cross-sectional view of the rod-like light-emitting device; fig. 6 is a cross-sectional view for illustration of electrode connections of the rod-like light-emitting device; fig. 7 is a perspective view of another rod-like light-emitting device having a rod shape whose cross section is hexagonal; fig. 8 is a perspective view of another rod-like light-emitting device having a rod shape whose cross section is hexagonal; fig. 9 is a perspective view of another rod-like light-emitting device having a rod shape whose cross section is hexagonal; fig. 10 is a perspective view of another rod-like light-emitting device having a rod shape whose cross section is hexagonal; fig. 11 is a cross-sectional view of a rod-like light-emitting device of embodiment 5 of this invention; fig. 12 is a schematic cross-sectional view of a main part of the rod-like light-emitting device; fig. 13 is a schematic cross-sectional view of a rod-like light-emitting device of a comparative example; fig. 14 is a cross-sectional view of a rod-like light-emitting device of embodiment 6 of this invention; fig. 15 is a schematic cross-sectional view of a main part of the rod-like light-emitting device; fig. 16 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of a comparative example; fig. 17a shows a process step of a method of manufacturing a rod-like light-emitting device of embodiment 7 of this invention; fig. 17b shows a process step following that of fig. 17a , showing the method of manufacturing rod-like light-emitting device; fig. 17c shows a process step following that of fig. 17b , showing the method of manufacturing rod-like light-emitting device; fig. 17d shows a process step following that of fig. 17c , showing the method of manufacturing rod-like light-emitting device; fig. 17e shows a process step following that of fig. 17d , showing the method of manufacturing rod-like light-emitting device; fig. 18a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 8 of this invention; fig. 18b shows a process step following that of fig. 18a , showing the method of manufacturing rod-like light-emitting device; fig. 18c shows a process step following that of fig. 18b , showing the method of manufacturing rod-like light-emitting device; fig. 18d shows a process step following that of fig. 18c , showing the method of manufacturing rod-like light-emitting device; fig. 18e shows a process step following that of fig. 18d , showing the method of manufacturing rod-like light-emitting device; fig. 19a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 9 of this invention; fig. 19b shows a process step following that of fig. 19a , showing the method of manufacturing rod-like light-emitting device; fig. 19c shows a process step following that of fig. 19b , showing the method of manufacturing rod-like light-emitting device; fig. 19d shows a process step following that of fig. 19c , showing the method of manufacturing rod-like light-emitting device; fig. 19e shows a process step following that of fig. 19d , showing the method of manufacturing rod-like light-emitting device; fig. 20 is a cross-sectional view of a rod-like light-emitting device of embodiment 10 of this invention; fig. 21 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of a comparative example; fig. 22 is a cross-sectional view of a main part of the rod-like light-emitting device of embodiment 10; fig. 23a is a cross-sectional view of a main part of a first modification of the rod-like light-emitting device of embodiment 10; fig. 23b is a cross-sectional view of a main part of a second modification of the rod-like light-emitting device of embodiment 10; fig. 23c is a cross-sectional view of a main part of a third modification of the rod-like light-emitting device of embodiment 10; fig. 24 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of a modification in which the outer peripheral surface of a cap layer is not covered with a semiconductor layer; fig. 25 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of another modification in which the outer peripheral surface of a cap layer is not covered with a semiconductor layer; fig. 26 is a cross-sectional view of a rod-like light-emitting device of embodiment 11 of this invention; fig. 27 is a cross-sectional view of a rod-like light-emitting device of embodiment 12 of this invention; fig. 28 is a schematic cross-sectional view of a main part of the rod-like light-emitting device; fig. 29a is a cross-sectional view of a main part of a first modification of the rod-like light-emitting device of embodiment 12; fig. 29b is a cross-sectional view of a main part of a second modification of the rod-like light-emitting device of embodiment 12; fig. 29c is a cross-sectional view of a main part of a third modification of the rod-like light-emitting device of embodiment 12; fig. 30 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of a modification in which the outer peripheral surface of a cap layer is not covered with a quantum well layer or a semiconductor layer; fig. 31 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of another modification in which the outer peripheral surface of a cap layer is not covered with a quantum well layer or a semiconductor layer; fig. 32 is a cross-sectional view of a rod-like light-emitting device of embodiment 13 of this invention; fig. 33 is a schematic cross-sectional view of a main part of the rod-like light-emitting device; fig. 34 is a cross-sectional view for illustration of electrode connections of the rod-like light-emitting device; fig. 35 is a perspective view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 14 of this invention; fig. 36 is a side view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 15 of this invention; fig. 37 is a cross-sectional view of the light-emitting apparatus; fig. 38 is a perspective view of a light-emitting apparatus of embodiment 16 of this invention; fig. 39 is a plan view of a main part of the light-emitting apparatus in which rod-like light-emitting devices adjacent to each other are opposite in orientation; fig. 40a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 17 of this invention; fig. 40b shows a process step following that of fig. 40a , showing the method of manufacturing rod-like light-emitting device; fig. 40c shows a process step following that of fig. 40b , showing the method of manufacturing rod-like light-emitting device; fig. 40d shows a process step following that of fig. 40c , showing the method of manufacturing rod-like light-emitting device; fig. 41a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 18 of this invention; fig. 41b shows a process step following that of fig. 41a , showing the method of manufacturing rod-like light-emitting device; fig. 41c shows a process step following that of fig. 41b , showing the method of manufacturing rod-like light-emitting device; fig. 41d shows a process step following that of fig. 41c , showing the method of manufacturing rod-like light-emitting device; fig. 41e shows a process step following that of fig. 41d , showing the method of manufacturing rod-like light-emitting device; fig. 42a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 19 of this invention; fig. 42b shows a process step following that of fig. 42a , showing the method of manufacturing rod-like light-emitting device; fig. 42c shows a process step following that of fig. 42b , showing the method of manufacturing rod-like light-emitting device; fig. 42d shows a process step following that of fig. 42c , showing the method of manufacturing rod-like light-emitting device; fig. 42e shows a process step following that of fig. 42d , showing the method of manufacturing rod-like light-emitting device; fig. 43 is a perspective view of a rod-like light-emitting device of embodiment 20 of this invention; fig. 44 is a cross-sectional view of the rod-like light-emitting device; fig. 45 is a schematic cross-sectional view of a rod-like light-emitting device of a comparative example; fig. 46 is a schematic cross-sectional view of a main part of a rod-like light-emitting device of embodiment 20; fig. 47 is a schematic cross-sectional view of a modification of the rod-like light-emitting device of embodiment 20; fig. 48 is a cross-sectional view of the main part of the rod-like light-emitting device for illustration of an electrode connection of an exposed portion of a semiconductor core of the rod-like light-emitting device; fig. 49 is a perspective view of a rod-like light-emitting device of embodiment 21 of this invention; fig. 50 is a schematic cross-sectional view of a main part of the rod-like light-emitting device of embodiment 21; fig. 51a is a schematic cross-sectional view of an exposed portion of a semiconductor core of the rod-like light-emitting device of embodiment 20; fig. 51b is a schematic cross-sectional view of an exposed portion of a semiconductor core of the rod-like light-emitting device of embodiment 21; fig. 51c is a schematic cross-sectional view of an exposed portion of a semiconductor core of a rod-like light-emitting device of a modification; fig. 52 is a perspective view of a rod-like light-emitting device of embodiment 22 of this invention; fig. 53 is a schematic cross-sectional view of a first modification of the rod-like light-emitting device of embodiment 22; fig. 54 is a schematic cross-sectional view of a second modification of the rod-like light-emitting device of embodiment 22; fig. 55 is a cross-sectional view of a rod-like light-emitting device of embodiment 23 of this invention; fig. 56 is a perspective view of the rod-like light-emitting device; fig. 57 is a cross-sectional view of a rod-like light-emitting device of embodiment 24 of this invention; fig. 58 is a perspective view of the rod-like light-emitting device; fig. 59 is a perspective view of a rod-like light-emitting device of embodiment 25 of this invention; fig. 60 is a perspective view of a rod-like light-emitting device of embodiment 26 of this invention; fig. 61 is a cross-sectional view of a rod-like light-emitting device of embodiment 27 of this invention; fig. 62 is a schematic sectional view of a main part of the rod-like light-emitting device of embodiment 27; fig. 63 is a perspective view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 28 of this invention; fig. 64 is a side view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 29 of this invention; fig. 65 is a cross-sectional view of the light-emitting apparatus; fig. 66 is a perspective view of a light-emitting apparatus of embodiment 30 of this invention; fig. 67 is a plan view of a main part of the light-emitting apparatus in which rod-like light-emitting devices adjacent to each other are opposite in orientation; fig. 68a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 31 of this invention; fig. 68b shows a process step following that of fig. 68a , showing the method of manufacturing rod-like light-emitting device; fig. 68c shows a process step following that of fig. 68b , showing the method of manufacturing rod-like light-emitting device; fig. 68d shows a process step following that of fig. 68c , showing the method of manufacturing rod-like light-emitting device; fig. 68e shows a process step following that of fig. 68d , showing the method of manufacturing rod-like light-emitting device; fig. 69a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 32 of this invention; fig. 69b shows a process step following that of fig. 69a , showing the method of manufacturing rod-like light-emitting device; fig. 69c shows a process step following that of fig. 69b , showing the method of manufacturing rod-like light-emitting device; fig. 69d shows a process step following that of fig. 69c , showing the method of manufacturing rod-like light-emitting device; fig. 69e shows a process step following that of fig. 69d , showing the method of manufacturing rod-like light-emitting device; fig. 70a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 33 of this invention; fig. 70b shows a process step following that of fig. 70a , showing the method of manufacturing rod-like light-emitting device; fig. 70c shows a process step following that of fig. 70b , showing the method of manufacturing rod-like light-emitting device; fig. 70d shows a process step following that of fig. 70c , showing the method of manufacturing rod-like light-emitting device; fig. 71a shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 34 of this invention; fig. 71b shows a process step following that of fig. 71a , showing the method of manufacturing rod-like light-emitting device; fig. 71c shows a process step following that of fig. 71b , showing the method of manufacturing rod-like light-emitting device; fig. 71d shows a process step following that of fig. 71c , showing the method of manufacturing rod-like light-emitting device; fig. 72 shows a process step of a method of manufacturing rod-like light-emitting device of embodiment 34 of this invention; fig. 73 shows a process step following that of fig. 72 , showing the method of manufacturing rod-like light-emitting device; fig. 74 shows a process step following that of fig. 73 , showing the method of manufacturing rod-like light-emitting device; fig. 75 shows a process step following that of fig. 74 , showing the method of manufacturing rod-like light-emitting device; fig. 76 shows a process step following that of fig. 75 , showing the method of manufacturing rod-like light-emitting device; fig. 77 shows a process step following that of fig. 76 , showing the method of manufacturing rod-like light-emitting device; fig. 78 shows a process step following that of fig. 77 , showing the method of manufacturing rod-like light-emitting device; fig. 79 shows a process step following that of fig. 78 , showing the method of manufacturing rod-like light-emitting device; fig. 80 shows a process step following that of fig. 79 , showing the method of manufacturing rod-like light-emitting device; fig. 81 shows a process step following that of fig. 80 , showing the method of manufacturing rod-like light-emitting device; fig. 82 shows a process step following that of fig. 81 , showing the method of manufacturing rod-like light-emitting device; fig. 83 shows a process step following that of fig. 82 , showing the method of manufacturing rod-like light-emitting device; fig. 84 shows a process step following that of fig. 83 , showing the method of manufacturing rod-like light-emitting device; fig. 85 shows a process step following that of fig. 84 , showing the method of manufacturing rod-like light-emitting device; fig. 86 shows a process step following that of fig. 85 , showing the method of manufacturing rod-like light-emitting device; fig. 87a is a plan view showing a process step of a method of manufacturing a display device using the rod-like light-emitting device shown in fig. 86 ; fig. 87b is a cross-sectional view of the display device taken along the line f 27 b-f 27 b of fig. 87a ; fig. 87c is a cross-sectional view of the display device taken along the line f 27 c-f 27 c of fig. 87a ; fig. 87d is a cross-sectional view of the display device taken along the line f 27 d-f 27 d of fig. 87a ; fig. 88a is a plan view showing a step subsequent to the steps shown in figs. 87a to 87d of the method of manufacturing a display device; fig. 88b is a cross-sectional view of the display device taken along the line f 28 b-f 28 b of fig. 88a ; fig. 88c is a cross-sectional view of the display device taken along the line f 28 c-f 28 c of fig. 88a ; fig. 88d is a cross-sectional view of the display device taken along the line f 28 d-f 28 d of fig. 88a ; fig. 89a is a plan view showing a step subsequent to the steps shown in figs. 88a to 88d of the method of manufacturing a display device; fig. 89b is a cross-sectional view of the display device taken along the line f 29 b-f 29 b of fig. 89a ; fig. 89c is a cross-sectional view of the display device taken along the line f 29 c-f 29 c of fig. 89a ; fig. 89d is a cross-sectional view of the display device taken along the line f 29 d-f 29 d of fig. 89a ; fig. 90a is a plan view showing a step subsequent to the steps shown in figs. 89a to 89d of the method of manufacturing a display device; fig. 90b is a cross-sectional view of the display device taken along the line f 30 b-f 30 b of fig. 90a ; fig. 90c is a cross-sectional view of the display device taken along the line f 30 c-f 30 c of fig. 90a ; fig. 90d is a cross-sectional view of the display device taken along the line f 30 d-f 30 d of fig. 90a ; fig. 91a is a plan view showing a step subsequent to the steps shown in figs. 90a to 90d of the method of manufacturing a display device; fig. 91b is a cross-sectional view of the display device taken along the line f 31 b-f 31 b of fig. 91a ; fig. 91c is a cross-sectional view of the display device taken along the line f 31 c-f 31 c of fig. 91a ; fig. 91d is a cross-sectional view of the display device taken along the line f 31 d-f 31 d of fig. 91a ; fig. 92a is a plan view showing a step subsequent to the steps shown in figs. 91a to 91d of the method of manufacturing a display device; fig. 92b is a cross-sectional view of the display device taken along the line f 32 b-f 32 b of fig. 92a ; fig. 92c is a cross-sectional view of the display device taken along the line f 32 c-f 32 c of fig. 92a ; fig. 92d is a cross-sectional view of the display device taken along the line f 32 d-f 32 d of fig. 92a ; fig. 93a is a plan view showing a step subsequent to the steps shown in figs. 92a to 92d of the method of manufacturing a display device; fig. 93b is a cross-sectional view of the display device taken along the line f 33 b-f 33 b of fig. 93a ; fig. 93c is a cross-sectional view of the display device taken along the line f 33 c-f 33 c of fig. 93a ; fig. 93d is a cross-sectional view of the display device taken along the line f 33 d-f 33 d of fig. 93a ; fig. 94a is a plan view showing a step subsequent to the steps shown in figs. 93a to 93d of the method of manufacturing a display device; fig. 94b is a cross-sectional view of the display device taken along the line f 34 b-f 34 b of fig. 94a ; fig. 94c is a cross-sectional view of the display device taken along the line f 34 c-f 34 c of fig. 94a ; fig. 94d is a cross-sectional view of the display device taken along the line f 34 d-f 34 d of fig. 94a ; fig. 95 is a schematic cross-sectional view of a rod-like light-emitting device of embodiment 36 of this invention; fig. 96a shows a process step of a method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96b shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96c shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96d shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96e shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96f shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96g shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96h shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96i shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96j shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 96k shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 36; fig. 97 is a schematic cross-sectional view of a rod-like light-emitting device of embodiment 37 of this invention; fig. 98a shows a process step of a method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98b shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98c shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98d shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98e shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98f shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98g shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98h shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98i shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98j shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98k shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98l shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 98m shows a process step of the method of manufacturing the rod-like light-emitting device of embodiment 37; fig. 99 is a plan view of an insulating substrate used for a backlight, an illuminating device and/or a display device each including the rod-like light-emitting devices of embodiment 38 of the invention; fig. 100 is a schematic cross-sectional view taken along the line 100 - 100 of fig. 99 ; fig. 101 illustrates the principle of aligning the rod-like light-emitting devices of the above embodiment; fig. 102 is a diagram for illustration of potentials applied to electrodes when the rod-like light-emitting devices of the above embodiment are aligned; fig. 103 is a plan view of an insulating substrate on which the rod-like light-emitting devices of the above embodiment are aligned; fig. 104 is a plan view of the display device; fig. 105 is a circuit diagram of a main part of a display unit of the display device; fig. 106 is a perspective view of a light-emitting apparatus of embodiment 39 of this invention; fig. 107 is a perspective view of a light-emitting apparatus of embodiment 40 of this invention; fig. 108 is a perspective view of a light-emitting apparatus of embodiment 41 of this invention; fig. 109 is a perspective view of a light-emitting apparatus of embodiment 42 of this invention; fig. 110 is a perspective view of a light-emitting apparatus of embodiment 43 of this invention; fig. 111 is a side view of a light-emitting apparatus of embodiment 44 of this invention; fig. 112 is a cross-sectional view of the light-emitting apparatus; fig. 113 is a cross-sectional view of a variation of the light-emitting apparatus; fig. 114 is a cross-sectional view of another variation of the light-emitting apparatus; fig. 115 is a side view of a light-emitting apparatus of embodiment 45 of this invention; fig. 116 is a perspective view of the light-emitting apparatus; fig. 117 is a plan view of an insulating substrate of a light-emitting apparatus used for a backlight, an illuminating device and/or a display device; fig. 118 is a schematic cross-sectional view taken along the line 118 - 118 of fig. 117 ; fig. 119 illustrates the principle of aligning the rod-like light-emitting devices of the above embodiment; fig. 120 is a diagram for illustration of potentials applied to electrodes when the rod-like light-emitting devices of the above embodiment are aligned; fig. 121 is a plan view of an insulating substrate on which the rod-like light-emitting devices are aligned; fig. 122 is a plan view of the display device; fig. 123 is a circuit diagram of a main part of a display unit of the display device; fig. 124 is a plan view of a light-emitting apparatus of embodiment 46 of this invention; fig. 125 is a perspective view of the light-emitting apparatus; and fig. 126 is a plan view of a main part of the light-emitting apparatus in which rod-like light-emitting devices adjacent to each other are opposite in orientation. description of embodiments a rod-like light-emitting device, a method of manufacturing a rod-like light-emitting device, a backlight, an illuminating device and a display device according to this invention, in embodiments shown in figures, are described in detail below. note that a first conductivity type is an n type, and a second conductivity type is a p type in the embodiments; however, the first conductivity type may be the p type, and the second conductivity type may be an n type. (embodiment 1) fig. 1 is a perspective view of a rod-like light-emitting device of embodiment 1 of this invention. the rod-like light-emitting device of embodiment 1, as shown in fig. 1 , includes a semiconductor core 11 made of n-type gan in a rod shape whose cross section is nearly circular, and a semiconductor layer 12 made of p-type gan and formed to cover part of the semiconductor core 11 . the semiconductor core 11 has, at one end thereof, an exposed portion 11 a in which an outer peripheral surface of the semiconductor core 11 is exposed. an end surface of the other end of the semiconductor core 11 is covered with the semiconductor layer 12 . the rod-like light-emitting device is manufactured in the following way. first, a mask having a growth hole is formed on a substrate made of n-type gan. silicon oxide (sio 2 ), silicon nitride (si 3 n 4 ) or another material that is selectively etchable with respect to the semiconductor core 11 and the semiconductor layer 12 is used as the material for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. next, the semiconductor core 11 shaped like a rod is formed by crystal growth of n-type gan on the substrate exposed through a growth hole of the mask using a metal organic chemical vapor deposition (mocvd) device. the temperature of the mocvd device is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 3 ) for n-type impurity supply and further hydrogen (h 3 ) as a carrier gas are supplied, so that a semiconductor core of n-type gan with si used as the impurity can be grown. at this point, the diameter of the semiconductor core 11 to be grown can be determined depending on the diameter of the growth hole of the mask. next, a semiconductor layer made of p-type gan is formed over the whole substrate so that the rod-like semiconductor core 11 is covered with the semiconductor layer. the temperature of the mocvd device is set to about 960° c., tmg and nh 3 are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, all of the region except for a portion covering the semiconductor core of the semiconductor layer, and the mask are removed by lift-off to expose the outer peripheral surface on the substrate side of the rod-like semiconductor core 11 , so that the exposed portion 11 a is formed. in this state, the end surface of the semiconductor core 11 opposite to the substrate is covered with the semiconductor layer 12 . in the case where a mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. in this embodiment, the length of the exposed portion 11 a of the semiconductor core 11 is determined depending on the thickness of the removed mask. the lift-off is used in the exposing step of this embodiment; however, part of the semiconductor core may be exposed by etching. next, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 11 covered with the semiconductor layer 12 so as to bend the root close to the substrate of the semiconductor core 11 that erects on the substrate. as a result, the semiconductor core 11 covered with the semiconductor layer 12 is separated from the substrate. in this way, the microscopic rod-like light-emitting device that is separated from the substrate made of n-type gan can be manufactured. moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer occurs radially outward from the outer peripheral surface of the semiconductor core 11 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 11 can be covered with the semiconductor layer 12 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. according to a rod-like light-emitting device having the above configuration, the semiconductor layer 12 made of p-type gan is formed to cover the semiconductor core 11 shaped like a rod and made of n-type gan, and to expose the outer peripheral surface of part of the semiconductor core 11 . this makes it possible to connect the exposed portion 11 a of the semiconductor core 11 to an n-side electrode and to connect a p-side electrode to a portion of the semiconductor layer 12 with which the semiconductor core 11 is covered, even when the rod-like light-emitting device is microscopic and has a size of the order of micrometers or of the order of nanometers. in the rod-like light-emitting device, with the n-side electrode connected to the exposed portion 11 a of the semiconductor core 11 and with the p-side electrode connected to the semiconductor layer 12 , a current is caused to flow from the p-side electrode to the n-side electrode to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the semiconductor core 11 and the inner peripheral surface of the semiconductor layer 12 . thus, light is emitted from the pn junction. in this rod-like light-emitting device, light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer 12 . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. accordingly, it is possible to implement a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and has a high light emitting efficiency. the above rod-like light-emitting device is not integral with the substrate, which allows great freedom in installing into an apparatus. the microscopic rod-like light-emitting device as used herein is a device, for example, in micrometer order size with a diameter of 1 μm and a length in the range of from 10 μm to 30 μm, or in nanometer order size in which at least the diameter of the diameter and the length of 1 μm or less. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductors used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and achieve low power consumption. the outer peripheral surface of one side of the above semiconductor core 11 is exposed, for example, in the axial direction by about 1 μm to 5 μm. this makes it possible to connect one electrode to the exposed portion 11 a of the outer peripheral surface of the semiconductor core 11 and to connect an electrode to the semiconductor layer 12 on the other side of the semiconductor core 11 . therefore, connections can be made with the electrodes separate from each other in both ends. thus, the electrode connected to the semiconductor layer 12 and the exposed portion of the semiconductor core 11 can easily be prevented from becoming short-circuited to each other. the end surface of the other end of the above semiconductor core 11 is covered with the semiconductor layer 12 . this makes it possible to easily connect the p-side electrode to a portion of the semiconductor layer 12 that covers the end surface of the semiconductor core 11 opposite to the exposed portion 11 a , without short-circuiting the p-side electrode to the semiconductor core 11 . in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device. the outer peripheral surface of the region covered with the semiconductor layer 12 of the semiconductor core 11 and the outer peripheral surface of the exposed region of the semiconductor core 11 are continuous with each other such that the exposed region of the semiconductor core 11 is thinner than the outer diameter of the semiconductor layer 12 , and therefore, in the manufacturing step, the side of the substrate of the exposed region of the semiconductor core 11 becomes more likely to be broken on the substrate side in the exposed region of the semiconductor core 11 , which facilitates manufacturing. (embodiment 2) fig. 2 is a perspective view of a rod-like light-emitting device of embodiment 2 of this invention. the rod-like light-emitting device of embodiment 2, as shown in fig. 2 , includes a semiconductor core 21 made of n-type gan in a rod shape whose cross section is nearly circular, a quantum well layer 22 made of p-type ingan and formed to cover part of the semiconductor core 21 , and a semiconductor layer 23 made of p-type gan and formed to cover the quantum well layer 22 . the semiconductor core 21 has, at one end thereof, an exposed portion 21 a in which the outer peripheral surface of the semiconductor core 21 is exposed. the end surface of the other end of the semiconductor core 21 is covered with the quantum well layer 22 and the semiconductor layer 23 . in the above rod-like light-emitting device of embodiment 2, like the rod-like light-emitting device of embodiment 1, the semiconductor core 21 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using the mocvd device. the above rod-like light-emitting device of embodiment 2 has effects similar to those of the rod-like light-emitting device of embodiment 1. the quantum well layer 22 is formed between the semiconductor core 21 and the semiconductor layer 23 . as a result, due to quantum confinement effects of the quantum well layer 22 , the light emitting efficiency can further be improved. after the semiconductor core of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 22 can be formed on the semiconductor core 21 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 23 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer, and may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. (embodiment 3) fig. 3 is a perspective view of a rod-like light-emitting device of embodiment 3 of this invention. the rod-like light-emitting device of embodiment 3, as shown in fig. 3 , includes the semiconductor core 11 made of n-type gan in a rod shape whose cross section is nearly circular, the semiconductor layer 12 made of p-type gan and formed to cover part of the semiconductor core 11 , and a transparent electrode 13 formed to cover the semiconductor layer 12 . the semiconductor core 11 has, at one end thereof, an exposed portion 11 a in which the outer peripheral surface of the semiconductor core 11 is exposed. the end surface of the other end of the semiconductor core is covered with the semiconductor layer 12 and the transparent electrode 13 . the transparent electrode 13 is formed of tin-doped indium oxide (ito) having a thickness of 200 nm. for deposition of ito, a vapor-deposition method or a sputtering method can be used. after the deposition of the ito film, heat treatment is performed at a temperature of 500° c. to 600° c., which makes it possible to reduce the contact resistance between the semiconductor layer 12 made of p-type gan and the transparent electrode 13 made of ito. note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm. for the deposition, a vapor-deposition method or a sputtering method can be used. to further decrease the resistance of the electrode layer, a laminated metal film of ag/ni may be deposited on the ito film. in the above rod-like light-emitting device of embodiment 3, like the rod-like light-emitting device of embodiment 1, the semiconductor core 11 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using the mocvd device. the above rod-like light-emitting device of embodiment 3 has effects similar to those of the rod-like light-emitting device of embodiment 1. forming the transparent electrode 13 so as to cover approximately the whole of the semiconductor layer 12 causes the semiconductor layer 12 to be connected through the transparent electrode 13 to an electrode, which allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that the whole device can emit light. thus, the light emitting efficiency is further improved. in particular, with a configuration of a semiconductor core made of an n-type semiconductor and a semiconductor layer made of a p-type semiconductor, the semiconductor layer made of the p-type semiconductor is less likely to increase the impurity concentration, and the resistance is high. however, the transparent electrode allows a wider current path to be formed, so that the whole device can emit light. thus, the light emitting efficiency is further improved. (embodiment 4) fig. 4 is a perspective view of a rod-like light-emitting device of embodiment 4 of this invention. the rod-like light-emitting device of embodiment 4, as shown in fig. 4 , includes the semiconductor core 21 made of n-type gan in a rod shape whose cross section is nearly circular, the quantum well layer 22 made of p-type ingan and formed to cover part of the semiconductor core 21 , the semiconductor layer 23 made of p-type gan and formed to cover the quantum well layer 22 , and a transparent electrode 24 formed to cover the semiconductor layer 23 . the semiconductor core 21 has, at one end thereof, an exposed portion 21 a in which the outer peripheral surface of the semiconductor core 21 is exposed. as shown in the cross-sectional view of fig. 5 , the end surface of the other end of the semiconductor core 21 is covered with the quantum well layer 22 , the semiconductor layer 23 , and the transparent electrode 24 . as such, connecting an electrode (or interconnection) to an end of the transparent electrode far from the exposed portion 21 a of the semiconductor core 21 can easily prevent short-circuiting between the electrode and the semiconductor core 21 , and the electrode (or interconnection) connected to the transparent electrode can be thick or have a large cross-sectional area to enable heat to be dissipated with a good efficiency through the electrode (or interconnection). in the rod-like light-emitting device, as shown in fig. 6 , an n-side electrode 25 is connected to the exposed portion 21 a of the semiconductor core 21 , and a p-side electrode 26 is connected to the transparent electrode 24 on the other side. the p-side electrode 26 is connected to an end of the transparent electrode 24 , and therefore the area obtained by shielding the light emitting region by the electrodes can be minimized to increase the light-extraction efficiency. in the above rod-like light-emitting device of embodiment 4, like the rod-like light-emitting device of embodiment 1, the semiconductor core 21 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using the mocvd device. the above rod-like light-emitting device of embodiment 4 has effects similar to those of the rod-like light-emitting device of embodiment 2. forming the transparent electrode 24 so as to cover nearly the whole of the semiconductor layer 23 causes the semiconductor layer 23 to be connected through the transparent electrode 24 to the p-side electrode 26 , which allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that the whole device can emit light. thus, the light emitting efficiency is further improved. in particular, with a configuration of a semiconductor core made of an n-type semiconductor and a semiconductor layer made of a p-type semiconductor, the semiconductor layer made of the p-type semiconductor is less likely to increase the impurity concentration, and the resistance is high. however, the transparent electrode allows a wider current path to be formed, so that the whole device can emit light. thus, the light emitting efficiency is further improved. while n-type gan doped with si and p-type gan doped with mg are used in embodiments 1 to 4 described above, impurities for doping gan are not limited to this case. for the n type, ge and the like can be used, and for the p type, zn and the like can be used. note that while, in the above embodiments 1 to 4, descriptions have been given of the rod-like light-emitting devices in which the semiconductor cores 11 and 21 having rod shapes whose cross-sections are nearly circular are covered with a semiconductor layer and a quantum well layer, this invention may be applied to a rod-like light-emitting device in which, for example, a semiconductor core having a rod shape whose cross-section has the shape of another polygon, such as approximately a hexagon, is covered with a semiconductor layer, a quantum well layer and the like. n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of approximately a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate is the c-axis direction. depending on growth conditions such as a growth direction and a growth temperature, the shape of the cross section tends to be nearly circular in cases where the semiconductor core to be grown has a small diameter in the range of from several tens of nanometers to several hundreds of nanometers. in cases where the diameter is large in the range of from about 0.5 μm to several micrometers, it becomes easier to grow the semiconductor core whose cross section is nearly hexagonal. for example, as shown in fig. 7 , there are included a semiconductor core 31 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, and a semiconductor layer 32 made of p-type gan and formed to cover part of the semiconductor core 31 . the semiconductor core 31 has, at one end thereof, an exposed portion 31 a in which the outer peripheral surface of the semiconductor core 31 is exposed. the end surface of the other end of the semiconductor core 31 is covered with the semiconductor layer 32 . as shown in fig. 8 , there are included a semiconductor core 41 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 42 formed to cover part of the semiconductor core 41 , and a semiconductor layer 43 made of p-type gan and formed to cover the quantum well layer 42 . the semiconductor core 41 has, at one end thereof, an exposed portion 41 a in which the outer peripheral surface of the semiconductor core 41 is exposed. the end surface of the other end of the semiconductor core 41 is covered with the quantum well layer 42 and the semiconductor layer 43 . as shown in fig. 9 , there are included the semiconductor core 31 made of n-type gan and having a rod shape whose cross section is nearly circular, the semiconductor layer 32 formed to cover part of the semiconductor core 31 , and a transparent electrode 33 made of ito and formed to cover the semiconductor layer 32 . the semiconductor core 31 has, at one end thereof, an exposed portion 31 a in which the outer peripheral surface of the semiconductor core 31 is exposed. the end surface of the other end of the semiconductor core 31 is covered with the semiconductor layer 32 and the transparent electrode 33 . as shown in fig. 10 , there are included the semiconductor core 41 made of n-type gan and having a rod shape whose cross section is nearly circular, the quantum well layer 42 made of p-type ingan and formed to cover part of the semiconductor core 41 , the semiconductor layer 43 made of p-type gan and formed to cover the quantum well layer 42 , and a transparent electrode 44 made of ito and formed to cover the semiconductor layer 43 . the semiconductor core 41 has, at one end thereof, an exposed portion 41 a in which the outer peripheral surface of the semiconductor core 41 is exposed. as shown in fig. 5 , the end surface of the other end of the semiconductor core 41 is covered with the quantum well layer 42 , the semiconductor layer 43 and the transparent electrode 44 . (embodiment 5) fig. 11 is a sectional view of a rod-like light-emitting device of embodiment 5 of this invention. the rod-like light-emitting device of embodiment 5, as shown in fig. 11 , includes a semiconductor core 51 made of n-type gan in a rod shape whose cross section is nearly circular, and a semiconductor layer 52 made of p-type gan and formed to cover part of the semiconductor core 51 . the semiconductor core 51 has, at one end thereof, an exposed portion 51 a in which an outer peripheral surface of the semiconductor core 51 is exposed. an end surface of the other end of the semiconductor core 51 is covered with the semiconductor layer 52 . the semiconductor layer 52 is formed such that the thickness in the axial direction of a portion 52 a that covers the end surface of the other end of the semiconductor core 51 is larger than the thickness in the radial direction of a portion 52 b that covers the outer peripheral surface of the semiconductor core 51 . fig. 12 is a schematic cross-sectional view of the main part of the above rod-like light-emitting device. in the semiconductor layer 52 , a thickness t 2 in the axial direction of the portion 52 a for covering the end surface of the other end of the semiconductor core 51 is larger than a thickness t 1 in the radial direction of the portion 52 b for covering the outer peripheral surface of the semiconductor core 51 . thus, an electrode 53 can be connected to the semiconductor layer 52 , which covers the end surface of the other end of the semiconductor core 51 , without overlapping the semiconductor core 51 . the light-extraction efficiency of the side surface of the semiconductor core 51 can therefore be improved. also, even in cases where the electrode 53 connected to the semiconductor layer 52 that covers the end surface of the other end of the semiconductor core 51 overlaps the semiconductor core 51 , the amount of overlapping can be reduced, and therefore the light-extraction efficiency can be improved. in the semiconductor layer 52 , the thickness t 2 in the axial direction of the portion 52 a covering the end surface of the other end of the semiconductor core 51 is larger than the thickness t 1 in the radial direction of the portion 52 b covering the outer peripheral surface of the semiconductor core 51 , and therefore the portion 52 a of the semiconductor layer 52 covering the end surface of the other side of the semiconductor core 51 has a high resistance. as a result, light emitting does not concentrate to the other side of the semiconductor core 51 . this can enhance light emitting in a side surface region of the semiconductor core 51 , and can reduce or eliminate the leakage current in the portion 52 a of the semiconductor layer 52 that covers the end surface of the other end of the semiconductor core 51 . in contrast, for example, as shown in a schematic cross-sectional view of the main part of a rod-like light-emitting device in a comparative example of fig. 13 , when, in a semiconductor layer 1052 , a thickness t 11 in the radial direction of a portion 1052 b covering the outer peripheral surface of a semiconductor core 1051 is approximately the same as a thickness t 12 in the axial direction of a portion 1052 a covering the end surface of the other end of the semiconductor core 1051 , light emission concentrates to the other side of the semiconductor core 1051 . therefore, light emission can be reduced in a side surface region of the semiconductor core 1051 , and a leakage current can occur in the portion 1052 a of the semiconductor layer 1052 covering the end surface of the other end of the semiconductor core 1051 . an electrode 1053 greatly overlaps the semiconductor core 1051 , and therefore the light-extraction efficiency decreases. the above rod-like light-emitting device of embodiment 5 has effects similar to those of the rod-like light-emitting device of embodiment 1. (embodiment 6) fig. 14 is a sectional view of a rod-like light-emitting device of embodiment 6 of this invention. the rod-like light-emitting device of embodiment 6, as shown in fig. 14 , includes a semiconductor core 61 made of n-type gan in a rod shape whose cross section is nearly circular, a quantum well layer 62 made of p-type ingan and formed to cover part of the semiconductor core 61 , and a semiconductor layer 63 made of p-type gan and formed to cover the quantum well layer 62 . the semiconductor core 61 has, at one end thereof, an exposed portion 61 a in which the outer peripheral surface of the semiconductor core 61 is exposed. the end surface of the other end of the semiconductor core 61 is covered with the quantum well layer 62 and the semiconductor layer 63 . the quantum well layer 62 is formed such that the thickness in the axial direction of a portion 62 a that covers the end surface of the other end of the semiconductor core 61 is larger than the thickness in the radial direction of a portion 62 b that covers the outer peripheral surface of the semiconductor core 61 . fig. 15 is a schematic cross-sectional view of the main part of the above rod-like light-emitting device. in the quantum well layer 62 , a thickness t 22 in the axial direction of the portion 62 a for covering the end surface of the other end of the semiconductor core 61 is larger than a thickness t 21 in the radial direction of the portion 62 b for covering the outer peripheral surface of the semiconductor core 61 . thus, an electrode 64 can be connected to the semiconductor layer 63 , which covers the end surface of the other end of the semiconductor core 61 , without overlapping the semiconductor core 61 . the light-extraction efficiency of the side surface of the semiconductor core 61 can therefore be improved. also, even in cases where the electrode 64 connected to the semiconductor layer 63 that covers the end surface of the other end of the semiconductor core 61 overlaps the semiconductor core 61 , the amount of overlapping can be reduced, and therefore the light-extraction efficiency can be improved. in the quantum well layer 62 , the thickness t 22 in the axial direction of the portion 62 a covering the end surface of the other end of the semiconductor core 61 is larger than the thickness t 21 in the radial direction of the portion 62 b covering the outer peripheral surface of the semiconductor core 61 . this can relax electric field concentration that occurs at a corner on the other side of the semiconductor core 61 to improve the breakdown voltage and increase the lifetime of the light-emitting device and can reduce or eliminate the leakage current in the portion 62 a of the quantum well layer 62 that covers the end surface of the other end of the semiconductor core 61 . in contrast, for example, as shown in a schematic cross-sectional view of the main part of a rod-like light-emitting device in a comparative example of fig. 16 , when, in a quantum well layer 1062 , a thickness t 31 in the radial direction of a portion 1062 b covering the outer peripheral surface of a semiconductor core 1061 is approximately the same as a thickness t 32 in the axial direction of a portion 1062 a covering the end surface of the other end of the semiconductor core 1061 , electric field concentration would occur at a corner of the other end of the semiconductor core 1061 so that the breakdown voltage would be lowered. therefore, light emission can be reduced in a side surface region of the semiconductor core 1061 , and a leakage current would occur in the portion 1062 a of the quantum well layer 1062 covering the end surface of the other end of the semiconductor core 1061 . an electrode 1064 greatly overlaps the semiconductor core 1061 , and therefore the light-extraction efficiency decreases. the above rod-like light-emitting device of embodiment 6 has effects and advantages similar to those of the rod-like light-emitting device of embodiment 1. (embodiment 7) figs. 17a to 17e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 7 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 17a , a catalyst metal island layer 75 is formed on a substrate 70 made of n-type gan (catalyst metal layer forming step). materials such as ni, fe and au that dissolve and take in compound semiconductor materials such as ga, n, in and al and impurity materials such as si and mg, and that are less likely to form compounds with themselves can be used for the catalyst metal layer. to form an island pattern, a catalyst metal layer having a thickness of from about 100 nm to 300 nm is formed on the substrate 70 , and then is patterned in the shape of islands of about 1 μm in diameter, in which semiconductor cores are to be grown, at appropriate intervals by way of a lithography method and dry etching. next, as shown in fig. 17b , on the substrate 70 on which the catalyst metal island layer 75 is formed, a rod-like semiconductor core 71 made of n-type gan is formed by crystal growth of n-type gan from an interface between the catalyst metal island layer 75 and the substrate 70 using a metal organic chemical vapor deposition (mocvd) device (semiconductor core forming step). the growth temperature is set to about 800° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 71 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 70 is the c-axis direction. next, as shown in fig. 17c , with the catalyst metal island layer 75 maintained at the tip of the semiconductor core 71 , a semiconductor layer 72 made of p-type gan is formed through crystal growth from the outer peripheral surface of the semiconductor core 71 and from an interface between the semiconductor core 71 and the catalyst metal island layer 75 such that semiconductor layer 72 covers the semiconductor core 71 (“semiconductor layer forming step”). in the semiconductor layer forming step, the growth temperature is set to about 900° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, as shown in fig. 17d , the outer peripheral surface on the side of the substrate 70 of the semiconductor core 71 is exposed by dry etching (exposing step). at this point, the catalyst metal island layer 75 is removed, and part of the upper end of the semiconductor core 71 is removed. in connection with the semiconductor layer 72 , the thickness in the axial direction of a portion 72 a thereof covering the end surface of an end of the semiconductor core 71 is larger than the thickness in the radial direction of a portion 72 b thereof covering the outer peripheral surface of the end of the semiconductor core 71 . in the exposing step, the use of sicl 4 for reactive ion etching (rie), which is dry etching, allows gan to be anisotropically etched with ease. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 70 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 71 covered with the semiconductor layer 72 so as to bend the root close to the substrate 70 of the semiconductor core 71 that erects on the substrate 70 . as a result, as shown in fig. 17e , the semiconductor core 71 covered with the semiconductor layer 72 is separated from the substrate 70 . in this way, the microscopic rod-like light-emitting device that is separated from the substrate 70 can be manufactured. in embodiment 7, the rod-like light-emitting device has a diameter of 1 μm and a length of 10 μm (in figs. 17a to 17e , the length of the rod-like light-emitting device is drawn shorter for the sake of clarity). moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer occurs radially outward from the outer peripheral surface of the semiconductor core 71 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 71 can be covered with the semiconductor layer 72 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. in the rod-like light-emitting device separated from the substrate 70 in this way, with one electrode connected to an exposed portion 71 a of the semiconductor core 71 and with the other electrode connected to the semiconductor layer 72 , a current is caused to flow between the electrodes to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the semiconductor core 71 and the inner peripheral surface of the semiconductor layer 72 . thus, light is emitted from the pn junction. in the above semiconductor layer forming step, under the condition where the catalyst metal island layer 75 is held at a tip of the semiconductor core 71 without removal of the catalyst metal island layer 75 , the p-type semiconductor layer 72 covering the surface of the semiconductor core 71 is formed. this facilitates crystal growth from an interface between the catalyst metal layer 75 and the semiconductor core 71 rather than that from the outer peripheral surface of the semiconductor core 71 . therefore, the semiconductor layer 72 in which the thickness in the axial direction of the portion 72 a covering the end surface of the other end of the semiconductor core 71 is larger than the thickness in the radial direction of the portion 72 b covering the outer peripheral surface of the semiconductor core 71 can be easily formed. with the fabricating method, a microscopic rod-like light-emitting device having great freedom in installing in an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. note that, before the semiconductor layer forming step to form the semiconductor layer 72 , a quantum well layer may be formed to cover the surface of the semiconductor core 71 , under the condition where the catalyst metal island layer 75 is held at the tip of the semiconductor core 71 without removal of the catalyst metal island layer 75 . thus, a quantum well layer in which the thickness in the axial direction of a portion covering the end surface of the other end of a semiconductor core is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core can be easily formed. the above rod-like light-emitting device of embodiment 7 has effects similar to those of the rod-like light-emitting device of embodiment 5. in the semiconductor layer 72 , the thickness in the axial direction of the portion 72 a covering the end surface of the other end of the semiconductor core 71 is larger than the thickness in the radial direction of the portion 72 b covering the outer peripheral surface of the semiconductor core 71 . as a result, an electrode to be connected to the side of the semiconductor layer 72 covering the end surface of the other end of the semiconductor core 71 can be connected just to the portion 72 a of the semiconductor layer 72 without overlapping up to the position of the end surface of the other end of the semiconductor core 71 . therefore, the light-extraction efficiency of the whole side surface of the semiconductor core 71 can be improved. in the semiconductor layer 72 , the thickness in the axial direction of the portion 72 a covering the end surface of the other end of the semiconductor core 71 is larger than the thickness in the radial direction of the portion 72 b covering the outer peripheral surface of the semiconductor core 71 . therefore, the portion 72 a of the semiconductor layer 72 covering the end surface of the other end of the semiconductor core 71 has a high resistance. as a result, light emitting does not concentrate to the other side of the semiconductor core 71 . this can enhance light emitting in a side surface region of the semiconductor core 71 , and can reduce or eliminate the leakage current in the portion 72 a of the semiconductor layer 72 that covers the end surface of the other end of the semiconductor core 71 . (embodiment 8) figs. 18a to 18d are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 8 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 18a , a semiconductor film 84 made of n-type gan is formed on an underlying substrate 80 , and an catalyst metal island layer 85 is formed on the semiconductor film 84 (catalyst metal layer forming step). materials such as ni, fe and au that dissolve and take in compound semiconductor materials such as ga, n, in and al and impurity materials such as si and mg, and that are less likely to form compounds with themselves can be used for the catalyst metal layer. to form an island pattern, a catalyst metal layer having a thickness of from about 100 nm to 300 nm is formed on the semiconductor film 84 , and then is patterned in the shape of islands of about 1 μm in diameter, in which semiconductor cores are to be grown, at appropriate intervals by way of a lithography method and dry etching. next, as shown in fig. 18b , on the semiconductor film 84 on which the catalyst metal island layer 85 is formed, a rod-like semiconductor core 81 made of n-type gan is formed by crystal growth of n-type gan from an interface between the catalyst metal island layer and the semiconductor film 84 using an mocvd device (“semiconductor core forming step”). the growth temperature is set to about 800° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 81 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the semiconductor film 84 is the c-axis direction. next, as shown in fig. 18c , with the catalyst metal island layer 85 maintained at the tip of the semiconductor core 81 , a semiconductor layer 82 made of p-type gan is formed through crystal growth from the outer peripheral surface of the semiconductor core 81 and from an interface between the semiconductor core 81 and the catalyst metal island layer 85 such that semiconductor layer 82 covers the semiconductor core 81 (“semiconductor layer forming step”). in the semiconductor layer forming step, the growth temperature is set to about 900° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, as shown in fig. 18d , the surface of the underlying substrate 80 and the outer peripheral surface on the side of the underlying substrate 80 of the semiconductor core 81 are exposed by dry etching (“exposing step”). at this point, the catalyst metal island layer 75 is removed, and part of the upper end of the semiconductor core 71 is removed. in connection with the semiconductor layer 72 , the thickness in the axial direction of a portion 72 a thereof covering the end surface of the other end of the semiconductor core 71 is larger than the thickness in the radial direction of a portion 72 b covering the outer peripheral surface of the semiconductor core 71 . in the exposing step, the use of sicl 4 for rie, which is dry etching, allows gan to be anisotropically etched with ease. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 70 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 81 covered with the semiconductor layer 82 so as to bend the root close to the underlying substrate 80 of the semiconductor core 81 that erects on the underlying substrate 80 . as a result, as shown in fig. 18e , the semiconductor core 81 covered with the semiconductor layer 82 is separated from the underlying substrate 80 . in this way, the microscopic rod-like light-emitting device that is separated from the underlying substrate 80 can be manufactured. in embodiment 8, the rod-like light-emitting device has a diameter of 1 μm and a length of 10 μm (in figs. 18a to 18e , the length of the rod-like light-emitting device is drawn shorter for the sake of clarity). moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer occurs radially outward from the outer peripheral surface of the semiconductor core 81 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 81 can be covered with the semiconductor layer 82 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. in the rod-like light-emitting device separated from the underlying substrate 80 in this way, with one electrode connected to an exposed portion 81 a of the semiconductor core 81 and with the other electrode connected to the semiconductor layer 82 , a current is caused to flow between the electrodes to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the semiconductor core 81 and the inner peripheral surface of the semiconductor layer 82 . thus, light is emitted from the pn junction. in the above semiconductor layer forming step, under the condition where the catalyst metal island layer 85 is held at a tip of the semiconductor core 81 without removal of the catalyst metal island layer 85 , the p-type semiconductor layer 82 covering the surface of the semiconductor core 81 is formed. this facilitates crystal growth from an interface between the catalyst metal layer 85 and the semiconductor core 81 rather than that from the outer peripheral surface of the semiconductor core 81 . therefore, the semiconductor layer 82 in which the thickness in the axial direction of the portion 82 a covering the end surface of the other end of the semiconductor core 81 is larger than the thickness in the radial direction of the portion 82 b covering the outer peripheral surface of the semiconductor core 81 can be easily formed. with the fabricating method, a microscopic rod-like light-emitting device having great freedom in installing in an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. the outer peripheral surface of the semiconductor layer 82 and the outer peripheral surface of the exposed portion 81 a of the semiconductor core 81 are continuous with each other without a step. therefore, when the microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon such that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 81 a of the semiconductor core 81 can be reliably and easily connected with the electrode because no step exists between the outer peripheral surface of the semiconductor layer 82 and the outer peripheral surface of the exposed portion 81 a of the semiconductor core 81 . note that, before the semiconductor layer forming step to form the semiconductor layer 82 , a quantum well layer may be formed to cover the surface of the semiconductor core 81 , under the condition where the catalyst metal island layer 85 is held at the tip of the semiconductor core 81 without removal of the catalyst metal island layer 85 . thus, a quantum well layer in which the thickness in the axial direction of a portion covering the end surface of the other end of a semiconductor core is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core can be easily formed. the above rod-like light-emitting device of embodiment 8 has effects similar to those of the rod-like light-emitting device of embodiment 5. in the semiconductor layer 82 , the thickness in the axial direction of the portion 82 a covering the end surface of the other end of the semiconductor core 81 is larger than the thickness in the radial direction of the portion 82 b covering the outer peripheral surface of the semiconductor core 81 . as a result, an electrode to be connected to the side of the semiconductor layer 82 covering the end surface of the other end of the semiconductor core 81 can be connected just to the portion 82 a of the semiconductor layer 82 without overlapping up to the position of the end surface of the other end of the semiconductor core 81 . therefore, the light-extraction efficiency of the whole side surface of the semiconductor core 81 can be improved. in the semiconductor layer 82 , the thickness in the axial direction of the portion 82 a covering the end surface of the other end of the semiconductor core 81 is larger than the thickness in the radial direction of the portion 82 b covering the outer peripheral surface of the semiconductor core 81 . therefore, the portion 82 a of the semiconductor layer 82 covering the end surface of the other end of the semiconductor core 81 has a high resistance. as a result, light emitting does not concentrate to the other side of the semiconductor core 81 . this can enhance light emitting in a side surface region of the semiconductor core 81 , and can reduce or eliminate the leakage current in the portion 82 a of the semiconductor layer 82 that covers the end surface of the other end of the semiconductor core 81 . (embodiment 9) figs. 19a to 19e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 9 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 19a , a mask 94 having a growth hole 94 a is formed on a substrate 90 made of n-type gan. for the mask 94 , a material capable of selectively etching the semiconductor core and the semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), can be used. to form the growth hole 94 a , known lithography and dry etching methods that are used for usual semiconductor processes can be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the growth hole 94 a of the mask 94 . next, an catalyst metal island layer 95 is formed on the substrate 90 exposed through the growth hole 94 a of the mask 94 (catalyst metal layer forming step). materials such as ni, fe and au that dissolve and take in compound semiconductor materials such as ga, n, in and al and impurity materials such as si and mg, and that are less likely to form compounds with themselves can be used for the catalyst metal layer. the catalyst metal island layer 95 on the substrate 90 exposed in the growth hole 94 a is obtained in such a way that, with a resist (not shown) that has been used for the formation of the growth hole 94 a by the lithography and dry etching methods remaining on the mask 94 , a catalyst metal layer having a thickness of from about 100 nm to 300 nm is formed on the resist and the substrate 90 , and the catalyst metal layer on the resist as well as the resist are removed by a lift-off method. next, as shown in fig. 19b , on the substrate 90 on which the catalyst metal island layer 95 is formed, a rod-like semiconductor core 91 made of n-type gan is formed by crystal growth of n-type gan from an interface between the catalyst metal island layer 95 and the substrate 90 using a mocvd device (“semiconductor core forming step”). the growth temperature is set to about 800° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 91 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 90 is the c-axis direction. next, as shown in fig. 19c , with the catalyst metal island layer 95 maintained at the tip of the semiconductor core 91 , a semiconductor layer 92 made of p-type gan is formed through crystal growth from the outer peripheral surface of the semiconductor core 91 and from an interface between the semiconductor core 91 and the catalyst metal island layer 95 such that semiconductor layer 92 covers the semiconductor core 91 (“semiconductor layer forming step”). in the semiconductor layer forming step, the growth temperature is set to about 900° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, as shown in fig. 19d , in an exposing step, all of the region of the semiconductor layer 92 , except for a portion thereof covering the semiconductor core 91 , and the mask 94 (shown in fig. 19c ) are removed by etching to expose the outer peripheral surface on the side of the substrate 90 of the rod-like semiconductor core 91 , which results in formation of an exposed portion 91 a . under this condition, the catalyst metal island layer 95 is removed, and part of the upper end of the semiconductor core 91 is removed. in the semiconductor layer 92 , the thickness in the axial direction of a portion 92 a covering the end surface of the other end of the semiconductor core 91 is larger than the thickness in the radial direction of a portion 92 b covering the outer peripheral surface of the semiconductor core 91 . in the case where a mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. in the exposing step of this embodiment, dry etching using cf 4 and xef 2 enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, so that the semiconductor layer (all of the region of the semiconductor layer except for the portion thereof covering the semiconductor core) on the mask as well as the mask can be removed. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 90 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 91 covered with the semiconductor layer 92 so as to bend the root close to the substrate 90 of the semiconductor core 91 that erects on the substrate 90 . as a result, as shown in fig. 19e , the semiconductor core 91 covered with the semiconductor layer 92 is separated from the substrate 90 . in this way, the microscopic rod-like light-emitting device that is separated from the substrate 90 can be manufactured. in embodiment 9, the rod-like light-emitting device has a diameter of 1 μm and a length of 10 μm (in figs. 19a to 19e , the length of the rod-like light-emitting device is drawn shorter for the sake of clarity). moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer 92 occurs radially outward from the outer peripheral surface of the semiconductor core 91 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 91 can be covered with the semiconductor layer 92 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. in the rod-like light-emitting device separated from the substrate 90 in this way, with one electrode connected to an exposed portion 91 a of the semiconductor core 91 and with the other electrode connected to the semiconductor layer 92 , a current is caused to flow between the electrodes to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the semiconductor core 91 and the inner peripheral surface of the semiconductor layer 92 . thus, light is emitted from the pn junction. in the above semiconductor layer forming step, under the condition where the catalyst metal island layer 95 is held at a tip of the semiconductor core 91 without removal of the catalyst metal island layer 95 , the p-type semiconductor layer 92 covering the surface of the semiconductor core 91 is formed. this facilitates crystal growth from an interface between the catalyst metal layer 95 and the semiconductor core 91 rather than that from the outer peripheral surface of the semiconductor core 91 . therefore, the semiconductor layer 92 in which the thickness in the axial direction of the portion 92 a covering the end surface of the other end of the semiconductor core 91 is larger than the thickness in the radial direction of the portion 92 b covering the outer peripheral surface of the semiconductor core 91 can be easily formed. with this fabricating method, a microscopic rod-like light-emitting device having great freedom in installing in an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductor used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. also because light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer, the light-emitting device is allowed to have an expanded light emitting region. this makes it possible to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and low power consumption. note that, before the semiconductor layer forming step to form the semiconductor layer 92 , a quantum well layer may be formed to cover the surface of the semiconductor core 91 , under the condition where the catalyst metal island layer 95 is held at the tip of the semiconductor core 91 without removal of the catalyst metal island layer 95 . thus, a quantum well layer in which the thickness in the axial direction of a portion covering the end surface of the other end of a semiconductor core is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core can be easily formed. the above rod-like light-emitting device of embodiment 9 has effects similar to those of the rod-like light-emitting device of embodiment 5. in the semiconductor layer 92 , the thickness in the axial direction of the portion 92 a covering the end surface of the other end of the semiconductor core 91 is larger than the thickness in the radial direction of the portion 92 b covering the outer peripheral surface of the semiconductor core 91 . as a result, an electrode to be connected to the side of the semiconductor layer 92 covering the end surface of the other end of the semiconductor core 91 can be connected just to the semiconductor layer 92 without overlapping up to the position of the end surface of the other end of the semiconductor core 91 . therefore, the light-extraction efficiency of the whole side surface of the semiconductor core 91 can be improved. in the semiconductor layer 92 , the thickness in the axial direction of the portion 92 a covering the end surface of the other end of the semiconductor core 91 is larger than the thickness in the radial direction of the portion 92 b covering the outer peripheral surface of the semiconductor core 91 . therefore, the portion 92 a of the semiconductor layer 92 covering the end surface of the other end of the semiconductor core 91 has a high resistance. as a result, light emitting does not concentrate to the other side of the semiconductor core 91 . this can enhance light emitting in a side surface region of the semiconductor core 91 , and can reduce or eliminate the leakage current in the portion 92 a of the semiconductor layer 92 that covers the end surface of the other end of the semiconductor core 91 . note that, in embodiments 1 to 4 described above, descriptions have been given of the rod-like light-emitting devices having the exposed portions 11 , 21 , 31 and in which the outer peripheral surfaces of one end portion of the semiconductor cores 11 , 21 , 31 and 41 are exposed. however, the rod-like light-emitting device is not limited to these cases, and may be that which has, at both ends thereof, exposed portions in which the outer peripheral surface of the semiconductor core are exposed and that which has, at a central portion thereof, an exposed portion in which the outer peripheral surface of the semiconductor core is exposed. in embodiments 1 to 9 described above, semiconductors whose base materials are gan are used for the semiconductor core and the semiconductor layer. however, this invention may be applied to light-emitting devices using semiconductors whose base materials are gaas, algaas, gaasp, ingan, algan, gap, znse, algainp and the like. while the semiconductor core is of n type and the semiconductor layer is of p type, this invention may be applied to a rod-like light-emitting device in which the conductivity types are reversed. the rod-like light-emitting devices having the semiconductor cores with hexagonal prism shapes have been described. however, the rod-like light-emitting device is not limited to this, and may have a rod shape whose cross section has a circle shape or an ellipse shape. this invention may be applied to a rod-like light-emitting device having a semiconductor core in a rod shape whose cross section has the shape of another polygon such as a triangle. in embodiments 1 to 9 described above, the rod-like light-emitting device has a size of the order of micrometers with a diameter of 1 μm and a length of from 10 μm to 30 μm. however, there may be used a device with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the diameter of the semiconductor core of the above rod-like light-emitting device is preferably 500 nm or more and 50 μm or less, which enables variations in diameter of the semiconductor core to be reduced compared to a rod-like light-emitting device having a semiconductor core whose diameter ranges from several tens of nanometers to several hundreds of nanometers. therefore, variations in the light emitting region, that is, variations in light emission characteristics can be decreased. this can lead to improvement in yields. in embodiments 1 to 4 and 7 to 9 described above, crystal growth of a semiconductor core is made using the mocvd device. however, the semiconductor core may be formed using another crystal growth device such as a molecular-beam epitaxy (mbe) device. the crystal growth of the semiconductor core is made on a substrate using a mask having a growth hole. however, metal species are placed on a substrate, and crystal growth of a semiconductor core may result from the metal species. in embodiments 1 to 4 and 7 to 9 described above, the semiconductor core covered with the semiconductor layer is separated from the substrate using ultrasonic waves. however, the way of separation is not limited to this, and the semiconductor core may be separated from the substrate by mechanically bending the semiconductor core with a cutting tool. in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be separated by a simple way for a short time. (embodiment 10) fig. 20 is a cross-sectional view of a rod-like light-emitting device of embodiment 10 of this invention. a rod-like light-emitting device a of embodiment 10, as shown in fig. 20 , includes a semiconductor core 111 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a cap layer 112 covering one end surface of the semiconductor core 111 , and a semiconductor layer 113 made of p-type gan and that covers the outer peripheral surface of a portion other than an exposed portion 111 a of the semiconductor core 111 such that a portion opposite to a portion covered with the cap layer 112 of the semiconductor core 111 is not covered, so that the exposed portion 111 a is provided. the outer peripheral surface of the semiconductor core 111 and the outer peripheral surface of the cap layer 112 are covered with the continuous semiconductor layer 113 . the cap layer 112 mentioned above uses, as a material having a higher electric resistance than the semiconductor layer 113 , for example, an insulating material, intrinsic gan, n-type gan of the same conductivity type as that of the semiconductor layer 113 and with a low impurity concentration, or p-type gan of a conductivity type different from that of the semiconductor layer 113 and with a low impurity concentration. according to the rod-like light-emitting device a having the above configuration, one end surface of the semiconductor core 111 made of n-type gan and shaped like a rod is covered with the cap layer 112 , and the outer peripheral surface of the portion other than the exposed portion 111 a of the semiconductor core 111 is covered with the semiconductor layer 113 made of p-type gan such that the portion opposite to the portion covered with the cap layer 112 of the semiconductor core 111 is not covered, so that the exposed portion 111 a is provided. as a result, even in cases where the rod-like light-emitting device is microscopic and has a size of the order of micrometers or of the order of nanometers, it becomes possible to connect the exposed portion 111 a of the semiconductor core 111 to an n-side electrode and to connect a p-side electrode to a portion the semiconductor layer 113 that covers the semiconductor core 111 . in the rod-like light-emitting device a, with the n-side electrode connected to the exposed portion 111 a of the semiconductor core 111 and with the p-side electrode connected to the semiconductor layer 113 , a current is caused to flow from the p-side electrode to the n-side electrode to result in recombination of electrons and holes in an interface (pn junction) between the outer peripheral surface of the semiconductor core 111 and the inner peripheral surface of the semiconductor layer 113 . thus, light is emitted. in the rod-like light-emitting device a, light is emitted from the whole side surface of the semiconductor core 111 covered with the semiconductor layer 113 . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. accordingly, it is possible to implement the microscopic rod-like light-emitting device a that allows electrode connections to be easily made with a simple configuration and has a high light emitting efficiency. the above rod-like light-emitting device a is not integral with the substrate, which allows great freedom in installing into an apparatus. the microscopic rod-like light-emitting device as used herein is a device, for example, in micrometer order size with a diameter of 1 μm and a length in the range of from 10 μm to 30 μm, or in nanometer order size in which at least the diameter of the diameter and the length of 1 μm or less. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductors used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and achieve low power consumption. the outer peripheral surface of one side of the above semiconductor core 111 is exposed, for example, in the axial direction by about 1 μm to 5 μm. this makes it possible to connect an n-side electrode to the exposed portion 111 a of the outer peripheral surface of the semiconductor core 111 and to connect a p-side electrode to the semiconductor layer 113 on the other side of the semiconductor core 111 . therefore, connections can be made with the electrodes separate from each other in both ends. thus, the p-side electrode connected to the semiconductor layer 113 and the exposed portion 111 a of the semiconductor core 111 can easily be prevented from becoming short-circuited to each other. one end surface of the semiconductor core 111 is covered with the cap layer 112 . this makes it possible to easily connect the p-side electrode to the portion of the semiconductor layer 113 covering the outer peripheral surface of the semiconductor core 111 opposite to the exposed portion 111 a , without short-circuiting the p-side electrode with the semiconductor core 111 . in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device a. fig. 21 is a schematic cross-sectional view of the main part of a rod-like light-emitting device of a comparative example, but not a rod-like light-emitting device of this invention. the rod-like light-emitting device of fig. 21 differs from the above rod-like light-emitting device a shown in fig. 20 of embodiment 10 in that the rod-like light-emitting device has no cap layer that covers one end surface of a semiconductor core 1011 , and a semiconductor layer 1013 covers the outer peripheral surface and the end surface of the semiconductor core 1011 . as shown in fig. 21 , when a p-side electrode 1014 is connected to the semiconductor layer 1013 on the end surface side of the semiconductor core 1011 , the resistance decreases in the film thickness direction (the resistance as seen from the side of the p-side electrode 1014 ), in which the cross-sectional area of the semiconductor layer 1013 covering the end surface side of the semiconductor core 1011 is large, whereas the resistance increases in the longitudinal direction (the resistance as seen from the side of the p-side electrode 1014 ), in which the cross-sectional area of the semiconductor layer 1013 covering the outer peripheral surface of the semiconductor core 1011 is small. for this reason, a current concentrates to the end surface of the semiconductor core 1011 , and light emission concentrates to the end surface of the semiconductor core 1011 . as a result, light is not efficiently emitted from the whole side surface of the semiconductor core 1011 . in contrast, as shown in a schematic cross-sectional view of fig. 22 , in the rod-like light-emitting device shown in fig. 20 of embodiment 10 mentioned above, one end surface of the semiconductor core 111 is covered with the cap layer 112 made of a material having a higher electric resistance than the semiconductor layer 113 . this, on the one hand, prevents a current from flowing between a p-side electrode 114 connected to the side of the cap layer 112 of the semiconductor core 111 and the semiconductor core 111 through the cap layer 112 , and on the other hand, allows a current to flow between the p-side electrode 114 and the outer peripheral surface side of the semiconductor core 111 through the semiconductor layer 113 having a lower resistance than the cap layer 112 . this reduces current concentration to the end surface on the side having the cap layer 112 thereon of the semiconductor core 111 is provided. as a result, without concentration of light emission to the end surface of the semiconductor core 111 , the efficiency of extracting light from the side surface of the semiconductor core 111 is improved. figs. 23a to 23c are cross-sectional views of the main parts of first to third modifications of the above rod-like light-emitting device of embodiment 10. in figs. 23a to 23c , although forms of the semiconductor layer 113 differ from that of fig. 20 , the same elements as those of fig. 20 are denoted by the same reference characters. in the rod-like light-emitting device of this invention, as shown in the first modification of fig. 23a , the semiconductor layer 113 may be formed to cover part on the side of the semiconductor core 111 of the outer peripheral surface of the cap layer 112 . as shown in the second modification of fig. 23b , the semiconductor layer 113 may also be formed to cover all the outer peripheral surface of the cap layer 112 and to protrude farther than the end surface of the cap layer 112 , and, as a result, the end surface of the cap layer 112 is exposed. further, in the rod-like light-emitting device of this invention, as shown in the third modification of fig. 23c , the semiconductor layer 113 may be formed to cover all the outer peripheral surface of the cap layer 112 and to cover the end surface of the cap layer 112 . fig. 24 and fig. 25 are schematic cross-sectional views of the main parts of the rod-like light-emitting devices of modifications in which the outer peripheral surface of a cap layer is not covered with a semiconductor layer. in fig. 24 and fig. 25 , reference characters 1021 and 1031 denote semiconductor cores, 1022 and 1032 denote cap layers, 1023 and 1033 denote semiconductor layers, and 1024 and 1034 denote p-side electrodes; materials used for elements are the same as those used for elements of the above rod-like light-emitting device of embodiment 10. in the rod-like light-emitting device of the modification shown in fig. 24 , just a little region near the semiconductor core 1021 of the outer peripheral surface of the cap layer 1022 is covered with the semiconductor layer 1023 , and therefore a current path might be formed in this portion to allow a leakage current to flow between the p-side electrode 1024 and the semiconductor core 1021 through the current path. also, in the rod-like light-emitting device of the modification shown in fig. 25 , the outer peripheral surface of the cap layer 1032 is not covered with the semiconductor layer 1033 , and therefore a current path might be formed in a portion where the end surface of the semiconductor layer 1033 comes in contact with the end surface of the cap layer 1032 to allow a leakage current to flow between the p-side electrode 1034 and the semiconductor core 1031 through this current path. in contrast, according to the above rod-like light-emitting device a shown in fig. 20 of embodiment 10, the outer peripheral surface of the semiconductor core 111 excepting the exposed portion 111 a and the outer peripheral surface of the cap layer 112 are covered with the continuous semiconductor layer 113 , which makes it possible to eliminate or reduce occurrence of a leakage current between the p-side electrode 14 connected to the side of the cap layer 112 of the semiconductor core 111 and the semiconductor core 111 . in the above rod-like light-emitting device a, the use of an insulating material for the cap layer 112 causes the semiconductor core 111 to be completely insulated from the electrode with the cap layer 112 , and therefore light emission from the end surface on the side on which the cap layer 112 of the semiconductor core 111 is provided can be reduced, and the occurrence of a leakage current between the semiconductor core 111 and the electrode can be eliminated or reduced in the vicinity of the end surface of the semiconductor core 111 . in the above rod-like light-emitting device a, in cases where an intrinsic semiconductor is used for the cap layer 112 , the semiconductor core 111 is completely insulated from the electrode with the cap layer 112 , and therefore light emission from the end surface on the side having the cap layer 112 thereon of the semiconductor core 111 can be reduced, and the occurrence of a leakage current between the semiconductor core 111 and the electrode can be eliminated or reduced in the vicinity of the end surface of the semiconductor core 111 . for example, in the case of using gan as the intrinsic semiconductor, an n-type semiconductor containing an impurity is actually obtained. however, the impurity concentration is low, and the resistance is high. therefore, little current flows on the side of the cap layer 112 , which enables a sufficient voltage to be applied between the semiconductor core 111 and the semiconductor layer 113 that covers the outer peripheral surface of the semiconductor core 111 . in the above rod-like light-emitting device a, in cases where the same n-type semiconductor as that used for the semiconductor core 111 is used for the cap layer 112 , the cap layer 112 has a higher resistance than the semiconductor layer 113 , and therefore light emission from the end surface on the side having the cap layer 112 thereon of the semiconductor core 111 can be reduced, and the occurrence of a leakage current between the semiconductor core 111 and the electrode can be eliminated or reduced in the vicinity of the end surface of the semiconductor core 111 . in the above rod-like light-emitting device a, in cases where the same p-type semiconductor as that used for the semiconductor layer 113 is used for the cap layer 112 , a light-emitting surface is formed in the end surface having the cap layer 112 thereon of the semiconductor core 111 , and therefore the light emitting region can be increased. the cap layer 112 has a higher resistance than the semiconductor layer, and therefore a little current flows on the side of the cap layer 112 , which enables a sufficient voltage to be applied between the semiconductor core 111 and the semiconductor layer 113 that covers the outer peripheral surface of the semiconductor core 111 . note that, in embodiment 10 described above, a description has been given of the rod-like light-emitting device in which the semiconductor core 111 having a rod shape whose cross section is nearly hexagonal is covered with the semiconductor layer. however, this invention may be applied to a rod-like light-emitting device in which, for example, a semiconductor core shaped like a rod having the shape of a circle or another polygon is covered with a semiconductor layer, a quantum well layer and the like. n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of approximately a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate is the c-axis direction. depending on growth conditions such as a growth direction and a growth temperature, the shape of the cross section tends to be nearly circular in cases where the semiconductor core to be grown has a small diameter in the range of from several tens of nanometers to several hundreds of nanometers. in cases where the diameter is large in the range of from about 0.5 μm to several micrometers, it becomes easier to grow the semiconductor core whose cross section is nearly hexagonal. (embodiment 11) fig. 26 is a cross-sectional view of a rod-like light-emitting device of embodiment 11 of this invention. a rod-like light-emitting device of this embodiment 11 has the same configuration as the rod-like light-emitting device of embodiment 10, except for the quantum well layer. a rod-like light-emitting device b of embodiment 11, as shown in fig. 26 , includes a semiconductor core 121 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 125 that is made of p-type ingan and that covers one end surface of the semiconductor core 121 , a cap layer 122 that covers the outer peripheral surface of the quantum well layer 125 , and a semiconductor layer 123 that is made of p-type gan and that covers the outer peripheral surface of a portion other than an exposed portion 121 a of the semiconductor core 121 such that a portion opposite to the portion covered with the cap layer 122 of the semiconductor core 121 is not covered, so that the exposed portion 121 a is provided. the outer peripheral surface of the semiconductor core 121 and the outer peripheral surface of the cap layer 122 are covered with the continuous semiconductor layer 123 . the above rod-like light-emitting device of embodiment 11 has effects similar to those of the rod-like light-emitting device of embodiment 10. in the above rod-like light-emitting device of embodiment 11, the quantum well layer 125 made of p-type ingan is formed between the end surface of the semiconductor core 121 and the cap layer 122 . as a result, due to quantum confinement effects of the quantum well layer 125 , the light emitting efficiency at an interface between the end surface of the semiconductor core 121 and the cap layer 122 can be improved. note that the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. (embodiment 12) fig. 27 is a cross-sectional view of a rod-like light-emitting device of embodiment 12 of this invention. a rod-like light-emitting device c of embodiment 12, as shown in fig. 27 , includes a semiconductor core 131 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a cap layer 132 that covers one end surface of the semiconductor core 131 , a quantum well layer 133 that is made of p-type ingan and that covers the outer peripheral surface of a portion other than an exposed portion 131 a of the semiconductor core 131 such that a portion opposite to the portion covered with the cap layer 132 of the semiconductor core 131 is not covered, so that the exposed portion 131 a is provided, and a semiconductor layer 134 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 133 . the outer peripheral surface of the above semiconductor core 131 and the outer peripheral surface of the cap layer 132 are covered with the quantum well layer 133 and the semiconductor layer 134 that are continuous with each other. the cap layer 132 mentioned above uses, as a material having a higher electric resistance than the semiconductor layer 134 , for example, an insulating material, intrinsic gan, n-type gan of the same conductivity type as that of the semiconductor layer 134 and with a low impurity concentration, or p-type gan of a conductivity type different from that of the semiconductor layer 134 and with a low impurity concentration. fig. 28 is a cross-sectional view of the main part of the above rod-like light-emitting device c. as shown in fig. 28 , in the above rod-like light-emitting device c of embodiment 12, one end surface of the semiconductor core 131 is covered with the cap layer 132 made of a material having a higher electric resistance than the semiconductor layer 134 . this prevents a current from flowing between a p-side electrode 135 connected to the side of the cap layer 132 of the semiconductor core 131 and the semiconductor core 131 through the cap layer 132 and, on the other hand, allows a current to flow between the p-side electrode 135 and the outer peripheral surface side of the semiconductor core 131 through the semiconductor layer 134 having a lower resistance than the cap layer 132 . this reduces current concentration to the end surface on the side having the cap layer 132 thereon of the semiconductor core 131 is provided. as a result, without concentration of light emission to the end surface of the semiconductor core 131 , the efficiency of extracting light from the side surface of the semiconductor core 131 is improved. note that, as shown in fig. 28 , in the configuration case in which the semiconductor layer 134 covering the cap layer 132 does not reach the end surface of the cap layer 132 , occurrence of a leakage current from the p-side electrode 135 to the semiconductor core 131 in the plane direction of the quantum well layer 133 is predicted. however, the resistance of the quantum well layer 133 is sufficiently large (the film thickness being small, and the distance from the p-side electrode 135 to the semiconductor core 131 being sufficiently long), and therefore the occurrence of a leakage current is extremely rare. this allows a sufficient voltage to be applied between the semiconductor core 131 and the semiconductor layer 134 . here, the distance from the p-side electrode 135 to the semiconductor core 131 in the quantum well layer 133 approximately corresponds to, for example, the length of from 1 μm to 5 μm of the cap layer 132 . the above rod-like light-emitting device of embodiment 12 has effects similar to those of the rod-like light-emitting device of embodiment 10. figs. 29a to 29c are cross-sectional views of the main parts of the first to third modifications of the above rod-like light-emitting device of embodiment 12. in figs. 29a to 29c , although forms of the quantum well layer 133 and the semiconductor layer 134 differ from those of fig. 27 , the same elements as those of fig. 27 are denoted by the same reference characters. in the rod-like light-emitting device of this invention, as shown in the first modification of fig. 29a , the quantum well layer 133 and the semiconductor layer 134 may be formed to cover part on the side of the semiconductor core 131 of the outer peripheral surface of the cap layer 132 . as shown in the second modification of fig. 29b , the quantum well layer 133 and the semiconductor layer 134 may also be formed to cover all the outer peripheral surface of the cap layer 132 and to protrude farther than the end surface of the cap layer 132 , so that the end surface of the cap layer 132 is exposed. further, in the rod-like light-emitting device of this invention, as shown in the third modification of fig. 29c , the quantum well layer 133 and the semiconductor layer 134 may be formed to cover all the outer peripheral surface of the cap layer 132 and to cover the end surface of the cap layer 132 . fig. 30 and fig. 31 are schematic cross-sectional views of the main parts of rod-like light-emitting devices of modifications in which the outer peripheral surface of a cap layer is not covered with a quantum well layer and a semiconductor layer. in fig. 30 and fig. 31 , reference characters 1041 and 1151 denote semiconductor cores, 1042 and 1152 denote cap layers, 1043 and 1153 denote quantum well layers, 1044 and 1154 denote semiconductor layers, and 1045 and 1155 denote p-side electrodes; materials used for elements are the same as those used for elements of the above rod-like light-emitting device of embodiment 12. in the rod-like light-emitting device of the modification shown in fig. 30 , just a little region near the semiconductor core 1041 of the outer peripheral surface of the cap layer 1042 is covered with the quantum well layer 1043 and the semiconductor layer 1044 , and therefore a current path might be formed in this portion to allow a leakage current to flow between the p-side electrode 1045 and the semiconductor core 1041 through this current path. also, in the rod-like light-emitting device of the modification shown in fig. 31 , the outer peripheral surface of the cap layer 1152 is not covered with the semiconductor layer 1154 , and therefore a current path might be formed in a portion where the end surface of the semiconductor layer 1154 comes in contact with the end surface of the cap layer 1152 to allow a leakage current to flow between the p-side electrode 1155 and the semiconductor core 1151 through this current path. in contrast, according to the above rod-like light-emitting device shown in fig. 27 of embodiment 12, the outer peripheral surface of the semiconductor core 131 excepting the exposed portion 131 a and the outer peripheral surface of the cap layer 132 are covered with the continuous semiconductor layer 134 , which makes it possible to eliminate or reduce occurrence of a leakage current to the semiconductor core 131 from the p-side electrode 135 connected to the side of the cap layer 132 of the semiconductor core 131 . in the above rod-like light-emitting device of embodiment 12, the quantum well layer 133 is formed between the outer peripheral surface of the semiconductor core 131 and the semiconductor layer 134 . as a result, due to quantum confinement effects of the quantum well layer 133 , the light emitting efficiency at an interface between the outer peripheral surface of the semiconductor core 131 and the semiconductor layer 134 can be improved. note that the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. according to the above rod-like light-emitting device, the outer peripheral surface of the semiconductor core 131 excepting the exposed portion 131 a and the outer peripheral surface of the cap layer 132 are covered with the continuous quantum well layer 133 , which makes it possible to eliminate or reduce occurrence of a leakage current between an electrode connected to the side of the cap layer 132 of the semiconductor core 131 and the semiconductor core 131 . (embodiment 13) fig. 32 is a cross-sectional view of a rod-like light-emitting device of embodiment 13 of this invention. the rod-like light-emitting device of this embodiment 13 has the same configuration as the rod-like light-emitting device of embodiment 12, except for a conductive layer. a rod-like light-emitting device d of embodiment 13, as shown in fig. 32 , includes a semiconductor core 141 made of n-type gan and having a rod shape whose cross section is nearly hexagonal; a cap layer 142 that covers one end surface of the semiconductor core 141 ; a quantum well layer 143 that is made of p-type ingan and that covers the outer peripheral surface of a portion other than an exposed portion 141 a of the semiconductor core 141 so as not to cover a portion opposite to the portion on the side of the semiconductor core 141 covered with the cap layer 142 , so that the exposed portion 141 a is provided; a semiconductor layer 144 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 143 ; and a conductive layer 145 that covers the outer peripheral surface of the semiconductor layer 144 . the outer peripheral surface of the above semiconductor core 141 and the outer peripheral surface of the cap layer 142 are covered with the quantum well layer 143 and the semiconductor layer 144 that are continuous with each other. the conductive layer 145 is formed of ito having a film thickness of 200 nm. for the deposition of ito, a vapor-deposition method or a sputtering method can be used. after the ito film is deposited, heat treatment is performed at a temperature of from 500° c. to 600° c., which makes it possible to decrease the contact resistance between the semiconductor layer 144 made of p-type gan and the conductive layer 145 made of ito. note that the conductive layer 145 is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used for the conductive layer 145 . for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. fig. 33 is a schematic cross-sectional view of the main part of the rod-like light-emitting device d. as shown in fig. 33 , in the rod-like light-emitting device d of this embodiment 13, one end surface of the semiconductor core 141 is covered with the cap layer 142 made of a material having a higher electric resistance than the semiconductor layer 144 . this prevents a current from flowing between a p-side electrode 146 connected to the side of the cap layer 142 of the semiconductor core 141 and the semiconductor core 141 through the cap layer 142 and, on the other hand, allows a current to flow between the p-side electrode 146 and the outer peripheral surface side of the semiconductor core 141 through the semiconductor layer 144 having a lower electric resistance than the cap layer 142 . this reduces current concentration to the end surface on the side having the cap layer 142 thereon of the semiconductor core 141 is provided. as a result, without concentration of light emission to the end surface of the semiconductor core 141 , the efficiency of extracting light from the side surface of the semiconductor core 141 is improved. the above rod-like light-emitting device of embodiment 13 has effects similar to those of the rod-like light-emitting device of embodiment 10. according to the above rod-like light-emitting device, the semiconductor layer 144 is connected through the conductive layer 145 , which has a lower resistance than the semiconductor layer 144 , to the electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that light can be efficiently emitted from the whole side surface of the semiconductor core 141 . thus, the light emitting efficiency is further improved. in the above rod-like light-emitting device, as shown in fig. 34 , an n-side electrode 147 as one example of the first electrode is connected to the exposed portion 141 a of the semiconductor core 141 , and a p-side electrode 148 as one example of the second electrode is connected to the side on which the cap layer 142 of the semiconductor core 141 is provided. in fig. 34 , one end surface of the semiconductor core 141 is not exposed owing to the cap layer 142 , and, through the semiconductor layer 144 and the conductive layer 145 , an electric connection between the semiconductor core 141 and the p-side electrode 148 can be easily made. this makes it possible to minimize the area of the side surface shielded with the p-side electrode 148 of the whole side surface of the semiconductor core 141 covered with the semiconductor layer 144 and the conductive layer 145 , which enables the light-extraction efficiency to be improved. this also eliminates or reduces current concentration to the end surface on the side having the cap layer 142 thereon of the semiconductor core 141 . as a result, without concentration of light emission to the end surface of the semiconductor core 141 , the efficiency of extracting light from the side surface of the semiconductor core 141 is improved. note that the semiconductor core 141 and the p-side electrode 148 may be electrically connected only through the conductive layer 145 in an end on the side of the cap layer 142 of the semiconductor core 141 . (embodiment 14) fig. 35 is a perspective view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 14 of this invention. in this embodiment 14, a rod-like light-emitting device having the same configuration as the rod-like light-emitting device c of embodiment 12 is used. note that, as the rod-like light-emitting device, any one of the above rod-like light-emitting devices of embodiments 1, 11 and 13 may be used. the light-emitting apparatus of this embodiment 14, as shown in fig. 35 , includes an insulating substrate 100 having metal electrodes 101 and 102 formed on a mounting surface thereof, and a rod-like light-emitting device e mounted on the insulating substrate 100 such that the longitudinal direction of the rod-like light-emitting device e is parallel to the mounting surface of the insulating substrate 100 . the rod-like light-emitting device e includes a semiconductor core 151 made of n-type gan and having a rod shape whose cross section is nearly hexagonal; a cap layer (not shown) that covers one end surface of the semiconductor core 151 ; a quantum well layer 153 that is made of p-type ingan and that covers the outer peripheral surface of a portion other than an exposed portion 151 a of the semiconductor core 151 so as not to cover a portion opposite to the side of a portion of the semiconductor core 151 covered with the cap layer 152 , so that the exposed portion 151 a is provided; and a semiconductor layer 154 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 153 . the semiconductor core 151 has, at one end thereof, an exposed portion 151 a in which the outer peripheral surface of the semiconductor core 151 is exposed. the end surface of the cap layer on the other side of the semiconductor core 151 is exposed without being covered with the quantum well layer 153 and the semiconductor layer 154 . as shown in fig. 35 , the exposed portion 151 a at one end of the rod-like light-emitting device e is connected to the metal electrode 101 , and the semiconductor layer 154 at the other end of the rod-like light-emitting device e is connected to the metal electrode 102 . here, in the rod-like light-emitting device e, its central portion is deformed to come in contact with the insulating substrate 100 . this deformation is caused by stiction that occurs when a droplet contracts in a clearance between the substrate surface and the rod-like light-emitting device because of vaporization during drying of an ipa aqueous solution in a method of aligning the rod-like light-emitting devices of embodiment 38 to be described later. according to the above light-emitting apparatus of the embodiment 14, in the rod-like light-emitting device e mounted on the insulating substrate 100 such that the longitudinal direction of the rod-like light-emitting device e is parallel to the mounting surface of the insulating substrate 100 , the outer peripheral surface of the semiconductor layer 154 comes in contact with the mounting surface of the insulating substrate 100 , and therefore heat generated in the rod-like light-emitting device e can be dissipated with a good efficiency from the semiconductor layer 154 to the insulating substrate 100 . accordingly, it is possible to implement the light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. note that, in a rod-like light-emitting device in which a conductive layer is formed to cover a semiconductor layer, the outer peripheral surface of the conductive layer comes in contact with a mounting surface of an insulating substrate, and thus the effects can be obtained similarly. in the above light-emitting apparatus, the rod-like light-emitting device e is arranged to lie on its side on the insulating substrate 100 . this allows the whole thickness of the rod-like light-emitting device e including the insulating substrate 100 to be decreased. in the above light-emitting apparatus, the microscopic rod-like light-emitting device e, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm is used. the use of the microscopic rod-like light-emitting device e enables the amount of semiconductors used to be decreased. using this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. (embodiment 15) fig. 36 is a side view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 15 of this invention. the light-emitting apparatus of this embodiment 15, as shown in fig. 36 , includes the insulating substrate 100 , a rod-like light-emitting device f mounted on the insulating substrate 100 such that the longitudinal direction of the rod-like light-emitting device f is parallel to the mounting surface of the insulating substrate 100 . the rod-like light-emitting device f includes a semiconductor core 161 made of n-type gan and having a rod shape whose cross section is nearly hexagonal; a cap layer 162 (shown in fig. 37 ) that covers one end surface of the semiconductor core 161 ; a quantum well layer 163 that is made of p-type ingan and that covers the outer peripheral surface of a portion other than an exposed portion 161 a of the semiconductor core 161 so as not to cover a portion opposite to the portion covered with the cap layer 162 of the semiconductor core 161 , so that the exposed portion 161 a is provided; a semiconductor layer 164 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 163 ; and a conductive layer 165 that covers the outer peripheral surface of the semiconductor layer 164 . the semiconductor core 161 has, at one end thereof, an exposed portion 161 a in which the outer peripheral surface of the semiconductor core 161 is exposed. a metal layer 166 as one example of the second conductive layer is formed on an insulating substrate 100 side portion of the conductive layer 165 . about the lower half of the outer peripheral surface of the conductive layer 165 is covered with the metal layer 166 . the conductive layer 165 is formed of ito. note that the conductive layer is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used. for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. the material used for the metal layer 166 is not limited to al, and cu, w, ag, au and the like may be used. the light-emitting apparatus of this embodiment 15, as shown in fig. 37 , includes the insulating substrate 100 having the metal electrodes 101 and 102 formed on the mounting surface thereof, and the rod-like light-emitting device f mounted on the insulating substrate 100 such that the longitudinal direction of the rod-like light-emitting device f is parallel to the mounting surface of the insulating substrate 100 . the exposed portion 161 a at one end of the rod-like light-emitting device f is connected to the metal electrode 101 by means of an adhesive joint 103 of a conductive adhesive or the like, and the metal layer 166 on the other end of the rod-like light-emitting device f is connected to the metal electrode 102 by means of an adhesive joint 104 of a conductive adhesive or the like. here, in the rod-like light-emitting device f, its central portion is deformed to come in contact with the insulating substrate 100 . this deformation is caused by stiction that occurs when a droplet contracts in a clearance between the substrate surface and the rod-like light-emitting device because of vaporization during drying of an ipa aqueous solution in a method of aligning the rod-like light-emitting devices of embodiment 38 to be described later. according to the above light-emitting apparatus of embodiment 15, the metal layer 166 , as one example of the second conductive layer, having a lower resistance than the semiconductor layer 164 is formed on the conductive layer 165 of the rod-like light-emitting device f and on the side of the insulating substrate 100 . on a side without the metal layer 166 , which is opposite to the side of the insulating substrate 100 of the rod-like light-emitting device f, the conductive layer 165 exists with which the outer peripheral surface of the semiconductor core 161 is covered. therefore, a lower resistance can be achieved by the metal layer 166 without sacrificing the ease of flow of a current to the whole semiconductor layer 164 having a high resistance. for the conductive layer 165 covering the outer peripheral surface of the semiconductor core 161 , a material having a low transmittance cannot be used in consideration of the light emitting efficiency, and therefore a material having a low resistance cannot be used. however, for the metal layer 166 , a conductive material for which a low resistance has precedence over the transmittance can be used. moreover, in the rod-like light-emitting device f mounted on the insulating substrate 100 such that the longitudinal direction of the rod-like light-emitting device f is parallel to the mounting surface of the insulating substrate 100 , the metal layer 166 comes in contact with the mounting surface of the insulating substrate 100 . therefore, heat generated in the rod-like light-emitting device f can be dissipated with a good efficiency through the metal layer 166 to the insulating substrate 100 . (embodiment 16) fig. 38 is a perspective view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 16 of this invention. in this embodiment 16, a rod-like light-emitting device having the same configuration as the rod-like light-emitting device c of embodiment 12 is used. note that, as the rod-like light-emitting device, any one of the above rod-like light-emitting devices of embodiments 10, 11 and 13 may be used. the light-emitting apparatus of this embodiment 16, as shown in fig. 38 , includes an insulating substrate 200 having metal electrodes 201 and 202 formed on a mounting surface thereof, and a rod-like light-emitting device g mounted on the insulating substrate 200 such that the longitudinal direction of the rod-like light-emitting device g is parallel to the mounting surface of the insulating substrate 200 . on the insulating substrate 200 , a third metal electrode 203 , as one example of the metal portion, is formed between the metal electrodes 201 and 202 on the insulating substrate 200 and below the rod-like light-emitting device g. in fig. 38 , only parts of the metal electrodes 201 , 202 and 203 are shown. the rod-like light-emitting device g includes a semiconductor core 171 made of n-type gan and having a rod shape whose cross section is nearly hexagonal; a cap layer (not shown) that covers one end surface of the semiconductor core 171 ; a quantum well layer 173 that is made of p-type ingan and that covers the outer peripheral surface of a portion other than an exposed portion 171 a of the semiconductor core 171 so as not to cover a portion opposite to the portion covered with the cap layer of the semiconductor core 171 , so that the exposed portion 171 a is provided; and a semiconductor layer 174 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 173 . the semiconductor core 171 has, at one end thereof, an exposed portion 171 a in which the outer peripheral surface of the semiconductor core 171 is exposed. the end surface of the cap layer on the other side of the semiconductor core 171 is exposed without being covered with the quantum well layer 173 and the semiconductor layer 174 . according to the above light-emitting apparatus of embodiment 16, the metal electrode 203 is formed between the electrodes 201 and 202 on the insulating substrate 200 and below the rod-like light-emitting device g, so that the central side of the rod-like light-emitting device g whose both ends are connected to the metal electrodes 201 and 202 is supported by bringing the central side into contact with the surface of the metal electrode 203 . as a result, the rod-like light-emitting device g, which is connected at both ends, is supported by the metal electrode 203 , without being deformed, and heat generated in the rod-like light-emitting device g can be dissipated with a good efficiency from the semiconductor layer 174 through the metal electrode 203 to the insulating substrate 200 . note that, as shown in fig. 39 , the metal electrodes 201 and 202 include base portions 201 a and 202 a that are nearly parallel to each other with a predetermined spacing therebetween, and pluralities of electrode portions 201 b and 202 b extending between the base portions 201 a and 202 a from positions facing each other in the base portions 201 a and 202 a , respectively. one rod-like light-emitting device g is aligned at the electrode portion 201 b of the metal electrode 201 and the electrode portion 202 b of the metal electrode 202 opposite thereto. between the electrode portion 201 b of the metal electrode 201 and the electrode portion 202 b of the metal electrode 202 opposite thereto, the third metal electrode 203 in the shape of a butterfly whose central portion is narrow is formed on the insulating substrate 200 . the third metal electrodes 203 adjacent to each other are electrically separated. as shown in fig. 39 , even in cases where the orientations of the rod-like light-emitting devices g adjacent to each other are reversed, the metal electrode 201 and the metal electrode 202 can be prevented from becoming short-circuited to each other through the metal electrode 203 . (embodiment 17) figs. 40a to 40d are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 17 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 40a , a mask (not shown) having a growth hole is formed on a substrate 300 made of n-type gan. a material capable of selectively etching a semiconductor core and a semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), can be used for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the above growth hole of the mask. next, in a semiconductor core forming step, a rod-like semiconductor core 301 is formed on the substrate 300 exposed through the growth hole of the mask by crystal growth of n-type gan using a metal organic chemical vapor deposition (mocvd) device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 301 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 300 is the c-axis direction. then, after the semiconductor core forming step, tmg and nh 3 are used as growth gases, and cp 2 mg is used for p-type impurity supply. thus, a cap layer 302 made of p-type gan is formed on the semiconductor core 301 . the cap layer 302 is adjusted so as to have a low impurity concentration by controlling the ratio of gases supplied, so that the cap layer 302 has a higher electric resistance than a semiconductor layer to be formed next. next, as shown in fig. 40b , in a quantum well layer and semiconductor layer forming step, a quantum well layer 303 made of p-type ingan is formed over the whole surface of the substrate 300 such that the rod-like semiconductor core 301 and the cap layer 302 are covered with the quantum well layer 303 , and further a semiconductor layer 304 is formed over the whole surface of the substrate 300 . after the semiconductor core of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 303 can be formed on the semiconductor core 301 of n-type gan and the cap layer 302 . thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 304 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer. also, the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. next, as shown in fig. 40c , in an exposing step, all of the regions of the quantum well layer 303 and the semiconductor layer 304 except for portions thereof covering the semiconductor core 301 is removed by dry etching so as to expose the outer peripheral surface on the side of the substrate 300 of the rod-like semiconductor core 301 , so that an exposed portion 301 a is formed, and an upper part of the cap layer 302 is etched to expose the end surface of the cap layer 302 a . in this case, use of sicl 4 for rie of dry etching allows gan to be anisotropically etched with ease. here, the outer peripheral surface of a semiconductor layer 304 a and the outer peripheral surface of an exposed portion 301 a of the semiconductor core 301 are continuous with each other without a step (no step also exists between the exposed portion of the outer peripheral surface of the quantum well layer 303 a and the outer peripheral surface of the exposed portion 301 a of the semiconductor core 301 ). thus, when a microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 301 a of the semiconductor core 301 can be reliably and easily connected with the electrode because no step exists between the outer peripheral surface of the semiconductor layer 304 a and the outer peripheral surface of the exposed portion 301 a of the semiconductor core 301 . in the above method of manufacturing a rod-like light-emitting device of embodiment 17, switching the impurity gas allows the cap layer 302 to be grown immediately after the growth of the semiconductor core 301 , and therefore the cap layer 302 can be easily formed. in the exposing step shown in fig. 40c , when the substrate 300 is engraved, the upper end of the semiconductor core 301 is not exposed because the cap layer 302 is formed at the edge of the semiconductor core 301 . next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 300 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 301 covered with the quantum well layer 303 a and the semiconductor layer 304 a so as to bend the root close to the substrate 300 of the semiconductor core 301 that erects on the substrate 300 . as a result, as shown in fig. 40d , the semiconductor core 301 covered with the quantum well layer 303 a and the semiconductor layer 304 a is separated from the substrate 300 . in this way, a microscopic rod-like light-emitting device h that is separated from the substrate 300 can be manufactured. in this embodiment 17, the rod-like light-emitting device h has a diameter of 1 μm and a length of 10 μm (in figs. 40a to 40d , the length of the rod-like light-emitting device h is drawn shorter for the sake of clarity). according to the above method of manufacturing a rod-like light-emitting device of embodiment 17, it is possible to implement the microscopic rod-like light-emitting device h that allows electrode connections to be easily made with a simple configuration and that has a high light emitting efficiency. the microscopic rod-like light-emitting device as used herein is a device, for example, in micrometer order size with a diameter of 1 μm and a length in the range of from 10 μm to 30 μm, or in nanometer order size in which at least the diameter of the diameter and the length of 1 μm or less. the above rod-like light-emitting device can decrease the amount of semiconductors used, makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and makes it possible to implement a light-emitting apparatus, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption. according to the above manufacturing method, the rod-like light-emitting device h is not integral with the substrate, and therefore it is possible to manufacture the microscopic rod-like light-emitting device h having great freedom in installing into an apparatus. the above rod-like light-emitting device h can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core covered with the semiconductor layer, which expands the light emitting region. therefore, a light-emitting apparatus, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. (embodiment 18) figs. 41a to 41e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 18 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 41a , a mask 410 having a growth hole 429 a is formed on a substrate 400 made of n-type gan. a material capable of selectively etching a semiconductor core and a semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), can be used for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. at this point, the diameter of a semiconductor core to be grown depends on the size of the above growth hole 429 a of the mask 410 . next, as shown in fig. 41b , in a semiconductor core forming step, a rod-like semiconductor core 401 is formed on the substrate 400 exposed through the growth hole 429 a of the mask 410 by crystal growth of n-type gan using a mocvd device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 401 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core shaped like a rod of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 400 is the c-axis direction. then, after the semiconductor core forming step, tmg and nh 3 are used as growth gases, and cp 2 mg is used for p-type impurity supply. thus, a cap layer 402 made of p-type gan is formed on the semiconductor core 401 . the cap layer 402 is adjusted so as to have a low impurity concentration by controlling the ratio of gases supplied, so that the cap layer 402 has a higher electric resistance than a semiconductor layer to be formed next. next, as shown in fig. 41c , in a quantum well layer and semiconductor layer forming step, a quantum well layer 403 made of p-type ingan is formed over the whole surface of the substrate 400 so as to cover the rod-like semiconductor core 401 and the cap layer 402 , and further a semiconductor layer 404 is formed over the whole surface of the substrate 400 . after the semiconductor core 401 of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 403 can be formed on the semiconductor core 401 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 404 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer. also, the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. next, as shown in fig. 41d , in an exposing step, all of the regions of the quantum well layer 403 and the semiconductor layer 404 , except for portions thereof covering the semiconductor core 401 , and the mask 410 (shown in fig. 41c ) are removed by etching so as to expose the outer peripheral surface on the side of the substrate 400 of the rod-like semiconductor core 401 to form an exposed portion 401 a . in this state, the end surface of the above semiconductor core 401 opposite to the substrate 400 is covered with the quantum well layer 403 a and the semiconductor layer 404 a . in the case where a mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. in the exposing step of this embodiment, dry etching using cf 4 and xef 2 enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, so that all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core, together with the mask can be removed. in the exposing step shown in fig. 41d , even when the quantum well layer 403 and the semiconductor layer 404 on the edge side of the semiconductor core 401 are removed by etching, the upper end of the semiconductor core 401 is not exposed because the cap layer 402 is formed. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 400 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 401 covered with the quantum well layer 403 a and the semiconductor layer 404 a so as to bend the root close to the substrate 400 of the semiconductor core 401 that erects on the substrate 400 . as a result, as shown in fig. 41e , the semiconductor core 401 covered with the quantum well layer 403 a and the semiconductor layer 404 a is separated from the substrate 400 . in this way, a microscopic rod-like light-emitting device i that is separated from the substrate 400 can be manufactured. in this embodiment 18, the rod-like light-emitting device i has a diameter of 1 μm and a length of 10 μm (in figs. 41a to 41e , the length of the rod-like light-emitting device i is drawn shorter for the sake of clarity). according to the above method of manufacturing a rod-like light-emitting device, it is possible to manufacture the microscopic rod-like light-emitting device i having great freedom in installing into an apparatus. the above rod-like light-emitting device can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core 401 , which expands the light emitting region. therefore, it is possible to implement a light-emitting apparatus, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption. (embodiment 19) figs. 42a to 42e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 19 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 42a , a semiconductor film 510 made of n-type gan is formed on an underlying substrate 500 , and a mask (not shown) having a growth hole is formed on the semiconductor film 510 . a material capable of selectively etching a semiconductor core and a semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), can be used for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the above growth hole of the mask. next, in a semiconductor core forming step, a semiconductor core 501 shaped like a rod is formed on the semiconductor film 510 exposed through the growth hole of the mask by crystal growth of n-type gan using a mocvd device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core 501 of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the underlying substrate 500 is the c-axis direction. then, after the semiconductor core forming step, tmg and nh 3 are used as growth gases, and cp 2 mg is used for p-type impurity supply. thus, a cap layer 502 made of p-type gan is formed on the semiconductor core 501 . the cap layer 502 is adjusted so as to have a low impurity concentration by controlling the ratio of gases supplied, so that the cap layer 502 has a higher electric resistance than a semiconductor layer to be formed next. note that the cap layer 502 is not limited to that of p-type gan, and may be made of another insulating material. next, as shown in fig. 42b , in a quantum well layer and semiconductor layer forming step, a quantum well layer 503 made of p-type ingan is formed over the whole surface of the underlying substrate 500 such that the rod-like semiconductor core 501 and the cap layer 502 are covered with the quantum well layer 503 , and further a semiconductor layer 504 is formed over the whole surface of the underlying substrate 500 . after the semiconductor core 501 of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 503 can be formed on the semiconductor core 501 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 504 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer. also, the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. next, as shown in fig. 42c , in an exposing step, all of the regions of the quantum well layer 503 and the semiconductor layer 504 , except for portions thereof covering the semiconductor core 501 , is removed by dry etching so as to expose the outer peripheral surface on the side of the underlying substrate 500 of the rod-like semiconductor core 501 to form an exposed portion 501 a , and an upper part of the cap layer 502 is also etched to expose the end surface of the cap layer 502 a . in this case, use of sicl 4 for rie of dry etching allows gan to be anisotropically etched with ease. here, the outer peripheral surface of a semiconductor layer 504 a and the outer peripheral surface of an exposed portion 501 a of the semiconductor core 501 are continuous with each other without a step (no step also exists between an exposed portion of the outer peripheral surface of the quantum well layer 503 a and the outer peripheral surface of the exposed portion 501 a of the semiconductor core 501 ). thus, when a microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 501 a of the semiconductor core 501 can be reliably and easily connected with the electrode because no step exists between the outer peripheral surface of the semiconductor layer 504 a and the outer peripheral surface of the exposed portion 501 a of the semiconductor core 501 . in the above method of manufacturing a rod-like light-emitting device of embodiment 19, switching the impurity gas allows the cap layer 502 to be grown immediately after the growth of the semiconductor core 501 , and therefore the cap layer 502 can be easily formed. in the exposing step shown in fig. 42c , when etching is performed until the underlying substrate 500 is exposed, the upper end of the semiconductor core 501 is not exposed because the cap layer 502 is formed at the edge of the semiconductor core 501 . next, as shown in fig. 42d , the underlying substrate 500 is isotropically etched to engrave the underlying substrate 500 up to the lower side of the semiconductor core 501 such that the diameter of edge of a protrusion 500 a formed in the underlying substrate 500 is less than the diameter of the semiconductor core 501 . next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the underlying substrate 500 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 501 covered with the quantum well layer 503 a and the semiconductor layer 504 a so as to bend the semiconductor core 501 that erects on the protrusion 500 a in the underlying substrate 500 . as a result, as shown in fig. 42e , the semiconductor core 501 covered with the quantum well layer 503 a and the semiconductor layer 504 a is separated from the substrate 500 . in this way, a microscopic rod-like light-emitting device j that is separated from the underlying substrate 500 can be manufactured. in embodiment 19, the rod-like light-emitting device j has a diameter of 1 μm and a length of 10 μm (in figs. 42a to 42e , the length of the rod-like light-emitting device j is drawn shorter for the sake of clarity). according to the above method of manufacturing a rod-like light-emitting device of embodiment 19, it is possible to implement the microscopic rod-like light-emitting device j that allows electrode connections to be easily made with a simple configuration and has a high light emitting efficiency. according to the above method of manufacturing a rod-like light-emitting device, it is possible to manufacture the microscopic rod-like light-emitting device j having great freedom in installing into an apparatus. the above rod-like light-emitting device j can decrease the amount of semiconductors used to make it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and emits light from the whole periphery of the semiconductor core covered with the semiconductor layer, which expands the light emitting region. therefore, a light-emitting apparatus, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. according to the above method of manufacturing a rod-like light-emitting device, when the semiconductor core 501 is separated from the substrate 500 , the position at which the semiconductor core 501 is broken is stable. this makes it possible to form rod-like light-emitting devices that are uniform in length. in embodiments 10 to 19 described above, semiconductors whose base materials are gan are used for the semiconductor core, the cap layer and the semiconductor layer. however, this invention may be applied to light-emitting devices using semiconductors whose base materials are gaas, algaas, gaasp, ingan, algan, gap, znse, algainp and the like. while the semiconductor core is of n type and the semiconductor layer is of p type, this invention may be applied to a rod-like light-emitting device in which the conductivity types are reversed. the rod-like light-emitting devices having the semiconductor cores with hexagonal prism shapes have been described. however, the rod-like light-emitting device is not limited to this, and may have a rod shape whose cross section has a circle shape or an ellipse shape. this invention may be applied to a rod-like light-emitting device having a semiconductor core in a rod shape whose cross section has the shape of another polygon such as a triangle. in embodiments 10 to 19 described above, the rod-like light-emitting device has a size of the order of micrometers with a diameter of 1 μm and a length of from 10 μm to 30 μm. however, there may be used a device with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the diameter of the semiconductor core of the above rod-like light-emitting device is preferably 500 nm or more and 100 μm or less, which enables variations in diameter of the semiconductor core to be reduced compared to a rod-like light-emitting device having a semiconductor core whose diameter ranges from several tens of nanometers to several hundreds of nanometers. therefore, variations in the light emitting region, that is, variations in light emission characteristics can be decreased. this can lead to improvement in yields. in embodiments 17 to 19 described above, crystal growth of the semiconductor cores 301 , 401 and 501 and the cap layers 302 , 402 and 502 are made using the mocvd device. however, the semiconductor core and the cap layer may be formed using another crystal growth device, such as a molecular-beam epitaxy (mbe) device. the crystal growth of the semiconductor core is made on a substrate using a mask having a growth hole. however, metal species are placed on a substrate, and crystal growth of a semiconductor core may result from the metal species. in embodiments 17 to 19 described above, the semiconductor cores 301 , 401 and 501 are separated from the substrate using ultrasonic waves. however, the way of separation is not limited to this, and the semiconductor core may be separated from the substrate by mechanically bending the semiconductor core with a cutting tool. in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be separated by a simple way for a short time. (embodiment 20) fig. 43 is a perspective view of a rod-like light-emitting device of embodiment 20 of this invention, and fig. 44 is a cross-sectional view of the rod-like light-emitting device. a rod-like light-emitting device a 2 of this embodiment 20, as shown in fig. 43 and fig. 44 , includes a semiconductor core 211 made of n-type gan and having a rod shape whose cross section is nearly circular, and a semiconductor layer 212 that is made of p-type gan and that covers a covered portion 211 b other than an end portion of the semiconductor core 211 such that the end portion not covered with the semiconductor layer 212 of the semiconductor core 211 provides an exposed portion 211 a . in the semiconductor core 211 , the exposed portion 211 a has a smaller diameter than the covered portion 211 b , and a step or riser portion 211 c is provided between the outer peripheral surface of the exposed portion 211 a and the outer peripheral surface of the covered portion 211 b . the end surface of the other end of the semiconductor core 211 is covered with the semiconductor layer 212 . the above rod-like light-emitting device a 2 is manufactured as follows. first, a mask having a growth hole is formed on a substrate made of n-type gan. silicon oxide (sio 2 ), silicon nitride (si 3 n 4 ) or another material that is selectively etchable with respect to the semiconductor core 211 and the semiconductor layer 212 is used as the material for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. next, a catalyst metal layer is formed on a substrate exposed through a growth hole of the mask. this catalyst metal layer is formed in such a way that, with a resist that has been used at the time of forming the growth hole by way of a lithography method and a dry etching method remaining on the mask, a catalyst metal layer having a thickness of from about 200 nm to 400 nm is deposited on the resist and the substrate exposed from the growth hole (exposed region within the growth hole), and the catalyst metal layer on the resist as well as the resist are removed by a lift-off method. for the catalyst metal layer, materials, such as ni, fe and au, can be used. these materials dissolve and take in compound semiconductor materials of ga, n, in, al and the like, and impurity materials of si, mg and the like, and do not form compounds with themselves. next, on the substrate on which the catalyst metal layer is formed in the growth hole of the mask, the rod-like semiconductor core 211 is formed by crystal growth of n-type gan from an interface between the catalyst metal layer and the substrate using a metal organic chemical vapor deposition (mocvd) device. the temperature of the mocvd device is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 3 ) for n-type impurity supply and further hydrogen (h 3 ) as a carrier gas are supplied, so that a semiconductor core of n-type gan with si used as the impurity can be grown. during the growing, when the semiconductor core 211 is being grown in the growth hole of the mask, the diameter of the semiconductor core 211 to be grown is determined depending on the internal diameter of the growth hole because the diameter of the catalyst metal layer does not extend beyond the internal diameter of the growth hole. however, after the diameter of the semiconductor core 211 being grown exceeds the height of the mask (the depth of the growth hole), the diameter of the semiconductor core 211 can be determined depending on the diameter of the catalyst metal layer that coagulates in the shape of an island. accordingly, in the case of forming the catalyst metal layer in the above thickness, when the height of the semiconductor core 211 being grown exceeds the height of the mask (the depth of the growth hole), the catalyst metal layer coagulates in the shape of an island with a diameter larger than the inner diameter of the growth hole. therefore, the covered portion 211 b of the semiconductor core 211 can be grown with a diameter larger than the diameter of the exposed portion 211 a of the semiconductor core 211 in the growth hole. next, with the catalyst metal island layer maintained at the edge of the semiconductor core 211 , a semiconductor layer made of p-type gan is formed over the whole surface of the substrate to cover the rod-like semiconductor core 211 . the temperature of the mocvd device is set to about 960° c., tmg and nh 3 are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, the above catalyst metal island layer is removed, and all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core, and the mask are removed by a lift-off method to expose the outer peripheral surface on the substrate side of the rod-like semiconductor core 211 , so that an exposed portion is formed. in this state, the end surface of the above semiconductor core 211 opposite to the substrate is covered with the semiconductor layer 212 , and the exposed portion 211 a having a smaller diameter than the covered portion 211 b of the semiconductor core 211 is formed. in the case where the mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion that covers the semiconductor core, and enables all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core, together with the mask to be removed by lift-off. in this embodiment, the length of the exposed portion 211 a of the semiconductor core 211 is determined depending on the thickness of the removed mask. the lift-off is used in the exposing step of this embodiment; however, part of the semiconductor core may be exposed by etching. next, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 211 covered with the semiconductor layer 212 so as to bend the root close to the substrate of the semiconductor core 211 that erects on the substrate. as a result, the semiconductor core 211 covered with the semiconductor layer 212 is separated from the substrate. in this way, the microscopic rod-like light-emitting device that is separated from the substrate made of n-type gan can be manufactured. the above semiconductor core is separated from the substrate using ultrasonic waves. however, the way of separation is not limited to this, and the semiconductor core may be separated from the substrate by mechanically bending the semiconductor core with a cutting tool. in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be separated by a simple way for a short time. moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer 212 occurs radially outward from the outer peripheral surface of the semiconductor core 211 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 211 can be covered with the semiconductor layer 212 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. according to the rod-like light-emitting device a 2 having the above configuration, the covered portion 211 b other than the exposed portion 211 a of the semiconductor core 211 is covered with the p-type semiconductor layer 212 so as not to cover one end of the n-type semiconductor core 211 shaped like a rod, so that the exposed portion 211 a is provided. as a result, even in cases where the rod-like light-emitting device is microscopic and has a size of the order of micrometers or of the order of nanometers, it becomes possible to connect the exposed portion 211 a of the semiconductor core 211 to an n-side electrode and to connect a p-side electrode to a portion of the semiconductor layer 212 that covers the semiconductor core 211 . in the rod-like light-emitting device a 2 , with the n-side electrode connected to the exposed portion 211 a of the semiconductor core 211 and with the p-side electrode connected to the semiconductor layer 212 , a current is caused to flow from the p-side electrode to the n-side electrode to result in recombination of electrons and holes in an interface (pn junction) between the outer peripheral surface of the semiconductor core 211 and the inner peripheral surface of the semiconductor layer 212 . thus, light is emitted. in the rod-like light-emitting device a 2 , light is emitted from the whole side surface of the semiconductor core 211 covered with the semiconductor layer 212 . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. accordingly, it is possible to implement the microscopic rod-like light-emitting device a 2 that allows electrode connections to be easily made with a simple configuration and has a high light emitting efficiency. the above rod-like light-emitting device a 2 is not integral with the substrate, which allows great freedom in installing into an apparatus. the microscopic rod-like light-emitting device as used herein is a device, for example, in micrometer order size with a diameter of 1 μm and a length in the range of from 10 μm to 30 μm, or in nanometer order size in which at least the diameter of the diameter and the length of 1 μm or less. the above rod-like light-emitting device can decrease the amount of semiconductors used, makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and makes it possible to implement a light-emitting apparatus, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption. the outer peripheral surface of one end portion of the above semiconductor core 211 is exposed, for example, by about 1 μm to 5 μm. this makes it possible to connect one n-side electrode to the exposed portion 211 a of the outer peripheral surface of the semiconductor core 211 and to connect the p-side electrode to the semiconductor layer 212 on the other end portion of the semiconductor core 211 . connections can be made with the electrodes separate at both ends. thus, the p-side electrode connected to the semiconductor layer 212 and the exposed portion 211 a of the semiconductor core 211 can easily be prevented from being short-circuited to each other. fig. 45 is a schematic cross-sectional view of the main part of a rod-like light-emitting device of a comparative example, but not a rod-like light-emitting device of this invention. the rod-like light-emitting device of fig. 45 differs from the above rod-like light-emitting device a 2 shown in fig. 43 and fig. 44 of embodiment 20 in that no step, or no level difference, exists between the outer peripheral surface of an exposed portion of a semiconductor core 1211 and a covered portion covered with a semiconductor layer 1212 of the semiconductor core 1211 . in this rod-like light-emitting device, in the case where an n-side electrode is connected to the exposed portion of the semiconductor core 1211 , because there exists no step portion, i.e., no difference in level, a distance l between an n-side electrode 1213 and the end surface of the semiconductor layer 1212 becomes shorter. as a result, there might be short-circuiting and a leakage current between the n-side electrode 1213 and the semiconductor layer 1212 . in this rod-like light-emitting device, as shown in fig. 45 , light with a large angle of incidence from the inside of the semiconductor core 1211 to the outer peripheral surface of the exposed portion is reflected from the inside of the semiconductor core 1211 and therefore extracting the light to the outside is difficult. in contrast, as shown in a schematic cross-sectional view of fig. 46 , in the above rod-like light-emitting device shown in fig. 43 and fig. 44 of embodiment 20, as shown in fig. 46 , a step or riser portion (i.e., level difference) 211 c is provided between the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 , which is not covered with the semiconductor layer 212 , and the outer peripheral surface of a covered portion of the semiconductor core 211 , which is covered with the semiconductor layer 212 . therefore, compared to the comparative example of fig. 45 in which the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 is coincident, or flush, with the outer peripheral surface of the covered portion 211 b such that there exists no step, the position of the end surface of the semiconductor layer 212 is determined depending on the step portion 211 c formed at the boundary between the exposed portion 211 a of the semiconductor core 211 and the semiconductor layer 212 . this can reduce or eliminate variations of the boundary position during manufacturing. in the case where, as the comparative example of fig. 45 , the outer peripheral surface of an exposed portion of a semiconductor core is coincident with the outer peripheral surface of a covered portion such that there exists no step, a clearance might be produced between the inner wall of a growth hole of a mask and the semiconductor core during growth of the semiconductor core. when a semiconductor layer is formed subsequently, the semiconductor layer can be formed in the clearance region between the inner wall of the growth hole of the mask and the semiconductor core. as a result, the boundary between the exposed portion of the semiconductor core and the covered portion, which is originally defined at the position of the top surface of the mask, can vary. in contrast, in the case where, as embodiment 20 shown in fig. 46 , a step exists between the outer peripheral surface of an exposed portion of a semiconductor core and the outer peripheral surface of a covered portion, the semiconductor core is grown with a diameter larger than the internal diameter of a growth hole after the height of the semiconductor core exceeds the height of a mask during manufacturing. therefore, if a clearance is produced between the inner wall of the growth hole of the mask and the semiconductor core, the semiconductor core is grown so as to close the clearance. thus, during formation of a semiconductor layer, the semiconductor layer can be prevented from being formed in a clearance region between the inner wall of the growth hole of the mask and the semiconductor core. in fig. 46 , the distance in the longitudinal direction between the n-side electrode 213 and the end surface of the semiconductor layer 212 is the same as the comparative case; however, the distance expands in the radial direction by the length of the step portion 211 c. the step portion 211 c provided between the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 and the outer peripheral surface of the covered portion 211 b allows the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 and the semiconductor layer 212 to be more distant from each other. therefore, when the n-side electrode is connected to the exposed portion 211 a of the semiconductor core 211 , short-circuiting and occurrence of a leakage current between the n-side electrode and the semiconductor layer 212 can be eliminated or reduced. moreover, it becomes easier to extract light to the outside from the step portion 211 c formed at the boundary between the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 and the outer peripheral surface of the covered portion 211 b , and therefore the light-extraction efficiency is improved. fig. 47 is a cross-sectional view of the main part of a modification of the above rod-like light-emitting device of embodiment 20. in a rod-like light-emitting device of this modification, an exposed portion 215 a of the semiconductor core 215 is larger in diameter than a covered portion 215 b , and a step portion 215 c is provided between the outer peripheral surface of the exposed portion 215 a and the outer peripheral surface of the covered portion 215 b . an n-side electrode 217 is connected to the exposed portion 215 a of the semiconductor core 215 . as shown in fig. 47 , the step portion 215 c is formed at the boundary between the outer peripheral surface of the exposed portion 215 a of the semiconductor core 215 and the outer peripheral surface of the covered portion 215 b , and therefore the efficiency of extracting light to the outside is improved. in the semiconductor core 215 , the diameter of the exposed portion 215 a is larger than that of the covered portion 215 b . this allows a large contact surface with the n-side electrode 217 connected to the exposed portion 215 a of the semiconductor core 215 to be taken. therefore, the contact resistance can be decreased. according to the above rod-like light-emitting device a 2 of embodiment 20, the perimeter of a cross section perpendicular to the longitudinal direction of the exposed portion 211 a of the semiconductor core 211 is made shorter than the perimeter of a cross section perpendicular to the longitudinal direction of the covered portion 211 b of the semiconductor core 211 , that is, the exposed portion 211 a has a smaller diameter than the covered portion 211 b of the semiconductor core 211 . therefore, in the manufacturing process, the exposed portion 211 a of the semiconductor core 211 formed so as to erect on the substrate is provided on the substrate side. as a result, the semiconductor core 211 becomes more likely to be broken, which facilitates manufacturing. as has already been described, the semiconductor core 211 is separated from the substrate by vibrating the semiconductor core 211 in ipa using ultrasonic waves. the exposed portion 211 a of the semiconductor core 211 is thin, which facilitates the separation. the exposed portion 211 a of the semiconductor core 211 is low in height relative to the step portion 211 c (the semiconductor layer 212 is high). this can increase the distance between the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 and the semiconductor layer 212 . therefore, when the n-side electrode is connected to the exposed portion 211 a of the semiconductor core 211 , short-circuiting and occurrence of a leakage current between the n-side electrode and the semiconductor layer 212 can be eliminated or reduced. note that the cross sections of the exposed portion 211 a and the covered portion 211 b of the semiconductor core 211 are not limited to being circular, and may have other polygonal shapes, such as hexagons. the cross sections of the exposed portion and the covered portion of the semiconductor core may have different shapes. such cross sections have the same effects if the exposed portion 211 a of the semiconductor core 211 has a smaller diameter than the covered portion 211 b. the cross section perpendicular to the longitudinal direction of the exposed portion 211 a of the semiconductor core 211 is nearly circular. therefore, the shape of a mask pattern for use in growth of the semiconductor core 211 in manufacturing processes may be a circle, limits of a mask layout aligned with the crystal orientation in the plane direction of the substrate are not imposed, and the alignment accuracy for aligning orientations is not required. consequently, manufacturing can be facilitated. fig. 48 is a cross-sectional view of the main part for illustration of an electrode connection of the exposed portion of the semiconductor core of the above rod-like light-emitting device a 2 . the rod-like light-emitting device a 2 is mounted on a substrate 210 such that the longitudinal direction of the device a 2 is parallel to a mounting surface, and the exposed portion 211 a of the semiconductor core 211 is connected to an n-side electrode 214 formed on the substrate 210 . as shown in fig. 48 , in the covered portion 211 b covered with the semiconductor layer 212 of the semiconductor core 211 , the outer shape of the exposed portion 211 a of the semiconductor core 211 is smaller than the outer shape of the semiconductor layer 212 . therefore, when the rod-like light-emitting device is mounted on the substrate 210 such that the longitudinal direction of the device is parallel to the plane of the substrate, contact between the outer peripheral surface of the semiconductor layer 212 and the substrate 210 becomes more likely to be made, which improves the heat dissipation efficiency. in other words, the exposed portion 211 a of the semiconductor core 211 is thin and therefore can be deformed. the deformed exposed portion 211 a is excellently connected to the n-side electrode 214 . therefore, the covered portion 211 b covered with the semiconductor layer 212 of the semiconductor core 211 can be brought into intimate contact with the substrate 210 , without deformation of the covered portion 211 b . thus, the rod-like light-emitting device is excellent in heat dissipation. on the other hand, in the case where the outer peripheral surface of the exposed portion 211 a of the semiconductor core 211 is coincident with the outer peripheral surface of the covered portion 211 b covered with the semiconductor layer 212 , or in the case where the outer shape of the exposed portion 211 a of the semiconductor core 211 is larger than the outer shape of the covered portion 211 b covered with the semiconductor layer 212 , the exposed portion 211 a of the semiconductor core 211 is less likely to be deformed. therefore, at the time when the exposed portion 211 a of the semiconductor core 211 is connected to the n-side electrode 214 , the covered portion 211 b covered with the semiconductor layer 212 of the semiconductor core 211 is deformed not to be brought into intimate contact with the substrate 210 . this deteriorates the heat dissipation. note that, in embodiment 20 described above, a description has been given of the rod-like light-emitting device a 2 in which the semiconductor core 211 having a rod shape whose cross section is nearly circular is covered with the semiconductor layer 212 . however, this invention may be applied to a rod-like light-emitting device in which, for example, a semiconductor core shaped like a rod of a hexagon or another polygon is covered with a semiconductor layer, a quantum well layer and the like. n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of approximately a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate is the c-axis direction. depending on growth conditions such as a growth direction and a growth temperature, the shape of the cross section tends to be nearly circular in cases where the semiconductor core to be grown has a small diameter in the range of from several tens of nanometers to several hundreds of nanometers. in cases where the diameter is large in the range of from about 0.5 μm to several micrometers, it becomes easier to grow the semiconductor core whose cross section is nearly hexagonal. (embodiment 21) fig. 49 is a perspective view of a rod-like light-emitting device of embodiment 21 of this invention. a rod-like light-emitting device b 2 of this embodiment 21, as shown in fig. 49 , includes a semiconductor core 221 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, and a semiconductor layer 222 that is made of p-type gan and that covers a covered portion 221 b other than an end portion of the semiconductor core 221 such that the end portion not covered with the semiconductor layer 222 of the semiconductor core 221 provides an exposed portion 221 a . in the semiconductor core 221 , the exposed portion 221 a has a smaller diameter than the covered portion 221 b , and a step portion 221 c is provided between the outer peripheral surface of the exposed portion 221 a and the outer peripheral surface of the covered portion 221 b . the end surface of the other end of the semiconductor core 221 is covered with the semiconductor layer 222 . the rod-like light-emitting device b 2 is manufactured in a similar method to that for the rod-like light-emitting device a 2 of embodiment 20. fig. 50 is a schematic cross-sectional view of the main part of the above rod-like light-emitting device of embodiment 21, and, in fig. 50 , reference character 223 denotes an n-side electrode. the rod-like light-emitting device b 2 of this embodiment 21 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. according to the above rod-like light-emitting device b 2 of embodiment 21, the cross section perpendicular to the longitudinal direction of the covered portion 221 b of the semiconductor core 221 is hexagonal. therefore, when this rod-like light-emitting device is mounted on the substrate such that the longitudinal direction of the device is parallel to the plane of the substrate, a contact surface between any outer peripheral surface of the semiconductor layer and the substrate can be easily produced. as a result, the efficiency of heat dissipation to the substrate is improved. accordingly, it can be eliminated or reduced for the temperature of the device to increase during light emission to decrease the light emitting efficiency. fig. 51a is a schematic cross-sectional view of the exposed portion of the semiconductor core of the above rod-like light-emitting device a 2 of embodiment 20, and fig. 51b is a schematic cross-sectional view of the exposed portion of the semiconductor core of the above rod-like light-emitting device b 2 of embodiment 21. fig. 51c is a schematic cross-sectional view of an exposed portion of a semiconductor core of a rod-like light-emitting device of a modification. in the rod-like light-emitting device of this modification, the cross section perpendicular to the longitudinal direction of the exposed portion 224 a of the semiconductor core 224 has the shape of an equilateral triangle. as such, a polygonal cross section (e.g., a regular hexagon shown in fig. 51b and an equilateral triangle shown in fig. 51c ) perpendicular to the longitudinal direction of the exposed portion of the semiconductor core can improve the light-extraction efficiency more than a circular cross section shown in fig. 51a can. the reason for this is that in the case where the cross section of the exposed portion of the semiconductor core has the shape of a polygon, in which the number of vertices is small, light is more likely to be emitted to the outside than in the case of a circular cross section. (embodiment 22) fig. 52 is a perspective view of a rod-like light-emitting device of embodiment 22 of this invention. a rod-like light-emitting device c 2 of this embodiment 22, as shown in fig. 52 , includes a semiconductor core 231 made of n-type gan and shaped like a rod, and a semiconductor layer 232 that is made of p-type gan and that covers a covered portion 231 b other than an end portion of the semiconductor core 231 such that the end portion not covered with the semiconductor layer 232 of the semiconductor core 231 provides an exposed portion 231 a . in the exposed portion 231 a of the semiconductor core 231 , the cross section perpendicular to the longitudinal direction is nearly rectangular. in the covered portion 231 b of the semiconductor core 231 , the cross section perpendicular to the longitudinal direction is nearly hexagonal. a step portion 231 c is provided between the outer peripheral surface of the exposed portion 231 a of the semiconductor core 231 and the outer peripheral surface of the covered portion 231 b . the end surface of the other end of the semiconductor core 231 is covered with the semiconductor layer 232 . the rod-like light-emitting device c 2 , except for the covered portion of the semiconductor core, is manufactured in a similar method to that for the rod-like light-emitting device a 2 of embodiment 20. here, regarding the shape of the exposed portion 231 a of the semiconductor core 231 , as described above, before the height of the semiconductor core 231 being grown exceeds the height of the growth hole of the above-mentioned mask, the diameter and the shape of the semiconductor core 231 to be grown are determined depending on the diameter and the shape of the growth hole, and after the height of the semiconductor core 231 being grown exceeds the height of the mask, the diameter and the shape of the semiconductor core 231 to be grown are determined depending on the diameter of the catalyst metal layer that coagulates in the shape of an island. in this embodiment 22, a rectangular growth hole is used. the rod-like light-emitting device c 2 of this embodiment 22 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. fig. 53 is a schematic cross-sectional view of a first modification of the above rod-like light-emitting device of embodiment 22. in the first modification, a semiconductor core 1231 has an exposed portion 1231 a whose cross section perpendicular to the longitudinal direction thereof is nearly circular, and has a covered portion 1231 b whose cross section perpendicular to the longitudinal direction thereof is nearly hexagonal. in the semiconductor core 1231 , the cross-sectional shape of the exposed portion 1231 a is larger than the cross-sectional shape of the covered portion 1231 b . in the semiconductor core 1231 , a step portion 1231 c is provided between the outer peripheral surface of the exposed portion 1231 a and the outer peripheral surface of the covered portion 1231 b. fig. 54 is a schematic cross-sectional view of a second modification of the above rod-like light-emitting device of embodiment 22. in the second modification, a semiconductor core 1241 has an exposed portion 1241 a whose cross section perpendicular to the longitudinal direction thereof is nearly circular, and has a covered portion 1241 b whose cross section perpendicular to the longitudinal direction thereof is nearly hexagonal. the perimeter of the cross section perpendicular to the longitudinal direction of the exposed portion 1241 a of the semiconductor core 1241 is shorter than the perimeter of the cross section perpendicular to the longitudinal direction of the covered portion 1241 b of the semiconductor core 1241 . that is, the cross-sectional shape of the exposed portion 1241 a of the semiconductor core 1241 is smaller than the cross-sectional shape of the covered portion 1241 b . in the semiconductor core 1241 , a step portion 1241 c is provided between the outer peripheral surface of the exposed portion 1241 a and the outer peripheral surface of the covered portion 1241 b. as such, in the rod-like light-emitting devices shown in figs. 52 to 54 , the shapes of cross sections perpendicular to the longitudinal directions of the exposed portions 231 a , 1231 a and 1241 a of the semiconductor cores 231 , 1231 and 1241 differ from the shapes of cross sections perpendicular to the longitudinal directions of the covered portions 231 b , 1231 b and 1241 b of the semiconductor cores 231 , 1231 and 1241 , respectively. as a result, the step portions 231 c , 1231 c and 1241 c are formed at boundaries between the outer peripheral surfaces of the exposed portions 231 a , 1231 a and 1241 a of the semiconductor cores 231 , 1231 and 1241 and the outer peripheral surfaces of the covered portions 231 b , 1231 b and 1241 b , respectively. therefore, the efficiency of extracting light to the outside improves. compared to the case where the outer peripheral surface of the exposed portion of the semiconductor core is coincident with the outer peripheral surface of the covered portion such that there exists no step, the positions of the end surfaces of the semiconductor layers 232 , 1232 and 1242 are determined depending on the step portions 231 c , 1231 c and 1241 c formed at the boundaries between the exposed portions 231 a , 1231 a and 1241 a of the semiconductor cores 231 , 1231 and 1241 and the semiconductor layers 232 , 1232 and 1242 . this can eliminate or reduce variations of the boundary position during manufacturing. in the case where the outer peripheral surface of an exposed portion of a semiconductor core is coincident with the outer peripheral surface of a covered portion such that there exists no step, a clearance might be produced between the inner wall of a growth hole of a mask and the semiconductor core during growth of the semiconductor core. when a semiconductor layer is formed subsequently, the semiconductor layer can be formed in the inner wall of the growth hole of the mask and the region of the clearance of the semiconductor core. this sometimes leads to variations of the boundary between the exposed portion of the semiconductor core and the covered portion, which is originally defined at the position of the top surface of the mask. however, in the case where a step exists between the outer peripheral surface of an exposed portion of a semiconductor core and the outer peripheral surface of a covered portion, the semiconductor core is grown with a diameter larger than the internal diameter of a growth hole after the height of the semiconductor core exceeds the height of a mask during manufacturing. therefore, if a clearance is produced between the inner wall of the growth hole of the mask and the semiconductor core, the semiconductor core is grown so as to close the clearance. thus, when a semiconductor layer is formed, the semiconductor layer can be prevented from being formed in a clearance region between the inner wall of the growth hole of the mask and the semiconductor core. (embodiment 23) fig. 55 is a cross-sectional view of a rod-like light-emitting device of embodiment 23 of this invention, and fig. 56 is a perspective view of the rod-like light-emitting device. a rod-like light-emitting device d 2 of this embodiment 23, as shown in fig. 55 and fig. 56 , includes a semiconductor core 241 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, and a semiconductor layer 242 that is made of p-type gan and that covers a covered portion 241 b other than an end portion of the semiconductor core 241 such that the end portion not covered with the semiconductor layer 242 of the semiconductor core 241 provides an exposed portion 241 a . in the semiconductor core 241 , the exposed portion 241 a has a smaller diameter than the covered portion 241 b , and a step portion 241 c is provided between the outer peripheral surface of the exposed portion 241 a and the outer peripheral surface of the covered portion 241 b . the end surface of the other end of the semiconductor core 241 is covered with the semiconductor layer 242 . an insulating layer 243 is formed to cover the step portion 241 c of the semiconductor core 241 and the end surface of a step portion 241 c side of the semiconductor layer 242 , and to cover a step portion 241 c side of the exposed portion 241 a of the semiconductor core 241 . an n-side electrode 244 is connected to the exposed portion 241 a of the semiconductor core 241 . the rod-like light-emitting device d 2 , except for the covered portion of the semiconductor core, is manufactured in a similar method to that for the rod-like light-emitting device a 2 of embodiment 20. here, regarding formation of the insulating layer 243 that covers the step portion 241 c of the semiconductor core 241 and the end surface of the semiconductor layer 242 on the side of the step portion 241 c , and that covers the exposed portion 241 a of the semiconductor core 241 on the side of the step portion 241 c , instead of removing all of the region of the semiconductor layer, except for the portion thereof covering the semiconductor core, and the mask in steps of manufacturing the rod-like light-emitting device a 2 of embodiment 20, first, anisotropic dry etching is performed, and then all of the region of the semiconductor layer, except for the portion thereof covering the semiconductor core, and the mask are etched. at a stage where the mask is etched halfway, the kind of etching is changed to isotropical dry etching and is performed. this enables the mask to partially remain as an insulating layer. in the case where the mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), reactive ion etching (rie) using a chlorine-based gas such as sicl 4 or a fluorine-based gas such as cf 4 or chf 3 can be used for anisotropic dry etching, and etching can be performed by using plasma of a gas containing cf 4 for isotropic dry etching. in this embodiment, the length of the insulating layer 243 is determined depending on the thickness of the mask removed by dry etching. at the time of isotropic dry etching, a gas containing sicl 4 is used, and etching proceeds while forming a protective film of a reaction product on the side wall of the mask. as shown in fig. 55 and fig. 56 , processing can be performed such that the outer peripheral surface of the semiconductor layer 242 is nearly coincident with the outer peripheral surface of the insulating layer 243 . the rod-like light-emitting device d 2 of this embodiment 23 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. in the rod-like light-emitting device d 2 , the outer peripheral surface of the exposed portion 241 a of the semiconductor core 241 is insulated from the semiconductor layer 242 by the insulating layer 243 , and therefore, when the n-side electrode 244 is connected to the exposed portion 241 a of the semiconductor core 241 , short-circuiting and occurrence of a leakage current between the n-side electrode 244 and the semiconductor layer 242 can be eliminated or reduced with reliability. (embodiment 24) fig. 57 is a cross-sectional view of a rod-like light-emitting device of embodiment 24 of this invention, and fig. 58 is a perspective view of the rod-like light-emitting device. a rod-like light-emitting device e 2 of this embodiment 24, as shown in fig. 57 and fig. 58 , includes a semiconductor core 251 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, and a semiconductor layer 252 that is made of p-type gan and that covers a covered portion 251 b other than an end portion of the semiconductor core 251 such that the end portion not covered with the semiconductor layer 252 of the semiconductor core 251 provides an exposed portion 251 a. the exposed portion 251 a of the semiconductor core 251 includes a small diameter portion 251 a - 1 that has a smaller diameter than the covered portion 251 b and that is on the side of a step portion 251 c , and a large diameter portion 251 a - 2 that is in line with the small diameter portion 251 a - 1 and that has a larger diameter than the covered portion 251 b and has the same outer diameter as the semiconductor layer 252 . in the semiconductor core 251 , the small diameter portion 251 a - 1 of the exposed portion 251 a has a smaller diameter than the covered portion 251 b , and the step portion 251 c is provided between the outer peripheral surface of the exposed portion 251 a and the outer peripheral surface of the covered portion 251 b . the end surface of the other end of the semiconductor core 251 is covered with the semiconductor layer 252 . an insulating layer 253 is formed to cover the step portion 251 c of the semiconductor core 251 and the end surface of the semiconductor layer 252 on the side of the step portion 251 c , and to cover the side of the small diameter portion 251 a - 1 of the exposed portion 251 a of the semiconductor core 251 . an n-side electrode 254 is connected to the large diameter portion 251 a - 2 of the exposed portion 251 a of the semiconductor core 251 . the rod-like light-emitting device e 2 , except for the covered portion of the semiconductor core, is manufactured in a method similar to that for the rod-like light-emitting device a 2 of embodiment 20. for the rod-like light-emitting device e 2 , the shape of the exposed portion 251 a of the semiconductor core 251 , which includes the small diameter portion 251 a - 1 that is smaller in diameter than the covered portion 251 b and is on the side of the step portion 251 c and the large diameter portion 251 a - 2 that is in line with the small diameter portion 251 a - 1 , and that is larger in diameter than the covered portion 251 b , and has the same outer diameter as the semiconductor layer 252 , and the insulating layer 253 that covers the step portion 251 c of the semiconductor core 251 and the end surface of the semiconductor layer 252 on the side of the step portion 251 c and that covers the side of the small diameter portion 251 a - 1 of the exposed portion 251 a of the semiconductor core 251 can be formed in the following way. in the steps of manufacturing the rod-like light-emitting device a 2 of embodiment 20, anisotropic dry etching is performed instead of the step of removing all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core, and the mask by lift-off, so that all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core 251 , the mask and even the substrate are etched. the rod-like light-emitting device e 2 of this embodiment 24 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. the rod-like light-emitting device e 2 includes the insulating layer 253 formed to cover the step portion 251 c of the semiconductor core 251 and the end surface on the side of the step portion 251 c of the semiconductor layer 252 and to cover the side of the step portion 251 c of the exposed portion 251 a of the semiconductor core 251 . this allows the outer peripheral surface of the exposed portion 251 a of the semiconductor core 251 to be insulated from the semiconductor layer 252 by the insulating layer 253 . therefore, in the case where the n-side electrode 254 is connected to the exposed portion 251 a of the semiconductor core 251 , short-circuiting and occurrence of a leakage current between the n-side electrode 254 and the semiconductor layer 252 can be eliminated or reduced with reliability. moreover, the large diameter portion 251 a - 2 of the exposed portion 251 a has a larger diameter than the covered portion 251 b of the semiconductor core 251 . this allows a large contact surface with the n-side electrode 254 connected to the exposed portion 251 a of the semiconductor core 251 to be taken. thus, the contact resistance can be decreased. (embodiment 25) fig. 59 is a cross-sectional view of a rod-like light-emitting device of embodiment 25 of this invention. a rod-like light-emitting device f 2 of this embodiment 25, as shown in fig. 59 , includes a semiconductor core 261 shaped like a rod and made of n-type gan, a semiconductor layer 262 made of p-type gan and covering a covered portion 261 b other than an end portion of the semiconductor core 261 such that the end portion not covered with the semiconductor layer 262 of the semiconductor core 261 provides an exposed portion 261 a , and a conductive layer 263 formed to cover the semiconductor layer 262 and made of a material having a lower electric resistance than the semiconductor layer 262 . the cross section perpendicular to the longitudinal direction of the exposed portion 261 a of the semiconductor core 261 is nearly circular, and the cross section perpendicular to the longitudinal direction of the covered portion 261 b of the semiconductor core 261 is nearly hexagonal. in the semiconductor core 261 , the exposed portion 261 a has a smaller diameter than the covered portion 261 b , and a step portion 261 c is provided between the outer peripheral surface of the exposed portion 261 a and the outer peripheral surface of the covered portion 261 b . the end surface of the other end of the semiconductor core 261 is covered with the semiconductor layer 262 . the conductive layer 263 is formed of ito having a film thickness of 200 nm. for the deposition of ito, a vapor-deposition method or a sputtering method can be used. after the ito film is deposited, heat treatment is performed at a temperature of from 500° c. to 600° c., which makes it possible to decrease the contact resistance between the semiconductor layer 262 made of p-type gan and the conductive layer 263 made of ito. note that the conductive layer 263 is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used for the conductive layer 263 . for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. the rod-like light-emitting device f 2 is manufactured in a method similar to that for the rod-like light-emitting device a 2 of embodiment 20. the rod-like light-emitting device f 2 can be formed in the following way. a catalyst metal layer is removed and then the semiconductor layer 262 covering the semiconductor core 261 is formed. further, an ito film as a conductive layer is formed to cover the semiconductor layer 262 , and then all of the region of the ito film, except for a portion thereof covering the semiconductor layer 262 , is removed by isotropic dry etching. subsequently, like embodiment 20, all of the region of the semiconductor layer, except for a portion thereof covering the semiconductor core 261 , and the mask are removed by lift-off. the rod-like light-emitting device f 2 of this embodiment 25 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. according to the above rod-like light-emitting device f 2 of embodiment 25, the cross section perpendicular to the longitudinal direction of the covered portion 261 b of the semiconductor core 261 is hexagonal. therefore, when this rod-like light-emitting device is mounted on the substrate such that the longitudinal direction of the device is parallel to the plane of the substrate, a contact surface between any outer peripheral surface of the semiconductor layer and the substrate can be easily produced. as a result, the efficiency of heat dissipation to the substrate is improved. accordingly, it can be eliminated or reduced for the temperature of the device to increase during light emission to decrease the light emitting efficiency. the shape of the cross section perpendicular to the longitudinal direction of the exposed portion 261 a of the semiconductor core 261 differs from the shape of the cross section perpendicular to the longitudinal direction of the covered portion 261 b of the semiconductor core 261 . as a result, the step portion 261 c is formed at the boundary between the outer peripheral surface of the exposed portion 261 a of the semiconductor core 261 and the outer peripheral surface of the covered portion 261 b . therefore, the efficiency of extracting light to the outside improves. the semiconductor layer 262 is connected through the conductive layer 263 , which is made of a material having a lower electric resistance than the semiconductor layer 262 , to the p-side electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that light can be efficiently emitted from the whole side surface of the semiconductor core 261 . thus, the light emitting efficiency is further improved. (embodiment 26) fig. 60 is a cross-sectional view of a rod-like light-emitting device of embodiment 26 of this invention. a rod-like light-emitting device g 2 of this embodiment 26, as shown in fig. 60 , includes a semiconductor core 271 shaped like a rod and made of n-type gan, a quantum well layer 272 made of p-type ingan and covering a portion other than one end portion of the semiconductor core 271 such that the one end portion of the semiconductor core 271 not covered with the quantum well layer 272 provides an exposed portion 271 a , a semiconductor layer 273 made of p-type gan and covering the outer peripheral surface of the quantum well layer 272 , and a conductive layer 274 formed to cover the semiconductor layer 273 and made of a material having a lower electric resistance than the semiconductor layer 273 . the cross section perpendicular to the longitudinal direction of the exposed portion 271 a of the semiconductor core 271 is nearly circular, and the cross section perpendicular to the longitudinal direction of a covered portion 271 b of the semiconductor core 271 is nearly hexagonal. in the semiconductor core 271 , the exposed portion 271 a has a smaller diameter than the covered portion 271 b , and a step portion 271 c is provided between the outer peripheral surface of the exposed portion 271 a and the outer peripheral surface of the covered portion 271 b . the end surface of the other end of the semiconductor core 271 is covered with the quantum well layer 272 . the conductive layer 274 is formed of ito having a film thickness of 200 nm. for the deposition of ito, a vapor-deposition method or a sputtering method can be used. after the ito film is deposited, heat treatment is performed at a temperature of from 500° c. to 600° c., which makes it possible to decrease the contact resistance between the semiconductor layer 272 made of p-type gan and the conductive layer 274 made of ito. note that the conductive layer 274 is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used for the conductive layer 274 . for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. the rod-like light-emitting device g 2 is manufactured in a method similar to that for the rod-like light-emitting device a 2 of embodiment 20. the rod-like light-emitting device g 2 can be formed in the following way. a catalyst metal layer is removed and then the quantum well layer 272 and the semiconductor layer 273 that cover the semiconductor core 271 are formed. further, an ito film as a conductive layer is formed to cover the semiconductor layer 273 , and subsequently all of the region of the ito film, except for a portion thereof covering the semiconductor layer 273 , is removed by anisotropic dry etching. thereafter, like embodiment 20, all of the regions of the quantum well layer and the semiconductor layer, except for portions thereof covering the semiconductor core, and the mask are removed by lift-off. the rod-like light-emitting device g 2 of this embodiment 26 has effects similar to those of the rod-like light-emitting device a 2 of embodiment 20. according to the above rod-like light-emitting device g 2 of embodiment 26, the cross section perpendicular to the longitudinal direction of the covered portion 271 b of the semiconductor core 271 is hexagonal. therefore, when this rod-like light-emitting device is mounted on the substrate such that the longitudinal direction of the device is parallel to the plane of the substrate, a contact surface between any outer peripheral surface of the semiconductor layer and the substrate can be easily produced. as a result, the efficiency of heat dissipation to the substrate is improved. accordingly, it can be eliminated or reduced for the temperature of the device to increase during light emission to decrease the light emitting efficiency. the shape of the cross section perpendicular to the longitudinal direction of the exposed portion 271 a of the semiconductor core 271 differs from the shape of the cross section perpendicular to the longitudinal direction of the covered portion 271 b of the semiconductor core 271 . as a result, the step portion 271 c is formed at the boundary between the outer peripheral surface of the exposed portion 271 a of the semiconductor core 271 and the outer peripheral surface of the covered portion 271 b . therefore, the efficiency of extracting light to the outside is improved. the semiconductor layer 273 is connected through the conductive layer 274 , which is made of a material having a lower electric resistance than the semiconductor layer 273 , to the p-side electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that light can be efficiently emitted from the whole side surface of the semiconductor core 271 . thus, the light emitting efficiency is further improved. the quantum well layer 272 is formed between the outer peripheral surface of the covered portion 271 b of the semiconductor core 271 and the semiconductor layer 273 . as a result, due to quantum confinement effects of the quantum well layer 272 , the light emitting efficiency can be improved. note that the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. (embodiment 27) fig. 61 is a cross-sectional view of a rod-like light-emitting device of embodiment 27 of this invention. the rod-like light-emitting device of this embodiment 27 has the same configuration as the rod-like light-emitting device of embodiment 26, except for the cap layer. a rod-like light-emitting device h 2 of this embodiment 27, as shown in fig. 61 , includes a semiconductor core 281 having a rod shape whose cross section is nearly hexagonal and made of n-type gan, a cap layer 282 covering one end surface of the semiconductor core 281 , a quantum well layer 283 made of p-type ingan and covering the outer peripheral surface of a covered portion 281 b other than one end portion of the semiconductor core 281 such that the one end portion of the semiconductor core 281 not covered with the quantum well layer 282 provides an exposed portion 281 a , a semiconductor layer 284 made of p-type gan and covering the outer peripheral surface of the quantum well layer 283 , and a conductive layer 285 covering the outer peripheral surface of the semiconductor layer 284 . in the semiconductor core 281 , the exposed portion 281 a has a smaller diameter than the covered portion 281 b , and a step portion 281 c is provided between the outer peripheral surface of the exposed portion 281 a and the outer peripheral surface of the covered portion 281 b . the outer peripheral surface of the above semiconductor core 281 and the outer peripheral surface of the cap layer 282 are covered with the quantum well layer 283 and the semiconductor layer 284 that are continuous with each other. the conductive layer 285 is formed of ito having a film thickness of 200 nm. for the deposition of ito, a vapor-deposition method or a sputtering method can be used. after the ito film is deposited, heat treatment is performed at a temperature of from 500° c. to 600° c., which makes it possible to decrease the contact resistance between the semiconductor layer 284 made of p-type gan and the conductive layer 285 made of ito. note that the conductive layer 285 is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used for the conductive layer 285 . for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. fig. 62 is a schematic cross-sectional view of the main part of the rod-like light-emitting device h 2 . as shown in fig. 62 , in the rod-like light-emitting device h 2 of this embodiment 27, one end surface of the semiconductor core 281 is covered with the cap layer 282 made of a material having a higher electric resistance than the semiconductor layer 284 . this prevents a current from flowing between a p-side electrode 286 connected to the side of the cap layer 282 of the semiconductor core 281 and the semiconductor core 281 through the cap layer 282 and, on the other hand, allows a current to flow between the p-side electrode 286 and the outer peripheral surface side of the semiconductor core 281 through the conductive layer 285 and the semiconductor layer 284 whose electric resistances are lower than that of the cap layer 282 . this reduces current concentration to the end surface on the side having the cap layer 282 thereon of the semiconductor core 281 is provided. as a result, without concentration of light emission to the end surface of the semiconductor core 281 , the efficiency of extracting light from the side surface of the semiconductor core 281 is improved. the above rod-like light-emitting device h 2 of embodiment 27 has effects similar to those of the rod-like light-emitting device of embodiment 26. in the above rod-like light-emitting device, when an n-side electrode (not shown) is connected to the exposed portion 281 a of the semiconductor core 281 , and the p-side electrode 286 is connected to the side having the cap layer 282 thereon of the semiconductor core 281 , one end surface of the semiconductor core 281 is not exposed owing to the cap layer 282 , and, through the semiconductor layer 284 and the conductive layer 285 in the end, an electric connection between the semiconductor core 281 and the p-side electrode 286 can be easily made. this makes it possible to minimize the area of the side surface shielded with the p-side electrode 286 of the whole side surface of the semiconductor core 281 covered with the semiconductor layer 284 and the conductive layer 285 . this makes it possible to improve the light-extraction efficiency. this also eliminates or reduces current concentration to the end surface on the side having the cap layer 282 thereon of the semiconductor core 281 . as a result, without concentration of light emission to the end surface of the semiconductor core 281 , the efficiency of extracting light from the side surface of the semiconductor core 281 is improved. note that, in the end on the side of the cap layer 282 of the semiconductor core 281 , the p-side electrode 286 may be electrically connected only to the conductive layer 285 , but not to the cap layer 282 . (embodiment 28) fig. 63 is a perspective view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 28 of this invention. the light-emitting apparatus of this embodiment 28 , as shown in fig. 63 , includes an insulating substrate 290 having metal electrodes 298 and 299 formed on a mounting surface, and a rod-like light-emitting device i 2 mounted on the insulating substrate 290 such that the longitudinal direction of the rod-like light-emitting device i 2 is parallel to the mounting surface. the rod-like light-emitting device i 2 includes a semiconductor core 291 shaped like a rod and made of n-type gan, a semiconductor layer 292 made of p-type gan and covering a covered portion 291 b other than one end portion 291 a of the semiconductor core 291 such that the one end portion of the semiconductor core 291 not covered with the semiconductor layer 292 provides an exposed portion 291 a. the cross section perpendicular to the longitudinal direction of the exposed portion 291 a of the semiconductor core 291 is nearly circular, and the cross section perpendicular to the longitudinal direction of the covered portion 291 b of the semiconductor core 291 is nearly hexagonal. in the semiconductor core 291 , the exposed portion 291 a has a smaller diameter than the covered portion 291 b , and a step portion 291 c is provided between the outer peripheral surface of the exposed portion 291 a and the outer peripheral surface of the covered portion 291 b. as shown in fig. 63 , the exposed portion 291 a on the one end side of the rod-like light-emitting device is connected to the metal electrode 298 , and the semiconductor layer 292 on the other side of the rod-like light-emitting device i 2 is connected to the metal electrode 299 . here, in the rod-like light-emitting device i 2 , its central portion is deformed to come in contact with the insulating substrate 290 . this deformation is caused by stiction that occurs when a droplet contracts in a clearance between the substrate surface and the rod-like light-emitting device because of vaporization during drying of an ipa aqueous solution in a method of aligning the rod-like light-emitting devices of embodiment 38 to be described later. according to the above light-emitting apparatus of embodiment 28, in the rod-like light-emitting device i 2 mounted on the insulating substrate 290 such that the longitudinal direction of the rod-like light-emitting device i 2 is parallel to the mounting surface of the insulating substrate 290 , the outer peripheral surface of the semiconductor layer 292 and the mounting surface of the insulating substrate 290 are brought into contact with each other. therefore, heat generated in the rod-like light-emitting device i 2 can be dissipated with a good efficiency from the semiconductor layer 292 to the insulating substrate 290 . accordingly, it is possible to implement the light-emitting apparatus in which the light emitting efficiency is high and the heat dissipation is good. note that, in a rod-like light-emitting device in which a conductive layer is formed to cover a semiconductor layer, the outer peripheral surface of the conductive layer and the mounting surface of an insulating substrate are brought into contact with each other, and therefore similar effects are obtained. in the above light-emitting apparatus, the rod-like light-emitting device i 2 is arranged to lie on its side on the insulating substrate 290 . this allows the whole thickness of the rod-like light-emitting device i 2 including the insulating substrate 290 to be decreased. in the above light-emitting apparatus, use of the microscopic rod-like light-emitting device i 2 , for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size of the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm can decrease the amount of semiconductors used. use of this light-emitting apparatus makes it possible to implement a backlight, an illuminating device, a display device and the like whose thicknesses and weights can be reduced. note that, as the rod-like light-emitting device in embodiment 28 described above, any one of the rod-like light-emitting devices of embodiments 20 to 28 may be used. (embodiment 29) fig. 64 is a side view of a light-emitting apparatus including a rod-like light-emitting device of embodiment 29 of this invention. the light-emitting apparatus of this embodiment 29, as shown in fig. 64 , includes an insulating substrate 600 , a rod-like light-emitting device j 2 mounted on the insulating substrate 600 such that the longitudinal direction of the rod-like light-emitting device j 2 is parallel to the mounting surface of the insulating substrate 600 . the rod-like light-emitting device j 2 includes a semiconductor core 601 shaped like a rod and made of n-type gan; a cap layer 602 (shown in fig. 65 ) that covers one end surface of the semiconductor core 601 ; a quantum well layer 603 that is made of p-type ingan and that covers the outer peripheral surface of a covered portion 601 b other than an exposed portion 601 a of the semiconductor core 601 such that a portion opposite to a portion of the semiconductor core 601 covered with the cap layer 602 , so that the exposed portion 601 a is provided; a semiconductor layer 604 that is made of p-type gan and that covers the outer peripheral surface of the quantum well layer 603 ; and a conductive layer 605 that covers the outer peripheral surface of the semiconductor layer 604 . the cross section perpendicular to the longitudinal direction of the exposed portion 601 a of the semiconductor core 601 is nearly circular, and the cross section perpendicular to the longitudinal direction of the covered portion 601 b of the semiconductor core 601 is nearly hexagonal. in the semiconductor core 601 , the exposed portion 601 a has a smaller diameter than the covered portion 601 b , and a step portion 601 c is provided between the outer peripheral surface of the exposed portion 601 a and the outer peripheral surface of the covered portion 601 b. a metal layer 606 as one example of the second conductive layer is formed on the conductive layer 605 and on the side of the insulating substrate 600 . about the lower half of the outer peripheral surface of the conductive layer 605 is covered with the metal layer 606 . the conductive layer 605 is formed of ito. note that the conductive layer is not limited to this, and, for example, a translucent laminated metal film of ag/ni or au/ni having a thickness of 5 nm may be used. for the deposition of the laminated metal film, a vapor-deposition method or a sputtering method can be used. moreover, to further decrease the resistance of the conductive layer, a laminated metal film of ag/ni or au/ni may be deposited on the ito film mentioned above. the material used for the metal layer 606 is not limited to al, and cu, w, ag, au and the like may be used. the light-emitting apparatus of this embodiment 29, as shown in fig. 65 , includes the insulating substrate 600 having metal electrodes 607 and 608 formed on a mounting surface, and the rod-like light-emitting device j 2 that is mounted on the insulating substrate 600 such that the longitudinal direction of the rod-like light-emitting device j 2 is parallel to the mounting surface of the insulating substrate 600 . the exposed portion 601 a of one end of the rod-like light-emitting device j 2 is connected to the metal electrode 607 by means of an adhesive joint 609 a such as a conductive adhesive, and the metal layer 606 at the other end portion of the rod-like light-emitting device j 2 is connected to the metal electrodes 608 by means of an adhesive joint 609 b such as a conductive adhesive. here, in the rod-like light-emitting device j 2 , its central portion is deformed to come in contact with the insulating substrate 600 . this deformation is caused by stiction that occurs when a droplet contracts in a clearance between the substrate surface and the rod-like light-emitting device because of vaporization during drying of an ipa aqueous solution in a method of aligning the rod-like light-emitting devices of embodiment 38 to be described later. according to the above light-emitting apparatus of embodiment 29, the metal layer 606 , as one example of the second conductive layer, made of a material having a lower resistance than the semiconductor layer 604 is formed on the conductive layer 605 of the rod-like light-emitting device j 2 and on the side of the insulating substrate 600 . on a side without the metal layer 606 , which is opposite to the side of the insulating substrate 600 of the rod-like light-emitting device j 2 , the conductive layer 605 covering the outer peripheral surface of the semiconductor core 601 exists. therefore, a lower resistance can be achieved by the metal layer 606 without sacrificing the ease of flow of a current to the whole semiconductor layer 604 having a high resistance. for the conductive layer 605 covering the outer peripheral surface of the semiconductor core 601 , a material having a low transmittance cannot be used in consideration of the light emitting efficiency, and therefore a material having a low resistance cannot be used. however, for the metal layer 606 , a conductive material for which a low resistance has precedence over the transmittance can be used. moreover, in the rod-like light-emitting device j 2 mounted on the insulating substrate 600 such that the longitudinal direction of the rod-like light-emitting device j 2 is parallel to the mounting surface of the insulating substrate 600 , the metal layer 606 is in contact with the mounting surface of the insulating substrate 600 . therefore, heat generated in the rod-like light-emitting device j 2 can be dissipated with a good efficiency through the metal layer 606 to the insulating substrate 600 . (embodiment 30) fig. 66 is a perspective view of a light-emitting apparatus of embodiment 30 of this invention. in this embodiment 30, a rod-like light-emitting device having the same configuration as the rod-like light-emitting device b 2 of embodiment 21 is used. note that, as the rod-like light-emitting device, any one of the above rod-like light-emitting devices of embodiments 20, and 22 to 29 may be used. the light-emitting apparatus of this embodiment 30, as shown in fig. 66 , includes an insulating substrate 700 having metal electrodes 701 and 702 formed on a mounting surface, and a rod-like light-emitting device k 2 mounted on the insulating substrate 700 such that the longitudinal direction of the rod-like light-emitting device k 2 is parallel to the mounting surface of the insulating substrate 700 . on the insulating substrate 700 , a third metal electrode 703 , as one example of the metal portion, is formed between the metal electrodes 701 and 702 on the insulating substrate 700 and below the rod-like light-emitting device k 2 . fig. 66 shows only parts of the metal electrodes 701 , 702 and 703 . the rod-like light-emitting device k 2 includes a semiconductor core 611 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, and a semiconductor layer 612 made of p-type gan and covering the outer peripheral surface of a covered portion 611 b other than one end portion 611 a of the semiconductor core 611 such that the one end portion of the semiconductor core 611 not covered with the semiconductor layer 612 provides an exposed portion 611 a . in the semiconductor core 611 , the exposed portion 611 a has a smaller diameter than the covered portion 611 b , and a step portion 611 c is provided between the outer peripheral surface of the exposed portion 611 a and the outer peripheral surface of the covered portion 611 b . the end surface of the other end of the semiconductor core 611 is covered with the semiconductor layer 612 . according to the above light-emitting apparatus of embodiment 30, the metal electrode 703 is formed between the electrodes 701 and 702 and below the rod-like light-emitting device k 2 on the insulating substrate 700 , so that the central side of the rod-like light-emitting device k 2 whose both ends are connected to the metal electrodes 701 and 702 is supported by bringing the central side into contact with the surface of the metal electrode 703 . as a result, the rod-like light-emitting device k 2 , which is connected at both ends, is supported by the metal electrode 703 , without being deformed, and heat generated in the rod-like light-emitting device k 2 can be dissipated with a good efficiency from the semiconductor layer 612 through the metal electrode 703 to the insulating substrate 700 . note that, as shown in fig. 67 , the metal electrodes 701 and 702 include base portions 701 a and 702 a that are nearly parallel to each other with a predetermined spacing therebetween, and pluralities of electrode portions 701 b and 702 b extending between the base portions 701 a and 702 a from positions facing each other in the base portions 701 a and 702 a , respectively. one rod-like light-emitting device k 2 is aligned with the electrode portion 701 b of the metal electrode 701 and the electrode portion 702 b of the metal electrode 702 opposite thereto. between the electrode portion 701 b of the metal electrode 701 and the electrode portion 702 b of the metal electrode 702 opposite thereto, the third metal electrode 703 in the shape of a butterfly whose central portion is narrow is formed on the insulating substrate 700 . the third metal electrodes 703 adjacent to one another are electrically separated from one another. as shown in fig. 67 , even when the orientations of the rod-like light-emitting devices k 2 adjacent to each other are reversed, the metal electrode 701 and the metal electrode 702 can be prevented from becoming short-circuited to each other through the metal electrode 703 . in embodiments 20 to 30 described above, semiconductors whose base materials are gan are used for the semiconductor core, the cap layer and the semiconductor layer. however, this invention may be applied to light-emitting devices using semiconductors whose base materials are gaas, algaas, gaasp, ingan, algan, gap, znse, algainp and the like. while the semiconductor core is of n type and the semiconductor layer is of p type, this invention may be applied to a rod-like light-emitting device in which the conductivity types are reversed. a description has been given of the rod-like light-emitting device having the semiconductor core shaped like a rod in the shape of a circle or a hexagon. the rod-like light-emitting device is not limited to this, and may have a rod shape whose cross section is elliptical. this invention may be applied to a rod-like light-emitting device having a semiconductor core in a rod shape whose cross section is in the shape of another polygon such as a triangle. in embodiments 20 to 30 described above, the rod-like light-emitting device has a size of the order of micrometers with a diameter of 1 μm and a length of from 10 μm to 30 μm. however, there may be used a device with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 mm. the diameter of the semiconductor core of the above rod-like light-emitting device is preferably 500 nm or more and 100 μm or less, which enables variations in diameter of the semiconductor core to be reduced compared to a rod-like light-emitting device having a semiconductor core whose diameter ranges from several tens of nanometers to several hundreds of nanometers. therefore, variations in the light emitting region, that is, variations in light emission characteristics can be decreased. this can lead to improvement in yields. in embodiments 20 to 30 described above, crystal growth of a semiconductor core is made using the mocvd device. however, the semiconductor core and the cap layer may be formed using another crystal growth device such as a molecular-beam epitaxy (mbe) device. the crystal growth of the semiconductor core is made on a substrate using a mask having a growth hole. however, metal species are placed on a substrate, and crystal growth of a semiconductor core may result from the metal species. (embodiment 31) figs. 68a to 68e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 31 of this invention. in this embodiment, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this. first, as shown in fig. 68a , a mask 812 having a growth hole 812 a is formed on a substrate 811 made of n-type gan. the mask 812 is made of a substance of inhibiting the formation of the semiconductor layer 814 , and covers part of the outer peripheral surface of the semiconductor core 813 , which is a portion to be exposed. after the semiconductor layer forming step, the mask 812 is removed to allow the part of the outer peripheral surface of the semiconductor core 813 to be easily exposed. here, a material that can selectively etch the semiconductor core and the semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), is used as the substance of inhibiting the formation of the semiconductor layer 814 . however, the substance of inhibiting the formation of the semiconductor layer is not limited to this, and may be selected as appropriate in accordance with the composition of the semiconductor layer, and the like. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the above growth hole of the mask. next, as shown in fig. 68b , in a semiconductor core forming step, a rod-like semiconductor core 813 is formed on the substrate 811 exposed through the growth hole 812 a of the mask 812 by crystal growth of n-type gan using a mocvd device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 811 is the c-axis direction. next, as shown in fig. 68c , in a semiconductor layer forming step, a semiconductor layer 814 made of p-type gan is formed over the whole surface of the substrate 811 such that the rod-like semiconductor core 813 is covered with the semiconductor layer 814 . the formation temperature is set to about 960° c., and trimethylgalium (tmg) and ammonia (nh 3 ) as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) for p-type impurity supply are used, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, as shown in fig. 68d , in an exposing step, all of the region of the semiconductor layer 814 , except for a portion thereof covering the semiconductor core 813 , and the mask 812 are removed by lift-off so as to expose the outer peripheral surface on the side of the substrate 811 of the rod-like semiconductor core 813 , so that an exposed portion 813 a is formed. in this state, the end surface of the semiconductor core 813 opposite to the substrate 811 is covered with a semiconductor layer 814 a . in the case where a mask is made of silicon oxide (sio 2 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. the lift-off is used in the exposing step of this embodiment; however, part of the semiconductor core may be exposed by etching. in the case of dry etching, use of cf 4 and xef 2 enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables all of the region of the semiconductor layer, except for the portion thereof covering the semiconductor core, together with the mask to be removed. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 811 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 813 covered with the semiconductor layer 814 a so as to bend the root close to the substrate 811 of the semiconductor core 813 that erects on the substrate 811 . as a result, as shown in fig. 68e , the semiconductor core 813 covered with the semiconductor layer 814 a is separated from the substrate 811 . in this way, a microscopic rod-like light-emitting device 810 that is separated from the substrate 811 can be manufactured. in this embodiment 31, the rod-like light-emitting device 810 has a diameter of 1 μm and a length of 10 μm. in the rod-like light-emitting device 810 , with one electrode connected to the exposed portion 813 a of the semiconductor core 813 , and with the other electrode connected to the semiconductor layer 814 a , a current is caused to flow from the p-type semiconductor layer 814 a to the n-type semiconductor core 813 to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the n-type semiconductor core 813 and the inner peripheral surface of the p-type semiconductor layer 814 a . thus, light is emitted. light is emitted from the whole periphery of the semiconductor core 813 covered with the semiconductor layer 814 a . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. according to a method of manufacturing a rod-like light-emitting device having the above configuration, the microscopic rod-like light-emitting device 810 having great freedom in installing into an apparatus can be manufactured. the above rod-like light-emitting device is used as a microscopic structure separated from the substrate. this can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core 813 covered with the semiconductor layer 814 a , which expands the light emitting region. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. in the exposing step for exposing part of the outer peripheral surface of the semiconductor core 813 , the outer peripheral surface on the side of the substrate 811 of the semiconductor core 813 is exposed, and in the semiconductor layer forming step, the end surface of the semiconductor core 813 opposite to the substrate 811 is covered with the semiconductor layer 814 . this enables the exposed portion 813 a on the side of the substrate 811 of the semiconductor core 813 to be connected to the n-side electrode. the end surface of the semiconductor core 813 opposite to the substrate 811 is covered with the semiconductor layer 814 a . this enables the p-side electrode to be connected to a portion of the semiconductor layer 814 a covering the side opposite to the substrate 811 of the semiconductor core 813 . in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device. in the above separating step, the substrate 811 is vibrated along the plane of the substrate 811 using ultrasonic waves. this causes stress to act on the semiconductor core 813 covered with the semiconductor layer 814 a so as to bend the root close to the substrate 811 of the semiconductor core 813 that erects on the substrate 811 . as a result, the semiconductor core 813 covered with the semiconductor layer 814 a is separated from the substrate 811 . accordingly, a plurality of microscopic rod-like light-emitting devices provided on the substrate 811 can easily be separated in a simple way. note that, in the above separating step, the semiconductor core 813 may be mechanically separated from the substrate 811 using a cutting tool. the root close to the substrate 811 of the semiconductor core 813 that erects on the substrate 811 is bent using a cutting tool. as a result, stress acts on the semiconductor core 813 covered with the semiconductor layer 814 a , so that the semiconductor core 813 covered with the semiconductor layer 814 a is separated from the substrate 811 . in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate 811 can be separated for a short time in a simple way. in the above exposing step, dry etching may be used, which can easily expose part of the outer peripheral surface of the semiconductor core 813 made of a semiconductor whose base material is gan. wet etching is difficult for the semiconductor whose base material is gan. therefore, in cases where the semiconductor core 813 and the semiconductor layer 814 a are made of the semiconductors whose base materials are gan, exposing part of the outer peripheral surface of the semiconductor core 813 by dry etching prior to the separating step is particularly effective for implementing a microscopic rod-like light-emitting device that is easy to mount. in the case of manufacturing a microscopic rod-like light-emitting device by separating the semiconductor core 813 covered with the semiconductor layer 814 a from the substrate 811 without the exposing step for exposing part of the outer peripheral surface of the semiconductor core 813 , it is possible to easily expose part of the outer peripheral surface of the semiconductor core 813 by dry etching for the purpose of electrode connection after the microscopic rod-like light-emitting device is aligned on the insulating substrate 811 . in the above exposing step, the outer peripheral surface of the region covered with the semiconductor layer 814 a of the semiconductor core 813 and the outer peripheral surface of the exposed region of the semiconductor core 813 are continuous with each other such that the exposed region of the semiconductor core 813 is thin. therefore, in the above separating step, the side of the substrate 811 of the exposed region of the semiconductor core 813 becomes more likely to be broken on the substrate 811 side in the exposed region of the semiconductor core 813 , which facilitates the separation. moreover, in a rod-like light-emitting device manufactured by the above method of manufacturing a rod-like light-emitting device, crystal growth of the semiconductor layer 814 a occurs radially outward from the outer peripheral surface of the semiconductor core 813 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 813 can be covered with the semiconductor layer 814 a having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. (embodiment 32) figs. 69a to 69e are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 32 of this invention. a rod-like light-emitting device of this embodiment 32 has the same configuration as the rod-like light-emitting device of embodiment 31, except for the quantum well layer. first, as shown in fig. 69a , a mask 822 having a growth hole 822 a is formed on a substrate 821 made of n-type gan. a material capable of selectively etching a semiconductor core and a semiconductor layer, such as silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), can be used for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the above growth hole of the mask. next, as shown in fig. 69b , in a semiconductor core forming step, a semiconductor core 823 shaped like a rod is formed on the substrate 821 exposed through the growth hole 822 a of the mask 822 by crystal growth of n-type gan using a mocvd device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core of n-type gan with si used as the impurity can be grown. here, n-type gan results in hexagonal crystal growth, and a semiconductor core shaped like a rod of a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate 821 is the c-axis direction. next, as shown in fig. 69c , in a quantum well layer and semiconductor layer forming step, a quantum well layer 824 made of p-type ingan is formed over the whole surface of the substrate 821 so as to cover the semiconductor core 823 shaped like a rod, and further a semiconductor layer 825 is formed over the whole surface of the substrate 821 . after the semiconductor core of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 824 can be formed on the semiconductor core 823 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 825 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer. also, the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. next, as shown in fig. 69d , in an exposing step, all of the regions of the quantum well layer 824 and the semiconductor layer 825 , except for portions thereof covering the semiconductor core 823 , and the mask 822 are removed by lift-off so as to expose the outer peripheral surface on the side of the substrate 821 of the rod-like semiconductor core 823 , so that an exposed portion 823 a is formed. in this state, the end surface of the above semiconductor core 823 opposite to the substrate 821 is covered with the quantum well layer 824 a and the semiconductor layer 825 a . in the case where a mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. the lift-off is used in the exposing step of this embodiment; however, part of the semiconductor core may be exposed by etching. in the case of dry etching, use of cf 4 and xef 2 enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables all of the region of the semiconductor layer, except for the portion thereof covering the semiconductor core, together with the mask to be removed. next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 821 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 823 covered with the quantum well layer 824 and the semiconductor layer 825 a so as to bend the root close to the substrate 821 of the semiconductor core 823 that erects on the substrate 821 . as a result, as shown in fig. 69e , the semiconductor core 823 covered with the quantum well layer 824 and the semiconductor layer 825 a is separated from the substrate 821 . in this way, a microscopic rod-like light-emitting device 820 that is separated from the substrate 821 can be manufactured. in this embodiment 32, the rod-like light-emitting device 820 has a diameter of 1 μm and a length of 10 μm. in the rod-like light-emitting device 820 , with the n-side electrode connected to the exposed portion 823 a of the semiconductor core 823 and with the p-side electrode connected to the semiconductor layer 825 a , a current is caused to flow from the p-type semiconductor layer 825 a to the n-type semiconductor core 823 to result in recombination of electrons and holes in the quantum well layer 824 a . thus, light is emitted. light is emitted from the whole periphery of the semiconductor core 823 covered with the semiconductor layer 825 a . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. according to a method of manufacturing a rod-like light-emitting device having the above configuration, the microscopic rod-like light-emitting device 820 having great freedom in installing into an apparatus can be manufactured. the above rod-like light-emitting device can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core 823 , which makes the light emitting region larger. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the above method of manufacturing a rod-like light-emitting device of embodiment 32 has effects similar to those of the rod-like light-emitting device of embodiment 31. electrons and holes recombine with each other to emit light in the quantum well layer 824 a formed between the n-type semiconductor core 823 and the p-type semiconductor layer 825 a . this can result in a more increased light emitting efficiency, which is due to quantum confinement effects of the quantum well layer 824 a , than embodiment 31. (embodiment 33) figs. 70a to 70d are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 33 of this invention. the rod-like light-emitting device of this embodiment 33 has the same configuration as the rod-like light-emitting device of embodiment 31, except for the exposed portion of the semiconductor core. first, as shown in fig. 70a , in a semiconductor core forming step, a rod-like semiconductor core 833 is formed on an n-type gan substrate 831 by crystal growth of n-type gan. this step of forming the semiconductor core 833 is performed in a similar manner to that of embodiment 31 to remove a mask. next, as shown in fig. 70b , in the semiconductor layer forming step, a semiconductor layer 834 made of p-type gan is formed over the whole surface of the substrate 831 to cover the semiconductor core 833 shaped like a rod. next, as shown in fig. 70c , in an exposing step, all of the region of the semiconductor layer 834 , except for a portion thereof covering the semiconductor core 833 , is removed by dry etching to expose the outer peripheral surface on the side of the substrate 831 of the rod-like semiconductor core 833 , so that an exposed portion 833 a is formed. in this case, use of sicl 4 for rie of dry etching allows gan to be anisotropically etched with ease. in this state, the end surface of the semiconductor core 833 opposite to the substrate 831 is exposed by dry etching. here, the outer peripheral surface of the semiconductor layer 834 a and the outer peripheral surface of the exposed portion 833 a of the semiconductor core 833 are continuous with each other without a step. thus, when a microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 833 a of the semiconductor core 833 can be reliably and easily connected with the electrode because no step exists between the outer peripheral surface of the semiconductor layer 834 a and the outer peripheral surface of the exposed portion 833 a of the semiconductor core 833 . next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 831 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 833 covered with the semiconductor layer 834 a so as to bend the root close to the substrate 831 of the semiconductor core 833 that erects on the substrate 831 . as a result, as shown in fig. 70d , the semiconductor core 833 covered with the semiconductor layer 834 a is separated from the substrate 831 . in this way, a microscopic rod-like light-emitting device 830 that is separated from the substrate 831 can be manufactured. in this embodiment 33, the rod-like light-emitting device 830 has a diameter of 1 μm and a length of 10 μm. in the rod-like light-emitting device 830 , with the n-side electrode connected to the exposed portion 833 a of the semiconductor core 833 and with the p-side electrode connected to the semiconductor layer 834 a , a current is caused to flow from the p-type semiconductor layer 834 a to the n-type semiconductor core 833 to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the n-type semiconductor core 833 and the inner peripheral surface of p-type semiconductor layer 834 a . thus, light is emitted. light is emitted from the whole periphery of the semiconductor core 833 covered with the semiconductor layer 834 a . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. according to a method of manufacturing a rod-like light-emitting device having the above configuration, the microscopic rod-like light-emitting device 830 having great freedom in installing into an apparatus can be manufactured. the above rod-like light-emitting device can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core covered with the semiconductor layer, which makes the light emitting region larger. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the above method of manufacturing a rod-like light-emitting device of embodiment 33 has effects similar to those of the rod-like light-emitting device of embodiment 31. as shown in fig. 70c , after the semiconductor layer forming step and before the separating step, all of the region of the semiconductor layer 834 , except for a portion thereof covering the surface of the semiconductor core 833 , and the part corresponding to the region in the thickness direction of the upper region of the n-type gan substrate 831 are removed by etching to expose part of the outer peripheral surface of the semiconductor core 833 . this can result in no step between the outer peripheral surface of the semiconductor layer 834 a and the exposed portion 833 a of the outer peripheral surface of the semiconductor core 833 . thus, when the microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 833 a of the semiconductor core 833 can be reliably and easily connected with the electrode. (embodiment 34) figs. 71a to 71d are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 34 of this invention. the rod-like light-emitting device of this embodiment 34 has the same configuration as the rod-like light-emitting device of embodiment 32, except for the exposed portion of the semiconductor core. first, as shown in fig. 71a , in a semiconductor core forming step, a rod-like semiconductor core 843 is formed on an n-type gan substrate 841 by crystal growth of n-type gan. this step of forming the semiconductor core 843 is performed in a similar manner to that of embodiment 31 to remove a mask. next, as shown in fig. 71b , in a quantum well layer and semiconductor layer forming step, a quantum well layer 844 made of p-type ingan is formed over the whole surface of the substrate 841 to cover the rod-like semiconductor core 843 , and further a semiconductor layer 845 is formed over the whole surface of the substrate 841 . note that this quantum well layer may have a multiple quantum well structure in which a barrier layer and a quantum well layer are laminated. next, as shown in fig. 71c , in an exposing step, all of the regions of the quantum well layer 844 and the semiconductor layer 845 , except for portions thereof covering the semiconductor core 843 , is removed by dry etching to expose the outer peripheral surface on the side of the substrate 841 of the rod-like semiconductor core 843 , so that an exposed portion 843 a is formed. in this case, use of sicl 4 for rie of dry etching allows gan to be anisotropically etched with ease. in this state, the end surface of the semiconductor core 843 opposite to the substrate 841 is exposed by dry etching. here, the outer peripheral surface of a semiconductor layer 845 a and the outer peripheral surface of an exposed portion 843 a of the semiconductor core 843 are continuous with each other without a step (no step also exists between an exposed portion of the outer peripheral surface of the quantum well layer 844 a and the outer peripheral surface of the exposed portion 843 a of the semiconductor core 843 ). thus, when a microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 843 a of the semiconductor core 843 can be reliably and easily connected with the electrode because no step exists between the outer peripheral surface of the semiconductor layer 845 a and the outer peripheral surface of the exposed portion 843 a of the semiconductor core 843 . next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 841 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 843 covered with the semiconductor layer 845 a so as to bend the root close to the substrate 841 of the semiconductor core 843 that erects on the substrate 841 . as a result, as shown in fig. 71d , the semiconductor core 843 covered with the semiconductor layer 845 a is separated from the substrate 841 . in this way, a microscopic rod-like light-emitting device 840 that is separated from the substrate 841 can be manufactured. in this embodiment 34, the rod-like light-emitting device 840 has a diameter of 1 μm and a length of 10 μm. in the rod-like light-emitting device 840 , with the n-side electrode connected to the exposed portion 843 a of the semiconductor core 843 and with the p-side electrode connected to the semiconductor layer 845 a , a current is caused to flow from the p-type semiconductor layer 845 a to the n-type semiconductor core 843 to result in recombination of electrons and holes in the quantum well layer 844 a . thus, light is emitted. light is emitted from the whole periphery of the semiconductor core 843 covered with the semiconductor layer 845 a . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. according to a method of manufacturing a rod-like light-emitting device having the above configuration, the microscopic rod-like light-emitting device 840 having great freedom in installing into an apparatus can be manufactured. the above rod-like light-emitting device can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core covered with the semiconductor layer, which makes the light emitting region larger. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the above method of manufacturing a rod-like light-emitting device of embodiment 34 has effects similar to those of the rod-like light-emitting device of embodiment 31. electrons and holes recombine with each other to emit light in the quantum well layer 844 a formed between the n-type semiconductor core 843 and the p-type semiconductor layer 845 a . this can result in a more increased light emitting efficiency, which is due to quantum confinement effects of the quantum well layer 844 a , than embodiment 33. as shown in fig. 71c , after the semiconductor layer forming step and before the separating step, all of the regions of the quantum well layer 844 and the semiconductor layer 845 , except for portions thereof covering the surface of the semiconductor core 843 , and the part corresponding to the above regions in the thickness direction of the upper region of the n-type gan substrate 841 are removed by etching to expose part of the outer peripheral surface of the semiconductor core 843 . this can result in no step between the outer peripheral surface of the semiconductor layer 844 a and the exposed portion 843 a of the outer peripheral surface of the semiconductor core 843 . thus, when the microscopic rod-like light-emitting device that has been separated is mounted on an insulating substrate having an electrode formed thereon in such a manner that the axial direction of the device is parallel to the plane of the substrate, the exposed portion 843 a of the semiconductor core 843 can be reliably and easily connected with the electrode. (embodiment 35) figs. 72 to 94 are process drawings of a method of manufacturing a rod-like light-emitting device of embodiment 35 of this invention. in this embodiment 35, n-type gan doped with si and p-type gan doped with mg are used. however, the impurity with which gan is doped is not limited to this case. first, the surface of a substrate 911 shown in fig. 72 is cleaned. as the substrate, substrates that allow growth of gan, such as si, sic and sapphire can be used. next, as shown in fig. 73 , a growth-mask layer (hereinbelow referred to as a “mask”) 912 is formed on the substrate 911 . a material that is selectively etchable with respect to a semiconductor core and a semiconductor layer of silicon oxide (sio 2 ) and the like can be used for the mask. next, as shown in fig. 74 , a hole 920 a is formed on a resist 920 applied onto the substrate 911 by patterning using a known lithography method for use in usual semiconductor processes. next, as shown in fig. 75 , a growth hole 912 a is formed in the mask 912 using the hole 920 a of the patterned resist 920 . a dry etching method can be utilized for the growth hole formation. next, as shown in fig. 76 , catalyst metal 913 for semiconductor core growth is deposited. a material, such as ni, fe or au, can be used for promoting the growth of the semiconductor of a semiconductor core. next, as shown in fig. 77 , the region of the catalyst metal 913 deposited on the region other than the growth hole 912 a (shown in fig. 75 ) and the resist 920 are removed. the lift-off is used here. however, a lithography method and etching may be used. at this point, the diameter of the semiconductor core to be grown depends on the size of the growth hole of the mask and the volume of the catalyst metal. next, as shown in fig. 78 , in a semiconductor core forming step, on the substrate 911 within the growth hole 912 a of the mask layer 912 having the catalyst metal 913 , a rod-like semiconductor core 914 is formed by crystal growth of n-type gan using a mocvd device. the growth temperature is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core of n-type gan with si used as the impurity can be grown. here, n-type gan is grown under the condition where a direction perpendicular to the surface of the substrate 911 is the c-axis direction. as a result, a semiconductor core having many non-polar surfaces or semi-polar surfaces is obtained. next, as shown in fig. 79 , in a quantum well layer and semiconductor layer forming step, a quantum well layer 915 made of p-type ingan is formed over the whole surface of the substrate 911 so as to cover the rod-like semiconductor core 914 , and further a semiconductor layer 916 is formed over the whole surface of the substrate 911 . after the semiconductor core of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 915 can be formed on the semiconductor core 914 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 916 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer. also, the quantum well layer may have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. next, as shown in fig. 80 , the catalyst metal 913 (shown in fig. 79 ) is removed by wet etching, and then, as shown in fig. 81 , a conductive film 917 is formed on the surface of the semiconductor layer 916 . next, as shown in fig. 82 , an edge portion 917 b (shown in fig. 81 ) and a substrate side portion 917 c (shown in fig. 81 ), which correspond to all of the region except for a cylindrical portion 917 of the conductive film 917 , are removed by anisotropic dry etching (rie). next, as shown in fig. 83 , all of the region of the semiconductor layer 916 and the quantum well layer 915 , except for portions thereof covering the semiconductor core 914 , is removed by dry etching. with reference to fig. 83 , the semiconductor core 914 is covered with the quantum well layer 915 a , the semiconductor layer 916 a and the conductive film 917 a. next, as shown in fig. 84 , the mask 912 (shown in fig. 83 ) is removed by wet etching. in the case where the mask is made of silicon oxide (sio 2 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core. next, as shown in fig. 85 , the substrate 911 is etched by dry etching. in this case, use of cf 4 and xef 2 enables the substrate 911 to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core. thus, a protrusion 911 a is formed in a region of the substrate 911 directly under the semiconductor core 914 . next, in a separating step, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate 911 using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 914 covered with the quantum well layer 915 a , the semiconductor layer 916 a and the conductive film 917 a so as to bend the root close to the substrate 911 of the semiconductor core 914 that erects on the substrate 911 . as a result, as shown in fig. 86 , the semiconductor core 914 covered with the conductive film 917 a , the semiconductor layer 916 a and the quantum well layer 915 a is separated from the substrate 911 . in this way, a microscopic rod-like light-emitting device 918 that is separated from the substrate 911 can be manufactured. in this embodiment 35, the rod-like light-emitting device 918 has a diameter of 1.5 μm and a length of 25 μm. note that the cross section of the rod-like light-emitting device 918 is in the shape of an equilateral triangle as shown in fig. 87c and fig. 87d to be referred to later. next, the rod-like light-emitting device 918 manufactured by the above method of manufacturing a rod-like light-emitting device is aligned on an insulating substrate. the alignment of the rod-like light-emitting device 918 is made using the method of manufacturing a display device of embodiment 38 to be described later, and will be described below with reference to figs. 87a to 94d . note that, in figs. 87a to 94d , the same elements as those of the rod-like light-emitting device 918 shown in fig. 86 are denoted by the same reference characters. in addition, while the cross section of the rod-like light-emitting device 918 is in the shape of an equilateral triangle, the cross-sectional shape of the rod-like light-emitting device is not limited to this. the rod shape may have a cross section that is hexagonal, circular or ellipsoidal. this invention may be applied to a method of manufacturing a rod-like light-emitting device having a semiconductor core in a rod shape whose cross section is in the shape of another polygon. fig. 87a is a plan view showing a step of a method of manufacturing a display device that uses the rod-like light-emitting device 918 shown in fig. 86 , fig. 87b is a cross-sectional view of the display device as taken along the line f 27 b-f 27 b of fig. 87a , fig. 87c is a cross-sectional view of the display device taken along the line f 27 c-f 27 c of fig. 87a , and fig. 87d is a cross-sectional view of the display device as taken along the line f 27 d-f 27 d of fig. 87a . first, as shown in figs. 87a to 87d , the rod-like light-emitting device 918 is aligned on an insulating substrate 930 formed thereon with an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided, and then cleaning is carried out. the method of aligning the rod-like light-emitting device 918 at a predetermined position in a predetermined orientation on the insulating substrate 930 has been described in detail in embodiment 5, and the detailed description thereof is omitted here. as shown in fig. 87b , metal electrodes 931 and 932 are formed with a predetermined spacing therebetween on the surface of the insulating substrate 930 , and an insulating film 133 is formed to cover the metal electrodes 931 and 932 . the insulating substrate 930 is such that a silicon oxide film is formed on the surface of an insulator, such as glass, ceramic, aluminum oxide or resin, or a semiconductor such as silicon, and the surface has insulating properties. in the case of using a glass substrate, it is desirable that an underlying insulating film such as a silicon oxide film or a silicon nitride film be formed on the surface. the insulating film that covers metal electrodes need not be provided. the metal electrodes 931 and 932 are formed in desired electrode shapes using a printing technique. note that a metal film and a photosensitive film may be formed by depositing the films all at once, exposing them in a desired electrode pattern, and etching them. here, portions of 3 μm in length at both ends of the rod-like light-emitting device 918 overlap the metal electrodes 931 and 932 , respectively. note that pads, which are omitted in figs. 87a to 87d , are formed on the metal electrodes 931 and 932 so as to allow potentials to be provided from the outside. in figs. 87a to 87d , one alignment region in which rod-like light-emitting devices are aligned is shown. however, any number of alignment regions may be arranged. note that the rod-like light-emitting device 918 is aligned to establish a bridge between two metal electrodes 931 and 932 on the insulating substrate 930 . as will be described later, two options are available for the orientation of the rod-like light-emitting device 918 . one is the orientation of the rod-like light-emitting device 918 depicted in figs. 87a to 87d , and the other is the orientation in which the left and right sides of the rod-like light-emitting device 918 are reversed. in fact, both the orientations are not distinguishable from each other in the light-emitting device 918 of this embodiment 35. with the method of manufacturing a display device of embodiment 38, the two orientations cannot be intentionally determined, and therefore the two orientations each have a 50% probability of occurrence. next, fig. 88a is a plan view showing a step subsequent to steps shown in figs. 87a to 87d of the method of manufacturing a display device. fig. 88b is a cross-sectional view of a display device as taken along the line f 28 b-f 28 b of fig. 88a , fig. 88c is a cross-sectional view of the display device as taken along the line f 28 c-f 28 c of fig. 88a , and fig. 88d is a cross-sectional view of the display device as taken along the line f 28 d-f 28 d of fig. 88a . as shown in figs. 88a to 88d , after a resist 940 is applied onto the insulating substrate 930 , patterning is performed by way of a lithography method to expose one end (left end in fig. 88a ) of the rod-like light-emitting device 918 . next, fig. 89a is a plan view showing a step subsequent to the steps shown in figs. 88a to 88d of the method of manufacturing a display device. fig. 89b is a cross-sectional view of a display device as taken along the line f 29 b-f 29 b of fig. 89a , fig. 89c is a cross-sectional view of the display device as taken along the line f 29 c-f 29 c of fig. 89a , and fig. 89d is a cross-sectional view of the display device as taken along the line f 29 d-f 29 d of fig. 89a . as shown in figs. 89a to 89d , after the conductive film 917 a is removed by wet etching using the patterned resist 94 , part of the semiconductor layer 916 a and part of the quantum well layer 915 a are removed by dry etching to obtain an exposed portion 914 a of the semiconductor core 914 . in this way, the semiconductor core 914 at one end of the rod-like light-emitting device 918 can be exposed. as described above, with reference to figs. 87a to 87d , at the time of aligning the rod-like light-emitting device 918 on the insulating substrate 930 , the orientation can be taken in two ways. here, the reason why two ways of the orientation are issued is the fact that the orientations between which left and right sides of the rod-like light-emitting device 918 are reversed are distinguished from each other in figs. 87a to 87d . in fact, the rod-like light-emitting device 918 is symmetric even when the left and right sides are reversed, and therefore both the orientations are not distinguishable. however, for example, the rod-like light-emitting devices of embodiments 31 to 34 are distinguishable when such reversal is made. in the method of manufacturing a rod-like light-emitting device of this embodiment 35, after the rod-like light-emitting device 918 is aligned on the insulating substrate 930 ( figs. 87a to 87d ), an exposing step ( figs. 89a to 89d ) for exposing part of the outer peripheral surface of the semiconductor 914 of the rod-like light-emitting device 918 is performed. therefore, even when the rod-like light-emitting device 918 is aligned in any orientation at the time of alignment, part of the outer peripheral surface of the semiconductor core 914 on a predetermined side of the rod-like light-emitting device 918 aligned on the insulating substrate 930 can be exposed. therefore, at the time of aligning the rod-like light-emitting devices 918 on the insulating substrate 930 , the orientations of rod-like light-emitting devices 918 need not be made uniform. the rod-like light-emitting devices 918 are diodes having anode and cathode electrodes, and it is important to make uniform the orientations of the rod-like light-emitting devices 918 . according to this embodiment 35, such a step of making the orientations uniform becomes unnecessary, which allows processes to be simplified. next, fig. 90a is a plan view showing a step subsequent to the steps shown in figs. 89a to 89d of the method of manufacturing a display device. fig. 90b is a cross-sectional view of a display device as taken along the line f 30 b-f 30 b of fig. 90a , fig. 90c is a cross-sectional view of the display device as taken along the line f 30 c-f 30 c of fig. 90a , and fig. 90d is a cross-sectional view of the display device as taken along the line f 30 d-f 30 d of fig. 90a . also, fig. 91a is a plan view showing a step subsequent to the steps shown in figs. 90a to 90d of the method of manufacturing a display device. fig. 91b is a cross-sectional view of a display device as taken along the line f 31 b-f 31 b of fig. 91a , fig. 91c is a cross-sectional view of the display device as taken along the line f 31 c-f 31 c of fig. 91a , and fig. 91d is a cross-sectional view of the display device as taken along the line f 31 d-f 31 d of fig. 91a . as shown in figs. 90a to 90d , an insulating film 941 made of sio 2 is deposited on the insulating substrate 930 , and then, as shown in figs. 91a to 91d , the insulating film 941 made of sio 2 is etched by way of dry etching. at this point, all of the insulating film 941 made of sio 2 is not removed, etching is performed such that the quantum well layer 915 a and the semiconductor layer 916 a between the semiconductor core 914 and the insulating substrate 930 are not exposed, and are wrapped in sio 2 of the insulating film 941 , and such that the exposed region 914 a of the semiconductor core 914 is exposed (see fig. 91c ). next, fig. 92a is a plan view showing a step subsequent to the steps shown in figs. 91a to 91d of the method of manufacturing a display device. fig. 92b is a cross-sectional view of a display device as taken along the line f 32 b-f 32 b of fig. 92a , fig. 92c is a cross-sectional view of the display device as taken along the line f 32 c-f 32 c of fig. 92a , and fig. 92d is a cross-sectional view of the display device as taken along the line f 32 d-f 32 d of fig. 92a . after the resist 940 used for etching is stripped, as shown in figs. 92a to 92d , a resist 942 is applied as the second resist application and then patterning is performed by way of a lithography method to expose the exposed region 914 a of the semiconductor core 914 at an end of the rod-like light-emitting device 918 and to expose the conductive film 917 a at the other end of the rod-like light-emitting device 918 . next, fig. 93a is a plan view showing a step subsequent to the steps shown in figs. 92a to 92d of the method of manufacturing a display device. fig. 93b is a cross-sectional view of a display device as taken along the line f 33 b-f 33 b of fig. 93a , fig. 93c is a cross-sectional view of the display device as taken along the line f 33 c-f 33 c of fig. 93a , and fig. 93d is a cross-sectional view of the display device as taken along the line f 33 d-f 33 d of fig. 93a . also, fig. 94a is a plan view showing a step subsequent to the steps shown in figs. 93a to 93d of the method of manufacturing a display device. fig. 94b is a cross-sectional view of a display device as taken along the line f 34 b-f 34 b of fig. 94a , fig. 94c is a cross-sectional view of the display device as taken along the line f 34 c-f 34 c of fig. 94a , and fig. 94d is a cross-sectional view of the display device as taken along the line f 34 d-f 34 d of fig. 94a . as shown in figs. 93a to 93d , metal is deposited by a vapor-deposition method and a sputtering method to form a metal layer 943 , and then, as shown in figs. 94a to 94d , lift-off is performed. thus, in the rod-like light-emitting device 918 , with one electrode 943 a connected to the exposed portion 914 a of the semiconductor core 914 and with the other electrode 943 b connected to the conductive film 917 a , a current is caused to flow from the p-type semiconductor layer 916 a through the conductive film 917 a to the n-type semiconductor core 914 to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the n-type semiconductor core 914 and the inner peripheral side of the p-type semiconductor layer 916 a . as a result, light is emitted. light is emitted from the whole periphery of the semiconductor core 914 covered with the semiconductor layer 916 a . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. in embodiment 35 described above, ito is used for the conductive film 917 a formed on the semiconductor layer 916 a to connect the semiconductor layer through transparent conductive film to an electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that light can be efficiently emitted from the whole element. thus, the light emitting efficiency is further improved. note that the conductive film is not limited to this, and, for example, a laminated metal film of ag/ni having a thickness of 5 nm may be used. according to a method of manufacturing a rod-like light-emitting device having the above configuration, the microscopic rod-like light-emitting device 918 having great freedom in installing into an apparatus can be manufactured. the rod-like light-emitting device 918 is used as a microscopic structure separated from the substrate. this can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device. light is emitted from the whole periphery of the semiconductor core 914 covered with the semiconductor layer 916 a . this makes the light emitting region larger. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the above exposing step is performed after the separating step, and therefore a small number of steps is required until the rod-like light-emitting device 918 is separated from the substrate. the rod-like light-emitting device 918 can be produced in high yields. in the above semiconductor layer forming step, the mask 912 made of a substance of inhibiting the formation of the semiconductor layer 916 covers part of the outer peripheral surface of the semiconductor core 914 , which is a portion to be exposed. after the semiconductor layer forming step, the mask 912 is removed to allow the part of the outer peripheral surface of the semiconductor core 914 to be easily exposed. here, a material that can selectively etch the semiconductor core and the semiconductor layer, such as silicon oxide (sio 2 ) and the like, is used as the substance of inhibiting the formation of the semiconductor layer 916 . however, the substance of inhibiting the formation of the semiconductor layer is not limited to this, and may be selected as appropriate in accordance with the composition of the semiconductor layer. in the above separating step, the substrate 911 is vibrated along the plane of the substrate 911 using ultrasonic waves. this causes stress to act on the semiconductor core 914 covered with the semiconductor layer 916 a so as to bend the root close to the substrate 911 of the semiconductor core 914 that erects on the substrate 911 . as a result, the semiconductor core 914 covered with the semiconductor layer 916 a is separated from the substrate 911 . accordingly, a plurality of microscopic rod-like light-emitting devices 918 provided on the substrate 911 can easily be separated in a simple way. note that, in the above separating step, the semiconductor core 914 may be mechanically separated from the substrate 911 using a cutting tool. the root close to the substrate 911 of the semiconductor core 914 that erects on the substrate 911 is bent using a cutting tool. as a result, stress acts on the semiconductor core 914 covered with the semiconductor layer 916 a , so that the semiconductor core 914 covered with the semiconductor layer 916 a is separated from the substrate 911 . in this case, a plurality of microscopic rod-like light-emitting devices 918 provided on the substrate 911 can be separated for a short time in a simple way. the rod-like light-emitting device 918 has a structure in which both sides are nearly symmetrical with respect to a linear line that passes through the midpoint of the longitudinal direction and is perpendicular to the longitudinal direction. therefore, the rod-like light-emitting devices 918 can be more easily aligned. thus, alignment with high yields can be made more reliably. in the exposing step for exposing part of the outer peripheral surface of the semiconductor core 914 after the rod-like light-emitting device 918 is aligned on the arrangement substrate (insulating substrate 930 ), the rod-like light-emitting device 918 has a nearly symmetrical structure in the longitudinal direction and allows the quantum well layer 915 a , the semiconductor layer 916 a and the conductive film 917 a at desired locations to be removed to expose the outer peripheral surface of an end of the semiconductor core 914 . therefore, a plurality of rod-like light-emitting devices (light emitting diodes) need not be aligned with their polarities aligned. the step of aligning the polarities (orientations) of a plurality of rod-like light-emitting devices (light emitting diodes) during manufacturing becomes unnecessary, which allows the steps to be simplified. to identify the polarity (orientation) of a rod-like light-emitting device (light emitting diode), a mark need not be attached to the rod-like light-emitting device. the need to produce the rod-like light-emitting device in a special shape is eliminated. therefore, manufacturing processes of a rod-like light-emitting device can be simplified, and the manufacturing costs can be reduced. note that, in the case of a small-sized light emitting diode, and in the case of a large number of light emitting diodes, the above manufacturing processes can be remarkably simplified compared to those in which light emitting diodes are aligned with their polarities made uniform. moreover, after the above exposing step, the exposed portion 914 a of the semiconductor core 914 is connected to the n-side electrode, and the other end of the semiconductor core 914 is covered with the quantum well layer, the semiconductor layer and the conductive film, which allows the p-side electrode to be connected to a portion of the conductive film. in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device. moreover, in a rod-like light-emitting device manufactured by the above method of manufacturing a rod-like light-emitting device, crystal growth of the semiconductor layer 916 occurs radially outward from the outer peripheral surface of the semiconductor core 914 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 914 can be covered with the semiconductor layer 916 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. in embodiments 31 to 35 described above, semiconductors whose base materials are gan is used for the substrates 811 , 821 , 831 and 841 , the semiconductor cores 813 , 823 , 833 , 843 and 914 , and the semiconductor layers 814 a , 825 a , 834 a , 845 a and 916 a . however, this invention may be applied to light-emitting devices using semiconductors whose base materials are gaas, algaas, gaasp, ingan, algan, gap, znse, algainp and the like. while the substrate and the semiconductor core are of n type and the semiconductor layer is of p type, this invention may be applied to a rod-like light-emitting device in which the conductivity types are reversed. a description has been given of the method of manufacturing a rod-like light-emitting device having a semiconductor core in the shape of a hexagonal prism or a triangular prism. however, the rod-like light-emitting device is not limited to this, and may have a rod shape whose cross section is in the shape of a circle or an ellipse. this invention may be applied to a method of manufacturing a rod-like light-emitting device having a semiconductor core in a rod shape whose cross section is in the shape of another polygon, such as a triangle. in embodiments 1 to 35 described above, the rod-like light-emitting device has a size of the order of micrometers with a diameter of 1 μm or 1.5 μm and a length of from 10 μm to 30 μm. however, there may be used a device with the size of the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the diameter of the semiconductor core of the above rod-like light-emitting device is preferably 500 nm or more and 50 μm or less, which enables variations in diameter of the semiconductor core to be reduced compared to a rod-like light-emitting device having a semiconductor core whose diameter ranges from several tens of nanometers to several hundreds of nanometers. therefore, variations in the light emitting region, that is, variations in light emission characteristics can be decreased. this can lead to improvement in yields. in embodiments 1 to 35 described above, crystal growth of the semiconductor cores 813 , 823 , 833 , 843 and 914 is made using the mocvd device. however, the semiconductor cores may be formed using other crystal growth devices such as a molecular-beam epitaxy (mbe) device. in embodiments 1 to 34 described above, crystal growth of the semiconductor core is made on a substrate using a mask having a growth hole. however, as in embodiment 35, metal species are placed on a substrate, and crystal growth of the semiconductor core may be made from the metal species. in embodiments 31 to 35 described above, the semiconductor cores 813 , 823 , 833 , 843 and 914 covered with the semiconductor layers 814 a , 825 a , 834 a , 845 a and 916 a are separated from the substrates 811 , 821 , 831 , 841 and 911 using ultrasonic waves. however, the way of separation is not limited to this, and the semiconductor core may be separated from the substrate by mechanically bending the semiconductor core with a cutting tool. in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be separated by a simple way for a short time. in embodiments 31 to 35 described above, transparent electrodes made of tin-doped indium oxide (ito) may be formed on the semiconductor layers 814 a , 825 a , 834 a , 845 a and 916 a . this causes the semiconductor layer to be connected through the transparent electrode to an electrode, which allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that light can be efficiently emitted from the whole element. thus, the light emitting efficiency is further improved. note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm may be used. in embodiment 35 described above, a potential difference is provided to the two metal electrodes 931 and 932 formed on the surface of the insulating substrate 930 , and the rod-like light-emitting devices 918 are aligned between the metal electrodes 931 and 932 . however, the alignment is not limited to this. rod-like light-emitting devices may be aligned at positions defined by the electrodes by forming a third electrode formed between two electrodes formed on the surface of the insulating substrate, and applying independent voltages to the three electrodes, respectively. in embodiment 35 described above, a description has been given of the display device including a rod-like light-emitting device. however, a rod-like light-emitting device manufactured by a method of manufacturing a rod-like light-emitting device of this invention is not limited to this application, and may be applied to other devices such as a backlight and an illuminating device. a method of manufacturing a rod-like light-emitting device of this invention includes the steps of forming a semiconductor core of a first conductivity type having a rod shape on a substrate, forming a semiconductor layer of a second conductivity type having a cylindrical shape covering the semiconductor core, exposing part of an outer peripheral surface of the semiconductor core, and separating from the substrate the semiconductor core including an exposed portion exposed in the exposing step. according to the above configuration, the semiconductor core of the first conductivity type having a rod shape is formed on the substrate, and then the semiconductor layer of the second conductivity type having a cylindrical shape is formed to cover the surface of the semiconductor core. here, the end surface of the semiconductor core opposite to the substrate may be covered with the semiconductor layer or may be exposed. next, part of the outer peripheral surface of the semiconductor core is exposed, and then the semiconductor core including the exposed portion is separated from the substrate, for example, by vibrating the substrate by means of ultrasonic waves, or by the use of a cutting tool. in the rod-like light-emitting device separated from the substrate in such a way, with one electrode connected to the exposed portion of the semiconductor core, and with the other electrode connected to the semiconductor layer, a current is caused to flow between the electrodes, so that electrons and holes recombine in a pn junction between the outer peripheral surface of the semiconductor core and the inner peripheral surface of the semiconductor layer. thus, light is emitted from the pn junction. in this way, a microscopic rod-like light-emitting device having great freedom in installing into an apparatus can be manufactured. the term “microscopic rod-like light-emitting device” as used herein refers to a device, for example, with the size of the order of micrometers in which the diameter is 1 μm and the length is 10 μm, or with the size in the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the above rod-like light-emitting device can decrease the amount of semiconductors used and makes it possible to reduce the thickness and weight of an apparatus that uses the light-emitting device, and emits light from the whole periphery of the semiconductor core covered with the semiconductor layer, which makes the light emitting region larger. therefore, a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. with a method of manufacturing a rod-like light-emitting device of an embodiment, in the exposing step, the outer peripheral surface on the side of the substrate of the semiconductor core is exposed, and in the semiconductor layer forming step, the end surface of the semiconductor core opposite to the substrate is covered with the semiconductor layer. according to the embodiment, exposing the outer peripheral surface on the substrate side of the semiconductor core in the exposing step and covering the end surface of the semiconductor core opposite to the substrate with the semiconductor layer in the semiconductor layer forming step causes the exposed portion on the substrate side of the semiconductor core to be connected to one electrode, and the end surface of the semiconductor core opposite to the substrate to be covered with the semiconductor layer. this allows the other electrode to be connected to a portion of the semiconductor layer covering a side of the semiconductor core opposite to the substrate. in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device. with the method of manufacturing a rod-like light-emitting device of an embodiment, in the separating step, the semiconductor core covered with the semiconductor layer is separated from the substrate using ultrasonic waves. according to the embodiment, in the separating step, the semiconductor core covered with the semiconductor layer is separated from the substrate using ultrasonic waves. for example, vibrating the substrate along the plane of the substrate using ultrasonic waves causes stress to act so as to bend the root close to the substrate of the semiconductor core that erects on the substrate, so that the semiconductor core covered with the semiconductor layer is separated from the substrate. accordingly, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be easily separated in a simple way. with the method of manufacturing a rod-like light-emitting device of an embodiment, in the separating step, the semiconductor core is mechanically separated from the substrate using a cutting tool. according to the embodiment, in the separating step, mechanically separating the semiconductor core from the substrate using a cutting tool allows a plurality of microscopic rod-like light-emitting devices provided on the substrate to be separated for a short time in a simple way. with the method of manufacturing a rod-like light-emitting device of an embodiment, the semiconductor core and the semiconductor layer are made of the semiconductors whose base materials are gan, and dry etching is used in the exposing step. according to the embodiment, using dry etching in the exposing step allows part of the outer peripheral surface of the semiconductor core made of the semiconductor whose base material is gan to be easily exposed. wet etching is difficult for the semiconductor whose base material is gan. therefore, in cases where the semiconductor core and the semiconductor layer are made of the semiconductors whose base materials are gan, exposing part of the outer peripheral surface of the semiconductor core by dry etching before the separating step is particularly effective for achieving a microscopic rod-like light-emitting device that is easy to mount. with the method of manufacturing a rod-like light-emitting device of an embodiment, in the exposing step, the outer peripheral surface of the semiconductor core is exposed so as to be continuous with the outer peripheral surface of the semiconductor layer without a step. according to the embodiment, in the exposing step, the outer peripheral surface of the semiconductor core is exposed so as to be continuous with the outer peripheral surface of the semiconductor layer without a step. as a result, when the microscopic rod-like light-emitting device after the separation is mounted on the insulating substrate having electrodes formed thereon in such a manner that the axial direction is parallel to the plane of the substrate, the exposed portion of the semiconductor core and the electrode can be connected reliably and easily because no step exists between the outer peripheral surface of the semiconductor layer and the exposed portion of the outer peripheral surface of the semiconductor core. with the method of manufacturing a rod-like light-emitting device of an embodiment, in the exposing step, the outer peripheral surface of a region covered with the semiconductor layer of the semiconductor core and the outer peripheral surface of an exposed region of the semiconductor core are continuous with each other. according to the embodiment, in the exposing step, the outer peripheral surface of the region covered with the semiconductor layer of the semiconductor core and the outer peripheral surface of the exposed region of the semiconductor core are continuous with each other such that the exposed region of the semiconductor core is thin. therefore, in the separating step, the side of the substrate of the exposed region of the semiconductor core becomes more likely to be broken on the substrate side in the exposed region of the semiconductor core, which facilitates the separation. with a method of manufacturing a display device of this invention, a method of manufacturing a display device including the rod-like light-emitting devices manufactured by any one of the methods of manufacturing rod-like light-emitting devices includes the steps of producing an insulating substrate formed thereon with an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided, applying a liquid containing the rod-like light-emitting devices in nanometer order size or micrometer order size onto the insulating substrate, and applying the independent potentials respectively to the at least two electrodes to align the rod-like light-emitting devices at positions defined by the at least two electrodes. according to the above configuration, the insulating substrate where an alignment region having as a unit at least two electrodes to which independent potentials are respectively to be provided is produced, and a liquid containing the rod-like light-emitting devices with the size of the order of nanometers or of the order of micrometers is applied onto the insulating substrate. thereafter, independent voltages are respectively applied to the at least two electrodes to align the microscopic rod-like light-emitting devices at positions defined by the at least two electrodes. thus, the above rod-like light-emitting devices can be easily aligned on the predetermined insulating substrate. with the above method of manufacturing the display device, the use of only microscopic rod-like light-emitting devices can decrease the amount of semiconductors used and can manufacture a display device whose thickness and weight can be reduced. in the above rod-like light-emitting device, light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer to expand the light emitting region. therefore, it is possible to implement a display device that has a high light-emitting efficiency and achieves low power consumption. (embodiment 36) fig. 95 is a schematic cross-sectional view showing a rod-like light-emitting device 2001 of embodiment 36 of this invention. the rod-like light-emitting device 2001 includes a semiconductor core 2011 made of n-type gan (gallium nitride) and having a rod shape whose cross section is nearly circular, a quantum well layer 2012 made of p-type ingan and covering the outer peripheral surface and axial-direction end surface of one end portion of the semiconductor core 2011 , a semiconductor layer 2013 made of p-type gan and covering the quantum well layer 2012 , and an insulator 2014 made of sio 2 (silicon oxide) or si 3 n 4 (silicon nitride) and covering the outer peripheral surface of the other end portion of the semiconductor core 2011 . note that the semiconductor core 2011 is one example of the semiconductor layer of the first conductivity type, the quantum well layer 2012 is one example of the quantum well layer, and the semiconductor layer 2013 is one example of the semiconductor layer of the second conductivity type. the outer peripheral surface on the other side of the semiconductor core 2011 is covered with the insulator 2014 . however, an axial-direction end surface 2011 a on the other side of the semiconductor core 2011 is not covered with the insulator 2014 and is exposed. here, the insulator 2014 covers the whole outer peripheral surface on the other side of the semiconductor core 2011 . note that, instead of the insulator 2014 , as indicated by a chain double-dashed line in fig. 95 , an insulator 2014 ′ may be formed that covers only a portion near the outer peripheral surface covered with the semiconductor layer 2013 of the semiconductor core 2011 , of the outer peripheral surface not covered with the semiconductor layer 2013 of the semiconductor core 2011 . the semiconductor core 2011 is doped with si as the donor impurity whereas the quantum well layer 2012 and the semiconductor layer 2013 are doped with mg as the acceptor impurity. however, the donor impurity is not limited to si, and the acceptor impurity is not limited to mg. on the outer peripheral surface of the semiconductor layer 2013 , a conductive film 2015 made of polysilicon or tin-doped indium oxide (ito) is formed. the conductive film 2015 is a film through which light from the quantum well layer 2012 is transmitted. the conductive film 2015 may be formed such that the outer peripheral surface thereof is continuous with the outer peripheral surface of the insulator 2014 without a step. that is, the outer peripheral surface of the conductive film 2015 may be flush with the outer peripheral surface of the insulator 2014 . hereinbelow, with reference to figs. 96a to 96k , a description is given of a method of manufacturing the above rod-like light-emitting device 2001 . first, as shown in fig. 96a , a substrate 2101 made of n-type gan is prepared. the substrate 2101 may be subjected to substrate cleaning with a detergent, pure water or the like, and subjected to substrate processing such as marking, as appropriate. next, as shown in fig. 96b , after a mask layer 2014 a made of an insulator is formed on the substrate 2101 , as shown in fig. 96c , a mask layer 2014 b having a growth hole 2016 is formed on the substrate 2101 by a lithography method and a dry etching method that are known (insulator forming step). note that the growth hole 2016 is one example of the through-hole, and the mask layer 2014 b is one example of the insulator. more specifically, after a resist is applied onto the surface of the mask layer 2014 a, and then exposure and development are performed, so that a resist pattern 2017 is formed. with the resist pattern 2017 used as a mask, dry etching is performed until part of the surface of the substrate 2101 is exposed. in this way, the mask layer 2014 b having the growth hole 2016 is formed on the substrate 2101 . at this point, sio 2 , silicon nitride (si 3 n 4 ) or another material that is selectively etchable with respect to the material for the quantum well layer 2012 is used as the material for the mask layer 2014 a or the mask layer 2014 b. next, deposition of a catalyst metal of ni or fe is carried out to form an island-like catalyst metal portion 2018 made of ni or fe on the surface of the substrate 2101 exposed from the growth hole 2016 as shown in fig. 96d (catalyst portion forming step). together with this, a catalyst metal layer 2019 made of ni or fe is formed on the resist pattern 2017 . the volume of the catalyst metal portion 2018 is increased to the extent that the cross-sectional shape of the catalyst metal portion 2018 is nearly rectangular. next, as shown in fig. 96e , the resist pattern 2017 is removed to lift off the catalyst metal layer 2019 , and then cleaning is carried out with, for example, pure water. next, as shown in fig. 96f , on the surface of the substrate 2101 on which the island-like catalyst metal portion 2018 is formed, that is, on the surface of the substrate 2101 overlapping the growth hole 2016 , a semiconductor core 2011 a made of n-type gan and shaped like a rod is formed by crystal growth of n-type gan from an interface between the substrate 2101 and the island-like catalyst metal portion 2018 using a metal organic chemical vapor deposition (mocvd) device (semiconductor core forming step). at this point, the growth temperature is set to about 800° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 4 ) for n-type impurity supply and further h 2 as a carrier gas are supplied, so that the semiconductor core 2011 a of n-type gan with si used as the donor impurity can be grown. next, under the condition where the island-like catalyst metal portion 2018 is held in one end of the semiconductor core 2011 a, a quantum well layer 2012 a made of p-type ingan and a semiconductor layer 2013 a made of p-type gan are formed, as shown in fig. 96g , by crystal growth from the outer peripheral surface of the semiconductor core 2011 a and crystal growth from an interface between the catalyst metal portion 2018 and the semiconductor core 2011 (semiconductor layer forming step). at this point, the growth temperature is set within the range of from 750° c. to 800° c., tmg, nh3 and trimethylindium (tmi) are used as the growth gases, cp 2 mg (bis(cyclopentadienyl)magnesium) is supplied for p-type impurity supply, and further h 2 is supplied as the carrier gas, so that p-type ingan with mg used as the impurity can be grown. also, the growth temperature is set to about 900° c., tmg and nh 3 are used as growth gases, cp 2 mg is supplied for p-type impurity supply, and further h 2 is supplied as the carrier gas, so that p-type gan with mg used as the impurity can be grown. the quantum well layer 2012 a and the semiconductor layer 2013 a are formed to cover the semiconductor core 2011 protruding from the growth hole 2016 . the structure of the quantum well layer 2012 a may be a single quantum well structure having one well layer, and may also be a multiple quantum well structure having a plurality of well layers. next, as shown in fig. 96h , the island-like catalyst metal portion 2018 in one end of the semiconductor core 2011 a is selectively removed by wet etching, and then cleaning is carried out with, for example, pure water. the island-like catalyst metal portion 2018 may be removed by reactive ion etching (rie) of dry etching. at this point, use of sicl 4 for rie allows gan to be anisotropically etched with ease. next, annealing is carried out for activation of p-type gan, and then, as shown in fig. 96i , a conductive film 2015 a made of polysilicon or ito is formed on the semiconductor layer 2013 a. further, an annealing process is performed to decrease the resistance between the semiconductor layer 2013 a and the conductive film 2015 a. next, the conductive film 2015 a, the semiconductor layer 2013 a, the quantum well layer 2012 a and the mask layer 2014 b are anisotropically etched in sequence, on the one hand, to cause the quantum well layer 2012 , the semiconductor layer 2013 and the conductive film 2015 to remain on one side of the semiconductor core 2011 , and on the other hand, to cause the insulator 2014 to remain on the other side of the semiconductor core 2011 , as shown fig. 96j (insulator etching step). at this point, part of the semiconductor layer 2013 a and part of the conductive film 2015 a are removed. in the quantum well layer 2012 a and the semiconductor layer 2013 a, the thickness in the axial direction of a portion covering the axial-direction end surface of the semiconductor core 2011 is larger than the thickness in the radial direction of a portion covering the outer peripheral surface of the semiconductor core 2011 , which makes it difficult to expose the axial-direction end surface of the semiconductor core 2011 . note that when the conductive film 2015 a, the semiconductor layer 2013 a, the quantum well layer 2012 a and the mask layer 2014 b are anisotropically etched in sequence, reducing the anisotropy at the time of etching the mask layer 2014 b enables the insulator 2014 ′ to be formed as indicated by a chain double-dashed line in fig. 96j . of the outer peripheral surface not covered with the semiconductor layer 2013 of the semiconductor core 2011 , only a portion near the outer peripheral surface covered with the semiconductor layer 2013 of the semiconductor core 2011 is covered with the insulator 2014 ′. the insulator 2014 or the insulator 2014 ′ is part of the mask layer 2014 b remaining on the substrate 2101 . while fig. 96j shows that one rod-like light-emitting device 2001 seems to be formed, a plurality of rod-like light-emitting devices 2001 are actually formed. next, the substrate 2101 is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate using ultrasonic waves of, for example, several tens of kilo-hertz. this causes stress to act on the semiconductor core 2011 and the insulator 2014 so as to bend the root close to the substrate 2101 of the semiconductor core 2011 that erects on the substrate 2101 . as a result, as shown in fig. 96k , the semiconductor core 2011 is separated from the substrate 2101 (separating step). in this way, a plurality of microscopic rod-like light-emitting devices 2001 that are separated from the substrate 2101 can be manufactured. the microscopic rod-like light-emitting device as used herein refers to, for example, a device that has such dimensions that the diameter is within the range of from 10 nm to 5 μm and the length is within the range of from 100 nm to 200 μm, and more preferably a device that has such dimensions that the diameter is within the range of from 100 nm to 2 μm and the length is within the range of from 1 μm to 50 μm. according to a method of manufacturing a rod-like light-emitting device with the above configuration, the microscopic rod-like light-emitting device 2001 is separated from the substrate 2101 , which makes it possible to increase the freedom in installing into an apparatus of the microscopic rod-like light-emitting device 2001 . on the surface of the substrate 2101 overlapping the substrate 2101 mentioned above, a semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the substrate 2101 . this enables the thickness of the semiconductor core to be uniform. the substrate 2101 is separated from the microscopic rod-like light-emitting device 2001 , and therefore need not be used at the time of light emission of the microscopic rod-like light-emitting device 2001 . accordingly, substrate options that are available at the time of light emission of the microscopic rod-like light-emitting device 2001 are expanded. this can increase the freedom in selecting the form of the apparatus on which the microscopic rod-like light-emitting devices 2001 are to be mounted. in the above separating step, vibrating the substrate 2101 along the plane of the substrate using ultrasonic waves causes stress to act on the semiconductor core 2011 and the insulator 2014 so as to bend the root close to the substrate 2101 of the semiconductor core 2011 that erects on the substrate 2101 , so that the semiconductor core 2011 and the insulator 2014 are separated from the substrate 2101 . accordingly, a plurality of microscopic rod-like light-emitting devices 2001 provided on the substrate 2101 can be easily separated in a simple way. if the above rod-like light-emitting device 2001 is not provided with the insulator 2014 , stress concentrates at a portion where a step is formed in the outer peripheral surface of the semiconductor core 2011 . the semiconductor core 2011 tends to be broken near this portion. when the semiconductor core 2011 is broken at the portion, it causes a problem of the device. accordingly, the rod-like light-emitting device 2001 includes the insulator 2014 . the insulator 2014 covers the outer peripheral surface of the vicinity of the above-mentioned portion of the semiconductor core 2011 , and therefore the semiconductor core 2011 can be prevented from being broken near the above-mentioned portion. as a result, even in cases where a plurality of microscopic rod-like light-emitting devices 2001 are manufactured, the lengths of the microscopic rod-like light-emitting devices 2001 can be made uniform. note that, as shown in fig. 95 , the insulator 2014 completely covers the entire outer peripheral surface on the other side of the semiconductor core 2011 , and therefore its effect to prevent the semiconductor core 2011 from being broken at some midpoint upon separation is higher than that of the insulator 2014 ′. as a result, the lengths of the plurality of microscopic rod-like light-emitting devices 2001 can be made uniform with reliability. the substrate 2101 can be reused for manufacturing the microscopic rod-like light-emitting device 2001 after the microscopic rod-like light-emitting device 2001 has been separated. this can reduce the manufacturing cost. the rod-like light-emitting device 2001 is microscopic, and therefore the amount of semiconductors used can be decreased. accordingly, it becomes possible to reduce the thicknesses and weights of apparatuses on which the rod-like light-emitting devices 2001 are to be mounted, which allows loads to the environment to be reduced. in the above catalyst portion forming step, the volume of the island-like catalyst metal portion 2018 formed in the growth hole 2016 is increased so that the cross-sectional shape of the catalyst metal portion 2018 is nearly rectangular. therefore, in the subsequent semiconductor core forming step, the diameter of a portion outside the growth hole 2016 of the semiconductor core 2011 a shaped like a rod is larger than the diameter of a portion inside the growth hole 2016 of the semiconductor core 2011 a having the rod shape. accordingly, it is possible to expand the pn junction to obtain a large light emitting region. in the above semiconductor layer forming step, under the condition where the island-like catalyst metal portion 2018 is held in one end of the semiconductor core 2011 a, without removing the island-like catalyst metal portion 2018 , the quantum well layer 2012 a made of p-type ingan and the semiconductor layer 2013 a made of p-type gan are formed. therefore, crystal growth from an interface between the catalyst metal portion 2018 and the semiconductor core 2011 is promoted more than crystal growth from the outer peripheral surface of the semiconductor core 2011 a. in other words, the speed of crystal growth from the interface between the catalyst metal portion 2018 and the semiconductor core 2011 is 10 to 100 times the speed of crystal growth from the outer peripheral surface of the semiconductor core 2011 a. accordingly, in the quantum well layer 2012 a and the semiconductor layer 2013 a, it is easy to make the thickness in the axial direction of the portion covering the axial-direction end surface on one side of the semiconductor core 2011 larger than the thickness in the radial direction of the portion covering the outer peripheral surface of the semiconductor core 2011 . as a result, the axial-direction end surface on one side of the semiconductor core 2011 is less likely to be exposed. therefore, it is possible to prevent the p-side electrode from being connected to the axial-direction end surface on one side of the n-type semiconductor core 2011 . in the microscopic rod-like light-emitting device 2001 manufactured by the above method of manufacturing a rod-like light-emitting device, with the n-side electrode connected to the axial-direction end surface 2011 a of the semiconductor core 2011 not covered with the insulator 2014 , and with the p-side electrode connected to the conductive film 2015 or the surface of the semiconductor layer 2013 exposed from the conductive film 2015 , a current is caused to flow from the p-type semiconductor layer 2013 to the n-type semiconductor core 2011 to result in recombination of electrons and holes in the quantum well layer 2012 . thus, light is emitted. at this point, because the quantum well layer 2012 and the semiconductor layer 2013 cover the whole peripheral surface and the axial-direction end surface on one side of the semiconductor core 2011 , light is emitted from nearly all of the quantum well layer 2012 to result in expansion of the light emitting region. accordingly, the amount of emitted light can be increased, and the light emitting efficiency can be raised. the light emitting efficiency of the rod-like light-emitting device 2001 can be increased. therefore, using the rod-like light-emitting device 2001 , a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the quantum well layer 2012 is formed between the semiconductor core 2011 and the semiconductor layer 2013 . therefore, due to quantum confinement effects of the quantum well layer 2012 , the amount of emitted light can be more increased, and the light emitting efficiency can be more increased. the axial-direction end surface 2011 a of the semiconductor core 2011 is exposed, and therefore the n-side electrode can be easily connected to the axial-direction end surface 2011 a. of all the outer peripheral surface not covered with the semiconductor layer 2013 of the semiconductor core 2011 , a portion near the outer peripheral surface covered with the semiconductor layer 2013 of the semiconductor core 2011 is covered with the insulator 2014 . as a result, the n-side electrode becomes less likely to be short-circuited to the p-side electrode, which facilitates formation of the n-side electrode and the p-side electrode. that is, even in the case where the p-side electrode to be connected to the semiconductor layer 2013 is formed near the step of the outer peripheral surface of the semiconductor core 2011 , the p-side electrode can be prevented from coming in contact with the semiconductor core 2011 , and therefore forming the n-side electrode and the p-side electrode is easy. such an effect can be obtained even in the case of forming the insulator 2014 ′ instead of the insulator 2014 . moreover, in the microscopic rod-like light-emitting device 2001 manufactured by the above method of manufacturing a rod-like light-emitting device, crystal growth of the quantum well layer 2012 a and the semiconductor layer 2013 a occurs radially outward from the outer peripheral surface of the semiconductor core 2011 a. the growth distance in the radial direction is short, and the defect deviates outward. accordingly, one side of the semiconductor core 2011 can be covered with the quantum well layer 2012 and the semiconductor layer 2013 having less crystal defects. this can make good the characteristics of the microscopic rod-like light-emitting device 2001 . in cases where the rod-like light-emitting devices 2001 are aligned on the substrate in such a manner that the axial direction of the rod-like light-emitting device 2001 is parallel to the surface of the substrate, the conductive film 2015 is formed such that the outer peripheral surface thereof is continuous with the outer peripheral surface of the insulator 2014 without a step. this can prevent the rod-like light-emitting device 2001 from being broken, and can prevent the rod-like light-emitting device 2001 from being inclined with respect to the surface of the substrate to be unstable. by preventing the rod-like light-emitting device 2001 from being inclined with respect to the surface of the substrate, the contact area of the rod-like light-emitting device 2001 with the surface of the substrate is increased. this makes it easier for the heat of the rod-like light-emitting device 2001 to diffuse to the substrate. (embodiment 37) fig. 97 is a schematic cross-sectional view showing a rod-like light-emitting device 2002 of embodiment 37 of this invention. the rod-like light-emitting device 2002 includes a semiconductor core 2021 made of n-type gan (gallium nitride) and having a rod shape whose cross section is nearly circular, a quantum well layer 2022 made of p-type ingan and covering the outer peripheral surface and axial-direction end surface of one end of the semiconductor core 2021 , a semiconductor layer 2023 made of p-type gan and covering the quantum well layer 2022 , an insulator 2024 made of sio 2 (silicon oxide) or si 3 n 4 (silicon nitride) and covering the outer peripheral surface of the other end of the semiconductor core 2021 , and an underlying layer 2030 adjoining the other end of the semiconductor core 2021 . note that the semiconductor core 2021 is one example of the semiconductor layer of the first conductivity type, the quantum well layer 2022 is one example of the quantum well layer, the semiconductor layer 2023 is one example of the semiconductor layer of the second conductivity type, and the underlying layer 2030 is one example of an underlying layer of the first conductivity type. the surface of the semiconductor core 2021 is covered with the quantum well layer 2022 or the insulator 2024 . here, the insulator 2024 covers the whole outer peripheral surface on the other side of the semiconductor core 2021 . note that, instead of the insulator 2024 , as indicated by a chain double-dashed line in fig. 97 , an insulator 2024 ′ may be formed that covers only an outer peripheral portion near the outer peripheral surface covered with the semiconductor layer 2023 of the semiconductor core 2021 , of all the outer peripheral surface not covered with the semiconductor layer 2023 of the semiconductor core 2021 . an axial-direction end surface 2030 a of the underlying layer 2030 opposite to the semiconductor core 2021 is not covered with the insulator 2024 to be exposed. a peripheral surface 2030 b of the underlying layer 2030 is not covered with the insulator 2024 and is exposed. the semiconductor core 2021 is doped with si as the donor impurity whereas the quantum well layer 2022 and the semiconductor layer 2023 are doped with mg as the acceptor impurity. however, the donor impurity is not limited to si, and the acceptor impurity is not limited to mg. on the outer peripheral surface of the semiconductor layer 2023 , a conductive film 2025 made of polysilicon or tin-doped indium oxide (ito) is formed. the conductive film 2025 is a film through which light from the quantum well layer 2022 is transmitted. the conductive film 2025 may be formed such that the outer peripheral surface thereof is continuous with the outer peripheral surface of the insulator 2024 without a step. that is, the outer peripheral surface of the conductive film 2025 may be flush with the outer peripheral surface of the insulator 2024 . hereinbelow, with reference to figs. 98a to 98m , a description is given of a method of manufacturing the rod-like light-emitting device 2002 mentioned above. first, as shown in fig. 98a , a substrate 2201 made of, for example, si is prepared. the substrate 2201 may be subjected to substrate cleaning with a detergent, pure water or the like, and subjected to substrate processing such as marking, as appropriate. next, as shown in fig. 98b , an underlying layer 2030 a made of n-type gan is formed on the substrate 2201 using a mocvd device (underlying layer forming step). at this point, the growth temperature is set to about 950° c., tmg and nh 3 are used as growth gases, sih 4 for n-type impurity supply is supplied, and further h 2 as a carrier gas is supplied, so that the underlying layer 2030 a of n-type gan with si used as the donor impurity can be grown. next, as shown in fig. 98c , after a mask layer 2024 a made of an insulator is formed on the substrate 2201 , as shown in fig. 98d , a mask layer 2024 b having a growth hole 2026 is formed on the substrate 2201 by a lithography method and a dry etching method that are known (insulator forming step). note that the growth hole 2026 is one example of the through-hole, and the mask layer 2024 b is one example of the insulator. more specifically, after a resist is applied onto the surface of the mask layer 2024 a, and then exposure and development are performed, so that a resist pattern 2027 is formed. with the resist pattern 2027 used as a mask, dry etching is performed until part of the surface of the underlying layer 2030 a is exposed. in this way, the mask layer 2024 b having the growth hole 2026 is formed on the underlying layer 2030 a. at this point, sio2, silicon nitride (si 3 n 4 ) or another material that is selectively etchable with respect to the material for the quantum well layer 2022 is used as the material for the mask layer 2024 a or the mask layer 2024 b. next, deposition of a catalyst metal of ni or fe is carried out to form an island-like catalyst metal portion 2028 made of ni or fe on the surface of the underlying layer 2030 a exposed from the growth hole 2026 as shown in fig. 98e (catalyst portion forming step). together with this, a catalyst metal layer 2029 made of ni or fe is formed on the resist pattern 2027 . the volume of the catalyst metal portion 2028 is increased to the extent that the cross-sectional shape of the catalyst metal portion 2028 is nearly rectangular. next, as shown in fig. 98f , the resist pattern 2027 is removed to lift off the catalyst metal layer 2029 , and then cleaning is carried out with, for example, pure water. next, as shown in fig. 98g , on the surface of the underlying layer 2030 a on which the island-like catalyst metal portion 2028 is formed, that is, on the surface of the underlying layer 2030 a overlapping the growth hole 2026 , a semiconductor core 2021 a made of n-type gan and shaped like a rod is formed by crystal growth of n-type gan from an interface between the island-like catalyst metal portion 2028 and the underlying layer 2030 a using a mocvd device (semiconductor core forming step). at this point, the growth temperature is set to about 800° c., tmg and nh 3 are used as growth gases, sih 4 for n-type impurity supply, and further h 2 is supplied as a carrier gas, so that the semiconductor core 2021 a of n-type gan with si used as the donor impurity can be grown. next, under the condition where the island-like catalyst metal portion 2028 is held in one end of the semiconductor core 2021 a, a quantum well layer 2022 a made of p-type ingan and a semiconductor layer 2023 a made of p-type gan are formed, as shown in fig. 98h , by crystal growth from the outer peripheral surface of the semiconductor core 2021 a and crystal growth from an interface between the catalyst metal portion 2028 and the semiconductor core 2021 (semiconductor layer forming step). at this point, the growth temperature is set within the range of from 750° c. to 800° c., tmg, nh 3 and tmi are used as the growth gases, cp 2 mg is supplied for p-type impurity supply, and further h 2 is supplied as the carrier gas, so that p-type ingan with mg used as the impurity can be grown. also, the growth temperature is set to about 900° c., tmg and nh 3 are used as growth gases, cp 2 mg is supplied for p-type impurity supply, and further h 2 is supplied as the carrier gas, so that p-type gan with mg used as the impurity can be grown. the quantum well layer 2022 a and the semiconductor layer 2023 a are formed to cover the semiconductor core 2021 protruding from the growth hole 2026 . the structure of the quantum well layer 2022 a may be a single quantum well structure having one well layer, and may also be a multiple quantum well structure having a plurality of well layers. next, as shown in fig. 98i , the island-like catalyst metal portion 2028 in one end of the semiconductor core 2021 a is selectively removed by wet etching, and then cleaning is carried out with, for example, pure water. the island-like catalyst metal portion 2028 may be removed by rie of dry etching. at this point, use of sicl 4 for rie allows gan to be anisotropically etched with ease. next, annealing is carried out for activation of p-type gan, and then, as shown in fig. 98j , a conductive film 2025 a made of polysilicon or ito is formed on the semiconductor layer 2023 a. further, an annealing process is performed to decrease the resistance between the semiconductor layer 2023 a and the conductive film 2025 a. next, the conductive film 2025 a, the semiconductor layer 2023 a, the quantum well layer 2022 a and the mask layer 2024 b are anisotropically etched in sequence, on the one hand, to cause the quantum well layer 2022 , the semiconductor layer 2023 and the conductive film 2025 to remain on one side of the semiconductor core 2021 , and on the other hand, to cause the insulator 2024 remain on the other side of the semiconductor core 2011 , as shown fig. 98k (insulator etching step). at this point, part of the semiconductor layer 2023 a and part of the conductive film 2025 a are removed. in the quantum well layer 2022 a and the semiconductor layer 2023 a, the thickness in the axial direction of the portion covering the axial-direction end surface on one side of the semiconductor core 2021 is larger than the thickness in the radial direction of the portion covering the outer peripheral surface of the semiconductor core 2021 , which makes it difficult to expose the axial-direction end surface on one side of the semiconductor core 2021 . note that when the conductive film 2025 a, the semiconductor layer 2023 a, the quantum well layer 2022 a and the mask layer 2024 b are anisotropically etched in sequence, reducing the anisotropy at the time of etching the mask layer 2024 b enables the insulator 2024 ′ to be formed as indicated by a chain double-dashed line in fig. 98k . of the outer peripheral surface not covered with the semiconductor layer 2023 on the other side of the semiconductor core 2021 , only a portion near the outer peripheral surface covered with the semiconductor layer 2023 on one side of the semiconductor core 2021 is covered with the insulator 2024 ′. the insulator 2024 or the insulator 2024 ′ is part of the mask layer 2024 b remaining on the substrate 2201 . while fig. 98k shows that one rod-like light-emitting device 2002 seems to be formed, a plurality of rod-like light-emitting devices 2002 are actually formed. note that the insulator etching step mentioned above is one example of the etching step. next, rie of the underlying layer 2030 a is carried out to form the underlying layer 2030 adjoining the other end of the semiconductor core 2021 as shown in fig. 98l (underlying layer etching step). note that the underlying layer etching step is one example of the etching step. next, the substrate 2201 is immersed in an ipa aqueous solution, and is vibrated along the plane of the substrate 2201 using ultrasonic waves of, for example, several tens of kilo-hertz. this causes stress to act on the semiconductor core 2021 and the insulator 2024 so as to bend the root close to the substrate 2201 of the semiconductor core 2021 that erects on the substrate 2201 . as a result, as shown in fig. 98m , the underlying layer 2030 is separated from the substrate 2201 (separating step). in this way, a plurality of microscopic rod-like light-emitting devices 2002 that are separated from the substrate 2201 can be manufactured. the microscopic rod-like light-emitting device as used herein refers to, for example, a device that has such dimensions that the diameter is within the range of from 10 nm to 5 μm, inclusive, and the length is within the range of from 100 nm to 200 μm, inclusive, and more preferably a device that has such dimensions that the diameter is within the range of from 100 nm to 2 μm and the length is within the range of from 1 μm to 50 μm inclusive. according to a method of manufacturing a rod-like light-emitting device with the above configuration, the microscopic rod-like light-emitting device 2002 is separated from the substrate 2201 , which makes it possible to increase the freedom in installing into an apparatus of the microscopic rod-like light-emitting device 2002 . on the surface of the substrate 2201 overlapping the substrate 2201 mentioned above, a semiconductor core of the first conductivity type shaped like a rod is formed to protrude from the substrate 2201 . this enables the thickness of the semiconductor core to be uniform. the substrate 2101 is separated from the microscopic rod-like light-emitting device 2002 , and therefore need not be used at the time of light emission of the microscopic rod-like light-emitting device 2002 . that is, a connection of an electrode to the substrate 2201 becomes unnecessary. accordingly, substrate options that are available at the time of light emission of the microscopic rod-like light-emitting device 2002 are expanded. this can increase the freedom in selecting the form of the apparatus on which the microscopic rod-like light-emitting devices 2002 are to be mounted. in the above separating step, vibrating the substrate 2201 along the plane of the substrate using ultrasonic waves causes stress to act on the semiconductor core 2021 and the insulator 2024 so as to bend the root close to the substrate 2201 of the semiconductor core 2021 that erects on the substrate 2201 , so that the semiconductor core 2021 and the insulator 2024 are separated from the substrate 2201 . accordingly, a plurality of microscopic rod-like light-emitting devices 2002 provided on the substrate 2201 can be easily separated in a simple way. if the above rod-like light-emitting device 2002 is not provided with the insulator 2024 , stress concentrates at a portion where a step is formed in the outer peripheral surface of the semiconductor core 2021 . the semiconductor core 2011 tends to be broken near this portion. when the semiconductor core 2021 is broken at the portion, it causes a problem of the device. accordingly, the rod-like light-emitting device 2002 includes the insulator 2024 . the insulator 2024 covers the outer peripheral surface of the vicinity of the above-mentioned portion of the semiconductor core 2021 , and therefore the semiconductor core 2021 can be prevented from being broken near the above-mentioned portion. as a result, even in cases where a plurality of microscopic rod-like light-emitting devices 2002 are manufactured, the lengths of the microscopic rod-like light-emitting devices 2002 can be made uniform. note that, as shown in fig. 97 , the insulator 2024 completely covers the entire outer peripheral surface on the other side of the semiconductor core 2021 , and therefore its effect to prevent the semiconductor core 2021 from being broken at some midpoint upon separation is higher than that of the insulator 2024 ′. as a result, the lengths of the plurality of microscopic rod-like light-emitting devices 2002 can be made uniform with reliability. the substrate 2201 can be reused for manufacturing the microscopic rod-like light-emitting device 2002 after the microscopic rod-like light-emitting device 2002 has been separated. this can reduce the manufacturing cost. the rod-like light-emitting device 2002 is microscopic, and therefore the amount of semiconductors used can be decreased. accordingly, it becomes possible to reduce the thicknesses and weights of apparatuses on which the rod-like light-emitting devices 2002 are to be mounted, which allows loads to the environment to be reduced. in the above catalyst portion forming step, the volume of the island-like catalyst metal portion 2028 formed in the growth hole 2026 is increased so that the cross-sectional shape of the catalyst metal portion 2028 is nearly rectangular. therefore, in the subsequent semiconductor core forming step, the diameter of a portion outside the growth hole 2026 of the semiconductor core 2021 a shaped like a rod is larger than the diameter of a portion inside the growth hole 2026 of the semiconductor core 2021 a having the rod shape. accordingly, it is possible to expand the pn junction to obtain a large light emitting region. in the above semiconductor core forming step, crystal growth of the semiconductor core 2021 a made of n-type gan occurs on the underlying layer 2030 a made of n-type gan. therefore, crystal growth of the semiconductor core 2021 a can easily occur, and variations in the initial crystal growth of the semiconductor core 2021 a can be reduced. in the above semiconductor layer forming step, under the condition where the island-like catalyst metal portion 2028 is held in one end of the semiconductor core 2021 a, without removing the island-like catalyst metal portion 2028 , the quantum well layer 2022 a made of p-type ingan and the semiconductor layer 2023 a made of p-type gan are formed. therefore, crystal growth from the interface between the catalyst metal portion 2028 and the semiconductor core 2021 is promoted more than crystal growth from the outer peripheral surface of the semiconductor core 2021 a. in other words, the speed of crystal growth from the interface between the catalyst metal portion 2028 and the semiconductor core 2021 is 10 to 100 times the speed of crystal growth from the outer peripheral surface of the semiconductor core 2021 a. accordingly, in the quantum well layer 2022 a and the semiconductor layer 2023 a, it is easy to make the thickness in the axial direction of the portion covering the axial-direction end surface on one side of the semiconductor core 2021 larger than the thickness in the radial direction of the portion covering the outer peripheral surface of the semiconductor core 2021 . as a result, the axial-direction end surface on one side of the semiconductor core 2021 is less likely to be exposed. therefore, it is possible to prevent the p-side electrode from being connected to the axial-direction end surface on one side of the n-type semiconductor core 2021 . in the microscopic rod-like light-emitting device 2002 manufactured by the above method of manufacturing a rod-like light-emitting device, with the n-side electrode connected to at least one of the axial-direction end surface 2030 a of the underlying layer 2030 not covered with the insulator 2024 and the peripheral surface 2030 b of the underlying layer 2030 not covered with the insulator 2024 , and with the p-side electrode connected to the conductive film 2025 or the surface of the semiconductor layer 2023 exposed from the conductive film 2025 , a current is caused to flow from the p-type semiconductor layer 2023 to the n-type semiconductor core 2021 to result in recombination of electrons and holes in the quantum well layer 2022 . thus, light is emitted. at this point, the quantum well layer 2022 and the semiconductor layer 2023 are formed to cover the whole peripheral surface and the axial-direction end surface on one side of the semiconductor core 2021 , and therefore light is emitted from nearly all of the quantum well layer 2022 to result in expansion of the light emitting region. accordingly, the amount of emitted light can be increased, and the light emitting efficiency can be raised. the light emitting efficiency of the rod-like light-emitting device 2002 can be increased. therefore, using the rod-like light-emitting device 2002 , a backlight, an illuminating device, a display device and the like that have high light-emitting efficiencies and achieve low power consumption can be implemented. the quantum well layer 2022 is formed between the semiconductor core 2021 and the semiconductor layer 2023 . therefore, due to quantum confinement effects of the quantum well layer 2022 , the amount of emitted light can be more increased, and the light emitting efficiency can be more increased. the axial-direction end surface 2030 a and the peripheral surface 2030 b of the underlying layer 2030 are exposed, and therefore the n-side electrode can be easily connected to at least one of the axial-direction end surface 2030 a and the peripheral surface 2030 b. of the outer peripheral surface not covered with the semiconductor layer 2023 on the other side of the semiconductor core 2021 , the portion near the outer peripheral surface covered with the semiconductor layer 2023 on one side of the semiconductor core 2021 is covered with the insulator 2024 . as a result, the n-side electrode becomes less likely to be short-circuited to the p-side electrode, which facilitates formation of the n-side electrode and the p-side electrode. that is, even in the case where the p-side electrode to be connected to the semiconductor layer 2023 is formed near the step of the outer peripheral surface of the semiconductor core 2021 , the p-side electrode can be prevented from coming in contact with the semiconductor core 2021 , and therefore forming the n-side electrode and the p-side electrode is easy. such an effect can be obtained even in the case of forming the insulator 2024 ′ instead of the insulator 2024 . moreover, in the rod-like light-emitting device 2002 manufactured by the above method of manufacturing a rod-like light-emitting device, crystal growth of the quantum well layer 2022 a and the semiconductor layer 2023 a occurs radially outward from the outer peripheral surface of the semiconductor core 2021 a. the growth distance in the radial direction is short, and the defect deviates outward. accordingly, one side of the semiconductor core 2021 can be covered with the quantum well layer 2022 and the semiconductor layer 2023 having less crystal defects. this can make good the characteristics of the microscopic rod-like light-emitting device 2002 . in cases where the rod-like light-emitting devices 2002 are aligned on the substrate in such a manner that the axial direction of the rod-like light-emitting device 2002 is parallel to the surface of the substrate, the conductive film 2025 is formed such that the outer peripheral surface thereof is continuous with the outer peripheral surface of the insulator 2024 without a step. this can prevent the rod-like light-emitting device 2002 from being broken, and can prevent the rod-like light-emitting device 2002 from being inclined with respect to the surface of the substrate to be unstable. by preventing the rod-like light-emitting device 2002 from being inclined with respect to the surface of the substrate, the contact area of the rod-like light-emitting device 2002 with the surface of the substrate is increased. this makes it easier for the heat of the rod-like light-emitting device 2002 to diffuse to the substrate. in embodiments 36 and 37 described above, a microscopic rod-like light-emitting device may be manufactured using a semiconductor whose base material is gaas, algaas, gaasp, ingan, algan, gap, znse, algainp or the like. in embodiments 36 and 37, the n-type semiconductor cores 2011 and 2021 , the p-type quantum well layers 2012 and 2022 , the p-type semiconductor layers 2013 and 2023 , and the n-type underlying layer 2030 are used. however, a p-type semiconductor core, an n-type quantum well layer, an n-type semiconductor layer and a p-type underlying layer may be used. that is, the conductivity types in embodiments 36 and 37 may be reversed. in embodiments 36 and 37 described above, when the diameters of the semiconductor cores 2011 and 2021 are 300 nm or more and 50 μm or less, variations in the diameters of the semiconductor cores 2011 and 2021 can be reduced compared to the case of the semiconductor core having a diameter ranging from several tens of nanometers to several hundreds of nanometers. variations in the light emitting region, that is, variations in light emission characteristics can be reduced, and yields can be improved. in embodiments 36 and 37, descriptions have been given of the rod-like light-emitting devices 2001 and 2002 in which one sides of the semiconductor cores 2011 and 2021 having rod shapes whose cross sections are nearly circular are covered with the quantum well layers 2012 and 2022 and the semiconductor layers 2013 and 2023 . however, this invention may be applied to, for example, a rod-like light-emitting device in which one side of a semiconductor core having a rod shape whose cross section is nearly elliptical is covered with a quantum well layer, a semiconductor layer and the like, and a rod-like light-emitting device in which one side of a semiconductor core having a rod shape whose cross section is nearly hexagonal or has another polygon is covered with a quantum well layer, a semiconductor layer and the like. n-type gan results in hexagonal crystal growth, and a semiconductor core in the shape that is approximately a hexagonal prism is obtained by growing the crystals under the condition where a direction perpendicular to the surface of the substrate is the c-axis direction. depending on growth conditions such as a growth direction and a growth temperature, there is a tendency to form semiconductor cores whose cross sections have shapes that are nearly circular in cases where the diameters of the growth holes 2016 and 2026 are small in the range of from several tens of nanometers to several hundreds of nanometers. in cases where the diameters are large in the range of from about 0.5 μm to several hundreds of micrometers, there is a tendency to form semiconductor cores whose cross sections are nearly hexagonal. in embodiments 36 and 37, the semiconductor cores 2011 and 2021 are formed in which the diameter on one side is larger than that on the other side. however, a semiconductor core in which the diameter on one side is the same as that on the other side may be formed. such a semiconductor core can be easily formed by decreasing the volume of the island-like metal portion formed in the growth hole 2016 so that the cross-sectional shape of the catalyst metal portion is nearly semi-circular. in embodiments 36 and 37, under the condition where the island-like catalyst metal portions 2018 and 2028 are held in one ends of the semiconductor cores 2011 a and 2021 a, the quantum well layers 2012 a and 2022 a made of p-type ingan and the semiconductor layers 2013 a and 2023 a made of p-type gan are formed. however, only semiconductor layers may be formed. that is, the quantum well layers 2012 a and 2022 a need not be formed. in embodiments 36 and 37, the conductive films 2015 and 2025 are formed such that their outer peripheral surfaces are continuous with the outer peripheral surfaces of the insulators 2014 and 2024 without any steps. however, the conductive films 2015 and 2025 need not be formed, and the semiconductor layers may be formed such that their outer peripheral surfaces are continuous with the outer peripheral surfaces of the insulators 2014 and 2024 without any steps. in embodiments 36 and 37, the semiconductor cores 2011 a and 2021 a, the quantum well layers 2012 a and 2022 a, and the semiconductor layers 2013 a and 2023 a are formed using the catalyst metal portions 2018 and 2028 . however, the semiconductor cores, the quantum well layers and the semiconductor layers may be formed without using the catalyst metal portions 2018 and 2028 . in the above case where the semiconductor cores, the quantum well layers and the semiconductor layers are formed without using the catalyst metal portions 2018 and 2028 , in the quantum well layers and the semiconductor layers, the thickness in the axial direction of the portion covering the axial-direction end surface on one side of the semiconductor core is nearly the same as the thickness in the radial direction of the portion covering the outer peripheral surface of the semiconductor core. for this reason, in the insulator etching step, the axial-direction end surface on one side of the semiconductor core becomes likely to be exposed. the axial-direction end surface on one side of the semiconductor core is allowed to be exposed. in the separating steps of embodiments 36 and 37, the semiconductor core 2011 and 2021 may be mechanically separated from the substrate 2101 and 2201 using a cutting tool. using the cutting tool, the root close to the substrate 2101 of the semiconductor core 2011 that erects on the substrate 2101 is bent to cause stress to act on the semiconductor core 2011 covered with the semiconductor layer 2013 , so that the semiconductor core 2011 covered with the semiconductor layer 2013 is separated from the substrate 2101 . in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate 2101 can be separated for a short time in a simple way. in the insulator etching steps of embodiments 36 and 37, by etching the mask layers 2014 b and 2024 b to cause parts of the mask layers 2014 b and 2024 b to remain around ends on the other side of the semiconductor cores 2011 and 2021 , the conductive films 2015 a and 2025 a, the semiconductor layers 2013 a and 2023 a and the quantum well layers 2012 a and 2022 a may be lifted off all at once. in embodiments 36 and 37, instead of a mocvd device, other crystal growth devices such as a molecular-beam epitaxy (mbe) device may be used. (embodiment 38) next, a backlight, an illuminating device and a display device that include a rod-like light-emitting device of embodiment 38 of this invention are described. in this embodiment 38, rod-like light-emitting devices described in any one of embodiments 1 to 37 or modifications thereof are aligned on an insulating substrate. the rod-like light-emitting devices are aligned using a technique according to an invention entitled “method for aligning microscopic structures and substrate having microscopic structures aligned, as well as integrated circuit apparatus and display element”, for which japanese patent application no. 2007-102848 (as published under jp 2008-260073 a) was filed by the assignee of the present invention. fig. 99 is a plan view of an insulating substrate for use in a backlight, an illuminating device and a display device of this embodiment 38. as shown in fig. 99 , the metal electrodes 2351 and 2352 are formed on the surface of an insulating substrate 2350 . the insulating substrate 2350 may be formed of an insulator, such as glass, ceramic, aluminum oxide or resin, or may be a substrate wherein a silicon oxide film is formed on a surface of a semiconductor such as silicon so that the surface of the substrate has insulating properties. in the case of using a glass substrate, it is desirable that an underlying insulating film such as a silicon oxide film or a silicon nitride film be formed on the surface of the substrate. the metal electrodes 2351 and 2352 are formed in desired electrode shapes utilizing a printing technique. note that the metal electrodes 2351 and 2352 may be formed by depositing a metal film and a photosensitive film over the substrate, then exposing the photosensitive film in a desired electrode pattern, and etching the films. pads, which are omitted in fig. 99 , are formed for the metal electrodes 2351 and 2352 so that potentials can be provided from the outside. the rod-like light-emitting devices are aligned in portions where the metal electrodes 2351 and 2352 face each other (alignment regions). while 2 by 2 alignment regions in which the rod-like light-emitting devices are to be aligned are shown in fig. 99 , any number of regions may be arranged. fig. 100 is a schematic cross-sectional view as taken along the line 100 - 100 in fig. 99 . first, as shown in fig. 100 , isopropyl alcohol (ipa) 361 containing the rod-like light-emitting devices 2360 is thinly applied onto the insulating substrate 2350 . instead of the ipa 361 , ethylene glycol, propylene glycol, methanol, ethanol and acetone or a mixture thereof may be used. alternatively, instead of the ipa 361 , a liquid made of another organic substance, water and the like can be used. note that the rod-like light-emitting device 2360 is a rod-like light-emitting device described in any one of embodiments 1 to 37, or a modification thereof. however, if a large current flows between the metal electrodes 2351 and 2352 through the liquid, a desired voltage difference cannot be applied across the metal electrodes 2351 and 2352 . in such a case, the whole surface of the insulating substrate 2350 may be coated with an insulating film of from about 10 to 30 nm so that the metal electrodes 2351 and 2352 are covered. the thickness at which the ipa 361 containing the rod-like light-emitting devices 2360 is applied is a thickness that allows movement of the rod-like light-emitting devices 2360 in the liquid so that the rod-like light-emitting devices 2360 can be aligned in the subsequent step of aligning the rod-like light-emitting devices 2360 . accordingly, the thickness of the applied ipa 361 is equal to or larger than the thickness of the rod-like light-emitting device 2360 , and ranges, for example, from several micrometers to several millimeters. in cases where the thickness of the applied ipa is too small, it becomes difficult for the rod-like light-emitting devices 2360 to move, whereas in cases where the thickness is too large, time for drying the liquid becomes long. the amount of the rod-like light-emitting device 2360 relative to the amount of ipa is preferably in the range of from 1×10 4 /cm 3 to 1×10 7 /cm 3 . in order to apply the ipa 361 containing the rod-like light-emitting devices 2360 , a frame is formed in the outer periphery of the metal electrodes where the rod-like light-emitting devices 2360 are to be aligned, and the frame may be filled with the ipa 361 containing the rod-like light-emitting devices 2360 so that the applied ipa has a desired thickness. however, in cases where the ipa 361 containing the rod-like light-emitting devices 2360 has viscosity, the ipa 361 can be applied to a desired thickness without requiring the frame. it is desirable for the aligning step for the rod-like light-emitting devices 2360 that a liquid such as ipa, ethylene glycol, propylene glycol, . . . , or a mixture thereof, or a liquid made of another organic substance or water have a viscosity as low as possible, and be likely to be evaporated by heat. next, a potential difference is applied across the metal electrodes 2351 and 2352 . in this embodiment 38, a potential difference of 1 v is appropriate. a potential difference in the range of from 0.1 to 10 v may be applied across the metal electrodes 2351 and 2352 . however, in the case of a potential difference of 0.1 v or less, the alignment of rod-like light-emitting devices 2360 is poor. in the case of a potential difference of 10 v or more, insulation between the metal electrodes becomes problematic. accordingly, the potential difference is preferably in the range of from 1 v to 5 v, and more preferably about 1 v. fig. 101 shows the principle of aligning the rod-like light-emitting devices 2360 on the metal electrodes 2351 and 2352 . as shown in fig. 101 , when a potential v l is applied to the metal electrode 2351 , and a potential v r (v l <v r ) is applied to the metal electrode 2352 , negative charge is induced on the metal electrode 2351 , and positive charge is induced on the metal electrode 2352 . as the rod-like light-emitting device 2360 approaches the electrodes, positive charge is induced on a side close to the metal electrode 2351 of the rod-like light-emitting device 2360 , and negative charge is induced on a side close to the metal electrode 2352 of the rod-like light-emitting device 2360 . this induction of charges in the rod-like light-emitting device 2360 is due to electrostatic induction. that is, in the rod-like light-emitting device 2360 placed in an electric field, charges are induced on its surface until the electric field inside the device is zero. as a result, attraction due to the electrostatic force acts between the electrodes and the rod-like light-emitting devices 2360 , and therefore the rod-like light-emitting devices 2360 are aligned along the line of electric force between the metal electrodes 2351 and 2352 . charges induced on the rod-like light-emitting devices 2360 are nearly the same, and therefore the rod-like light-emitting devices 2360 are regularly aligned in a fixed direction at nearly regular intervals because of repulsive forces due to charges. however, for example, with the rod-like light-emitting devices 2001 shown in fig. 95 of embodiment 36, the orientations of the axial-direction end surfaces 2011 a are not fixed, but in a random fashion (this is true with the rod-like light-emitting devices in other embodiments and modifications). as described above, charges are generated in the rod-like light-emitting device 2360 by an external electric field generated between the metal electrodes 2351 and 2352 , and the force of attraction of charges causes the rod-like light-emitting device 2360 to be adsorbed to the metal electrodes 2351 and 2352 . therefore, the size of the rod-like light-emitting device 2360 need be large enough to allow the rod-like light-emitting device 2360 to move or migrate in the liquid. accordingly, the size of the rod-like light-emitting device 2360 should be selected in accordance with the amount (thickness) of the applied liquid. in cases where the amount of applied liquid is small, the rod-like light-emitting device 2360 needs to have a size in the order of nanometers. in contrast, in cases where the amount of applied liquid is large, the rod-like light-emitting device 2360 may have a size of the order of micrometers. in cases where the rod-like light-emitting devices 2360 are not electrically neutral but positively or negatively charged, just applying a static potential difference (dc) across the metal electrodes 2351 and 2352 would not make it possible to stably align the rod-like light-emitting devices 2360 . for example, in cases where the rod-like light-emitting devices 2360 are positively charged as a whole, attraction between the devices and the metal electrode 2352 on which positive charge is induced becomes relatively weak. therefore, the alignment of the rod-like light-emitting devices 2360 becomes asymmetrical. in such a case, as shown in fig. 102 , it is preferable that an ac voltage be applied across the metal electrodes 2351 and 2352 . in fig. 102 , a reference potential is applied to the metal electrode 2352 , and an alternating current (ac) voltage with an amplitude of v ppl /2 is applied to the metal electrode 2351 . in this way, even in cases where the rod-like light-emitting devices 2360 are charged, the alignment can be kept symmetrical. note that the frequency of the ac voltage applied to the metal electrode 2352 in this case is preferably in the range of from 10 hz to 1 mhz, and more preferably in the range of from 50 hz to 1 khz in which the alignment is most stable. moreover, the ac voltage applied across the metal electrodes 2351 and 2352 is not limited to being a sine wave, and may be a periodically varying wave, such as a rectangular wave, a triangular wave or a saw wave. note that v ppl is preferably about 1 v. next, the rod-like light-emitting devices 2360 are aligned and arranged on the metal electrodes 2351 and 2352 , and then the insulating substrate 2350 is heated, so that the liquid is evaporated and dried. the rod-like light-emitting devices 2360 are aligned and adhered along the line of electric force between the metal electrodes 2351 and 2352 at regular intervals. fig. 103 is a plan view of the insulating substrate 2350 on which the rod-like light-emitting devices 2360 are aligned. the insulating substrate 2350 on which the rod-like light-emitting devices 2360 are aligned is used for a backlight of a liquid crystal display device or the like. this makes it possible to implement a backlight whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. also, using as an illuminating device the insulating substrate 2350 having the rod-like light-emitting devices 2360 aligned thereon makes it possible to implement an illuminating device whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. fig. 104 is a plan view of a display device that uses an insulating substrate on which the rod-like light-emitting devices 2360 are aligned. as shown in fig. 104 , a display device 2300 has a display unit 2301 , a logic circuit unit 2302 , a logic circuit unit 2303 , a logic circuit unit 2304 and a logic circuit unit 2305 which are formed on the insulating substrate 2310 . in the display unit 2301 , the rod-like light-emitting devices 2360 are aligned at pixels arranged in a matrix. fig. 105 is a circuit diagram of a main part of the display unit 2301 of the display device 2300 . the display unit 2301 of the display device 2300 , as shown in fig. 105 , includes a plurality of scanning signal lines gl (just one line of which is shown in fig. 105 ) intersecting with a plurality of data signal lines sl (just one line of which is shown in fig. 105 ). the pixels are arranged in a matrix form, with one pixel placed in a portion enclosed by two adjacent scanning signal lines gl and two adjacent data signal lines sl. the pixel includes a switching element q 1 whose gate is connected to a scanning signal line gl and whose source is connected to a data signal line sl, a switching element q 2 whose gate is connected to the drain of the switching element q 1 , a pixel capacitor c of which one end is connected to the gate of the switching element q 2 , and a plurality of light emitting diodes d 1 to dn (rod-like light-emitting devices 2360 ) driven by the switching element q 2 . polarities of p and n of the rod-like light-emitting devices 2360 are not aligned, but arranged at random. therefore, at the time of driving, the rod-like light-emitting devices 2360 with different polarities alternately emit light when driven by an ac voltage. according to the above-described method of manufacturing a display device, the insulating substrate 2350 is produced where an alignment region are formed having as a unit the two electrodes 2351 and 2352 to which independent potentials are respectively to be provided, and a liquid containing the rod-like light-emitting devices 2360 with the size of the order of nanometers or of the order of micrometers is applied onto the insulating substrate 2350 . thereafter, independent voltages are respectively applied to the two electrodes 2351 and 2352 to align the microscopic rod-like light-emitting devices 2360 at positions defined by the two electrodes 2351 and 2352 . thus, the rod-like light-emitting devices 2360 can be easily aligned on the predetermined insulating substrate 2350 . with the above-described method of manufacturing a display device, the amount of semiconductors used can be decreased, and a display device whose thickness and weight can be reduced can be manufactured. the rod-like light-emitting device 2360 emits light from the whole periphery of the semiconductor core covered with the semiconductor layer. as a result, the light emitting region becomes larger. therefore, a display device that has a high light-emitting efficiency and achieves low power consumption can be implemented. in embodiment 38, a potential difference is provided between the two metal electrodes 2351 and 2352 formed on the surface of the insulating substrate 2350 , and the rod-like light-emitting devices 2360 are aligned between the metal electrodes 2351 and 2352 . however, the alignment is not limited to this. rod-like light-emitting devices may be aligned at positions defined by the electrodes by forming a third electrode between two electrodes formed on the surface of the insulating substrate, and applying independent voltages to the three electrodes, respectively. in embodiment 38, a description has been given of a display device including rod-like light-emitting devices. however, the rod-like light-emitting devices manufactured by the method of manufacturing a rod-like light-emitting device of this invention is not limited to this application, and may be applied other apparatuses such as a backlight and an illuminating device. (embodiment 39) fig. 106 is a perspective view of a light-emitting apparatus of embodiment 39 of this invention. the light-emitting apparatus of this embodiment 39, as shown in fig. 106 , includes an insulating substrate 316 , and a rod-like light-emitting device 310 mounted on the insulating substrate 316 such that the longitudinal direction of the rod-like light-emitting device 360 is parallel to the mounting surface of the insulating substrate 316 . the rod-like light-emitting device 310 includes a semiconductor core 311 made of n-type gan having a rod shape whose cross section is nearly hexagonal, a semiconductor layer 312 made of p-type gan and formed to cover part of the semiconductor core 311 . the semiconductor core 311 has, at one end thereof, an exposed portion 311 a in which the outer peripheral surface of the semiconductor core 311 is exposed. the end surface of the other end of the semiconductor core 311 is covered with the semiconductor layer 312 . in the rod-like light-emitting device 310 mounted on the insulating substrate 316 such that the longitudinal direction of the rod-like light-emitting device 310 is parallel to the mounting surface of the insulating substrate 316 , the outer peripheral surface of the semiconductor layer 312 is in contact with the mounting surface of the insulating substrate 316 . therefore, heat generated in the rod-like light-emitting device 310 can be dissipated with a good efficiency from the semiconductor layer 312 to the insulating substrate 316 . accordingly, even in cases where a plurality of rod-like light-emitting devices are arranged, heat is less likely to be absorbed to the adjacent rod-like light-emitting devices. therefore, it is possible to implement a light-emitting apparatus having a high light-extraction efficiency and good heat dissipation compared to traditional techniques. in the above-mentioned light-emitting apparatus, the rod-like light-emitting device 310 is arranged to lie on its side on the insulating substrate 316 . this allows the whole thickness of the rod-like light-emitting device 310 including the insulating substrate 316 to be decreased. the rod-like light-emitting device 310 is manufactured as follows. first, a mask having a growth hole is formed on a substrate made of n-type gan. silicon oxide (sio 2 ), silicon nitride (si 3 n 4 ) or another material that is selectively etchable with respect to the semiconductor core 311 and the semiconductor layer 312 is used as the material for the mask. to form a growth hole, a lithography method and a dry etching method, which are known and used for usual semiconductor processes, can be used. next, the semiconductor core 311 shaped like a rod is formed by crystal growth of n-type gan on the substrate exposed through a growth hole of the mask using a metal organic chemical vapor deposition (mocvd) device. the temperature of the mocvd device is set to about 950° c., trimethylgalium (tmg) and ammonia (nh 3 ) are used as growth gases, and silane (sih 3 ) for n-type impurity supply and further hydrogen (h 2 ) as a carrier gas are supplied, so that the semiconductor core of n-type gan with si used as the impurity can be grown. at this point, the diameter of the semiconductor core 311 to be grown can be determined depending on the diameter of the growth hole of the mask. the grown n-type gan results in a hexagonal crystal growth, and the semiconductor core in the shape of a hexagonal prism is obtained by growing n-type gan under the condition where a direction perpendicular to the surface of the substrate is the c-axis direction. next, a semiconductor layer made of p-type gan is formed over the whole substrate so that the rod-like semiconductor core 311 is covered with the semiconductor layer. the temperature of the mocvd device is set to about 960° c., tmg and nh 3 are used as growth gases, and bis(cyclopentadienyl)magnesium (cp 2 mg) is used for p-type impurity supply, so that p-type gan with magnesium (mg) used as the impurity can be grown. next, all of the region except for a portion covering the semiconductor core of the semiconductor layer, and the mask are removed by lift-off to expose the outer peripheral surface on the substrate side of the rod-like semiconductor core 311 , so that the exposed portion 311 a is formed. in this state, the end surface of the semiconductor core 311 opposite to the substrate is covered with the semiconductor layer 312 . in the case where a mask is made of silicon oxide (sio 2 ) or silicon nitride (si 3 n 4 ), use of a solution containing hydrofluoric acid (hf) enables the mask to be easily etched without affecting the semiconductor core and the semiconductor layer portion covering the semiconductor core, and enables the mask together with the semiconductor layer on the mask (all of the region of the semiconductor layer except for a portion thereof covering the semiconductor core) to be removed by lift-off. in this embodiment, the length of the exposed portion 311 a of the semiconductor core 311 is determined depending on the thickness of the removed mask. the lift-off is used in the exposing step of this embodiment; however, part of the semiconductor core may be exposed by etching. next, the substrate is immersed in an isopropyl alcohol (ipa) aqueous solution, and is vibrated along the plane of the substrate using ultrasonic waves (e.g., several tens of kilo-hertz). this causes stress to act on the semiconductor core 311 covered with the semiconductor layer 312 so as to bend the root close to the substrate of the semiconductor core 311 that erects on the substrate. as a result, the semiconductor core 311 covered with the semiconductor layer 312 is separated from the substrate. in this way, the microscopic rod-like light-emitting device that is separated from the substrate made of n-type gan can be manufactured. the rod-like light-emitting devices separated from the substrate made of n-type gan are obtained in a state in which the devices are dispersed in an ipa aqueous solution. this dispersion liquid is applied onto the mounting surface of the insulating substrate 316 and then is dried, so that the rod-like light-emitting devices can be arranged in parallel to the mounting surface of the insulating substrate 316 . moreover, in the rod-like light-emitting device described above, crystal growth of the semiconductor layer 312 occurs radially outward from the outer peripheral surface of the semiconductor core 311 . the growth distance in the radial direction is short and the defect deviates outward, and therefore the semiconductor core 311 can be covered with the semiconductor layer 312 having less crystal defects. accordingly, a rod-like light-emitting device having good characteristics can be implemented. according to a rod-like light-emitting device having the above configuration, the semiconductor layer 312 made of p-type gan is formed to cover the semiconductor core 11 shaped like a rod and made of n-type gan, and to expose the outer peripheral surface of part of the semiconductor core 311 . this makes it possible to connect the exposed portion 311 a of the semiconductor core 311 to an n-side electrode and to connect a p-side electrode to a portion of the semiconductor layer 312 with which the semiconductor core 311 is covered, even when the rod-like light-emitting device is microscopic and has a size of the order of micrometers or of the order of nanometers. in the rod-like light-emitting device, with the n-side electrode connected to the exposed portion 311 a of the semiconductor core 311 and with the p-side electrode connected to the semiconductor layer 312 , a current is caused to flow from the p-side electrode to the n-side electrode to result in recombination of electrons and holes in a pn junction between the outer peripheral surface of the semiconductor core 311 and the inner peripheral surface of the semiconductor layer 312 . thus, light is emitted from the pn junction. in this rod-like light-emitting device, light is emitted from the whole periphery of the semiconductor core 311 covered with the semiconductor layer 312 . the light emitting region therefore becomes larger, which results in a high light emitting efficiency. accordingly, it is possible to implement a microscopic rod-like light-emitting device that allows electrode connections to be easily made with a simple configuration and has a high light emitting efficiency. the above rod-like light-emitting device is not integral with the substrate, which allows great freedom in installing into an apparatus. the microscopic rod-like light-emitting device as used herein is a device, for example, in micrometer order size with a diameter of 1 μm and a length in the range of from 10 μm to 30 μm, or in nanometer order size in which at least the diameter of the diameter and the length of 1 μm or less. the rod-like light-emitting device mentioned above allows a decrease in the amount of semiconductors used. this makes it possible to reduce the thickness and weight of an apparatus using the light-emitting device, and to implement a backlight, an illuminating device and a display device that have high light emitting efficiencies and achieve low power consumption. the outer peripheral surface of the region covered with the semiconductor layer 312 of the semiconductor core 311 and the outer peripheral surface of the exposed region of the semiconductor core 311 are continuous with each other such that the exposed region of the semiconductor core 311 is thinner than the outer diameter of the semiconductor layer 312 , and therefore, in the manufacturing step, the side of the substrate of the exposed region of the semiconductor core 311 becomes more likely to be broken on the substrate side in the exposed region of the semiconductor core 311 , which facilitates manufacturing. the outer peripheral surface on one side of the above semiconductor core 311 is exposed, for example, by about 5 μm. this makes it possible to easily connect one electrode (interconnection) to the exposed portion 311 a of the outer peripheral surface of the semiconductor core 311 and connect the electrode (interconnection) to the semiconductor layer 312 on the other side of the semiconductor core 311 using known semiconductor processes having normal processing accuracy, such as a lift-off method and a nanoimprint method. therefore, connections can be made with the electrodes separate from each other in both ends. thus, the electrode connected to the semiconductor layer 312 and the exposed portion of the semiconductor core 311 can easily be prevented from becoming short-circuited to each other. the end surface of the other end of the semiconductor core 311 is covered with the semiconductor layer 312 . this makes it possible to easily connect the electrode to the portion of the semiconductor layer 312 covering the end surface of the semiconductor core 311 opposite to the exposed portion 311 a , without causing the electrode to be short-circuited to the semiconductor core 311 . in this way, electrodes can easily be connected to both ends of the microscopic rod-like light-emitting device. the outer peripheral surface of the region covered with the semiconductor layer 312 of the semiconductor core 311 and the outer peripheral surface of the exposed region of the semiconductor core 311 are continuous with each other such that the exposed region of the semiconductor core 311 is thinner than the outer diameter of the semiconductor layer 312 , and therefore, in the manufacturing step, the side of the substrate of the exposed region of the semiconductor core 311 becomes more likely to be broken on the substrate side in the exposed region of the semiconductor core 311 that erects on the substrate, which facilitates manufacturing. (embodiment 40) fig. 107 is a perspective view of a light-emitting apparatus of embodiment 40 of this invention. the light-emitting apparatus of this embodiment 40, as shown in fig. 107 , includes an insulating substrate 326 , and a rod-like light-emitting device 320 mounted on the insulating substrate 326 such that the longitudinal direction of the rod-like light-emitting device 320 is parallel to the mounting surface of the insulating substrate 326 . the rod-like light-emitting device 320 includes a semiconductor core 321 made of n-type gan having a rod shape whose cross section is nearly hexagonal, a quantum well layer 322 made of p-type ingan and formed to cover part of the semiconductor core 321 , and a semiconductor layer 323 made of p-type gan and formed to cover the quantum well layer 322 . the semiconductor core 321 has, at one end thereof, an exposed portion 321 a in which the outer peripheral surface of the semiconductor core 311 is exposed. the end surface of the other end of the semiconductor core 321 is covered with the quantum well layer 322 and the semiconductor layer 323 . in the above-described light-emitting apparatus of embodiment 40, like the rod-like light-emitting device of the light-emitting apparatus of embodiment 39, the semiconductor core 321 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using a mocvd device. the above-described light-emitting apparatus of embodiment 40 has effects similar to those of the light-emitting apparatus of embodiment 39. the quantum well layer 322 is formed between the semiconductor core 321 and the semiconductor layer 323 . as a result, due to quantum confinement effects of the quantum well layer 322 , the light emitting efficiency can further be improved. after the semiconductor core 321 of n-type gan has been grown in the mocvd device as described above, the set temperature is changed from 600° c. to 800° c. in accordance with the wavelength of emitted light, and nitrogen (n 2 ) is supplied to the carrier gas and tmg, nh 3 and trimethylindium (tmi) are supplied to the growth gas. in this way, the ingan quantum well layer 322 can be formed on the semiconductor core 321 of n-type gan. thereafter, further, the set temperature is changed to 960° c., and tmg and nh 3 are used as the growth gases as mentioned above, and cp 2 mg is used for p-type impurity supply. in this way, the semiconductor layer 323 made of p-type gan can be formed. note that the quantum well layer may have a p-type algan layer as an electron block layer inserted between the ingan layer and the p-type gan layer, and may also have a multiple quantum well structure in which barrier layers of gan and quantum well layers of ingan are alternately laminated. (embodiment 41) fig. 108 is a perspective view of a light-emitting apparatus of embodiment 41 of this invention. the light-emitting apparatus of this embodiment 41, as shown in fig. 108 , includes an insulating substrate 336 , and a rod-like light-emitting device 330 mounted on the insulating substrate 336 such that the longitudinal direction of the rod-like light-emitting device 360 is parallel to the mounting surface of the insulating substrate 336 . the rod-like light-emitting device 330 includes a semiconductor core 331 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a semiconductor layer 332 made of p-type gan and formed to cover part of the semiconductor core 331 , and a transparent electrode 333 formed to cover the semiconductor layer 332 . the semiconductor core 331 has, at one end thereof, an exposed portion 331 a in which the outer peripheral surface of the semiconductor core 331 is exposed. the end surface of the other end of the semiconductor core 331 is covered with the semiconductor layer 332 and the transparent electrode 333 . the transparent electrode 333 is formed of tin-doped indium oxide (ito) having a thickness of 200 nm. after the formation up to the semiconductor layer 332 made of p-type gan using the mocvd device, the rod-like light-emitting device 330 together with the substrate made of n-type gan is transferred from the mocvd device to a vapor deposition device or a sputtering device, and an ito film is deposited to cover the semiconductor layer 332 . after the deposition of the ito film, heat treatment is performed at a temperature of from 500° c. to 600° c., which makes it possible to decrease the resistance between the semiconductor layer 332 made of p-type gan and the transparent electrode 333 made of ito. note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm. for the deposition of the laminated metal film ag/ni, a vapor-deposition method or a sputtering method can be used. in order to further decrease the resistance of the electrode layers, a laminated metal film of ag/ni may be formed after the deposition of the ito film. connecting an electrode (or interconnection) to an end of the transparent electrode 333 far from the exposed portion 331 a of the semiconductor core 331 can easily prevent short-circuiting between the electrode and the semiconductor core 331 , and the electrode (or interconnection) connected to the transparent electrode 333 can be thick to enable heat to be dissipated with a good efficiency through the electrode (or interconnection). in the rod-like light-emitting device 330 , an n-side electrode (not shown) is connected to the exposed portion 331 a of the semiconductor core 331 , and a p-side electrode (not shown) is connected to the transparent electrode 334 on the other side. the p-side electrode is connected to an end of the transparent electrode 333 , and therefore the area obtained by shielding the light emitting region by the electrodes can be minimized to increase the light-extraction efficiency. in the above rod-like light-emitting device of embodiment 41, like the rod-like light-emitting device of the light-emitting apparatus of embodiment 39, the semiconductor core 331 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using a mocvd device. the above-described light-emitting apparatus of embodiment 41 has effects similar to those of the light-emitting apparatus of embodiment 39. forming the transparent electrode 333 to cover the semiconductor layer 332 causes the semiconductor layer 332 to be connected through the transparent electrode 333 to the electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that the whole device can emit light. thus, the light emitting efficiency is further improved. in particular, with a configuration of a semiconductor core made of an n-type semiconductor and a semiconductor layer made of a p-type semiconductor, the semiconductor layer made of the p-type semiconductor is less likely to increase the impurity concentration, and the resistance is high. therefore, a current is likely to be concentrated to the electrode connection portion. however, the transparent electrode allows a wide current path to be formed. this enables the whole device to emit light. thus, the light emitting efficiency is further improved. (embodiment 42) fig. 109 is a perspective view of a light-emitting apparatus of embodiment 42 of this invention. the light-emitting apparatus of this embodiment 42, as shown in fig. 109 , includes an insulating substrate 346 , and a rod-like light-emitting device 340 mounted on the insulating substrate 346 such that the longitudinal direction of the rod-like light-emitting device 340 is parallel to the mounting surface of the insulating substrate 346 . the rod-like light-emitting device 340 includes a semiconductor core 341 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 342 made of p-type ingan and formed to cover part of the semiconductor core 341 , a semiconductor layer 343 made of p-type gan and formed to cover the quantum well layer 342 , and a transparent electrode 344 formed to cover the semiconductor layer 343 . the semiconductor core 341 has, at one end thereof, an exposed portion 341 a in which the outer peripheral surface of the semiconductor core 341 is exposed. the end surface of the other end of the semiconductor core 341 is covered with the quantum well layer 342 , the semiconductor layer 343 and the transparent electrode 344 . the transparent electrode 344 is formed of tin-doped indium oxide (ito). note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm. connecting an electrode (or interconnection) to an end of the transparent electrode 344 far from the exposed portion 341 a of the semiconductor core 341 can easily prevent the electrode from being short-circuited to the side of the semiconductor core 341 , and the electrode (or interconnection) connected to the transparent electrode 344 can be made thick or the cross-sectional area of the electrode can be increased. therefore, heat can be dissipated with a good efficiency through the electrode (or interconnection). in the rod-like light-emitting device 340 , an n-side electrode (not shown) is connected to the exposed portion 341 a of the semiconductor core 341 , and a p-side electrode (not shown) is connected to the transparent electrode 344 on the other side. the p-side electrode is connected to an end of the transparent electrode, and therefore the area obtained by shielding the light emitting region by the electrodes can be minimized. as a result, the light-extraction efficiency can be increased. in the above rod-like light-emitting device of embodiment 42, like the rod-like light-emitting device of the light-emitting apparatus of embodiment 39, the semiconductor core 341 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using a mocvd device. the above-described light-emitting apparatus of embodiment 42 has effects similar to those of the light-emitting apparatus of embodiment 40. forming the transparent electrode 344 to cover the semiconductor layer 343 allows the semiconductor layer 343 to be connected through the transparent electrode 344 to the p-side electrode. this allows a wide current path to be formed without a current being concentrated to an electrode connection portion and being unbalanced, so that the whole device can emit light. thus, the light emitting efficiency is further improved. in particular, with a configuration of a semiconductor core made of an n-type semiconductor and a semiconductor layer made of a p-type semiconductor, the semiconductor layer made of the p-type semiconductor is less likely to increase the impurity concentration, and the resistance is high. therefore, a current is likely to be concentrated to the electrode connection portion. however, the transparent electrode allows a wide current path to be formed. this enables the whole device to emit light. thus, the light emitting efficiency is further improved. (embodiment 43) fig. 110 is a side view of a light-emitting apparatus of embodiment 43 of this invention. the light-emitting apparatus of this embodiment 43, as shown in fig. 110 , includes an insulating substrate 356 , and a rod-like light-emitting device 350 mounted on the insulating substrate 356 such that the longitudinal direction of the rod-like light-emitting device 350 is parallel to the mounting surface of the insulating substrate 356 . the rod-like light-emitting device 350 includes a semiconductor core 351 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a semiconductor layer 352 made of p-type gan and formed to cover part of the semiconductor core 351 , and a transparent electrode 353 formed to cover the semiconductor layer 352 . the semiconductor core 351 has, at one end thereof, an exposed portion 351 a in which the outer peripheral surface of the semiconductor core 351 is exposed. a metal layer 354 made of al is formed on the transparent electrode 353 and on the side of the insulating substrate 356 . the metal layer 354 covers about the lower half of the outer peripheral surface of the transparent electrode 353 . the end surface of the other end of the semiconductor core 351 is covered with the semiconductor layer 352 and the transparent electrode 353 . the transparent electrode 353 is formed of ito. note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm. the material used for the metal layer 354 is not limited to al, and cu, w, ag, au and the like may be used. in the above-described light-emitting apparatus of embodiment 43, like the rod-like light-emitting device of the light-emitting apparatus of embodiment 41, the semiconductor core 351 shaped like a rod is formed by crystal growth of n-type gan on the substrate made of n-type gan using a mocvd device. after the formation up to the semiconductor layer 352 made of p-type gan in the mocvd device, the rod-like light-emitting device is transferred to a vapor deposition device, and the transparent electrode 353 made of ito is formed to cover the semiconductor layer 352 . heat treatment is performed at a temperature of from 500° c. to 600° c. after the deposition of the ito film. then, the transfer to a vapor deposition device is made, and an al film is deposited to cover the transparent electrode 353 . subsequently, like embodiment 39, the semiconductor layer, the transparent electrode and the al layer that cover the semiconductor core, and a mask are removed by lift-off to expose part of the semiconductor core 351 , and then the rod-like light-emitting device is separated from the substrate made of n-type gan utilizing ultrasonic waves. the longitudinal direction of the rod-like light-emitting device is arranged in parallel to the mounting surface of the insulating substrate 356 . further, of the metal layer made of al, a portion that is on the transparent electrode 353 and is not on the side of the insulating substrate 356 is etched back by isotropic dry etching, so that the metal layer 354 covering about the lower half of the outer peripheral surface of the transparent electrode 353 can be formed. as the etch-back of the metal layer made of al, a known al dry etching method for use in semiconductor processes can be used. the above-described light-emitting apparatus of embodiment 43 has effects similar to those of the light-emitting apparatus of embodiment 41. due to the metal layer 354 formed on the transparent electrode 353 and on the side of the insulating substrate 356 , light emitted from the rod-like light-emitting device 350 toward the insulating substrate 356 is reflected from the metal layer 354 . therefore, the light-extraction efficiency is improved. (embodiment 44) fig. 111 is a side view of a light-emitting apparatus of embodiment 44 of this invention. the light-emitting apparatus of this embodiment 44, as shown in fig. 111 , includes an insulating substrate 366 , and a rod-like light-emitting device 360 mounted on the insulating substrate 366 such that the longitudinal direction of the rod-like light-emitting device 360 is parallel to the mounting surface of the insulating substrate 366 . the rod-like light-emitting device 360 includes a semiconductor core 361 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 362 made of p-type ingan and formed to cover part of the semiconductor core 361 , a semiconductor layer 363 made of p-type gan and formed to cover the quantum well layer 362 , and a transparent electrode 364 formed to cover the semiconductor layer 363 . the semiconductor core 361 has, at one end thereof, an exposed portion 361 a in which the outer peripheral surface of the semiconductor core 361 is exposed. a metal layer 365 made of al is formed on the transparent electrode 364 and on the side of the insulating substrate 366 . the metal layer 365 covers about the lower half of the outer peripheral surface of the transparent electrode 364 . the transparent electrode 364 is formed of ito. note that the transparent electrode is not limited to this, and a laminated metal film of, for example, ag/ni having a thickness of 5 nm. the material used for the metal layer 365 is not limited to al, and cu, w, ag, au and the like may be used. fig. 112 is a cross-sectional view of the above-described light-emitting apparatus, in which the end surface of the other end of the semiconductor core 361 is covered with the quantum well layer 362 , the semiconductor layer 363 and the transparent electrode 364 . the above-described light-emitting apparatus of embodiment 44 has effects similar to those of the light-emitting apparatus of embodiment 42. due to the metal layer 365 formed on the transparent electrode 364 and on the side of the insulating substrate 366 , light emitted from the rod-like light-emitting device 360 toward the insulating substrate 366 is reflected from the metal layer 365 . therefore, the light-extraction efficiency is improved. while n-type gan doped with si and p-type gan doped with mg are used in embodiments 39 to 44 described above, impurities for doping gan are not limited to this case. for the n type, ge and the like can be used, and for the p type, zn and the like can be used. in embodiments 39 to 44, descriptions have been given of a rod-like light-emitting device that includes a semiconductor core having a rod shape whose cross section is nearly hexagonal. this invention is not limited to this. the cross section of the rod shape may be circular or ellipsoidal, and this invention may be applied to a rod-like light-emitting device that includes a semiconductor core having a rod shape whose cross section is in the shape of another polygon such as a triangle. depending on growth conditions such as a growth direction and a growth temperature, the shape of the cross section tends to be nearly circular in cases where the semiconductor core to be grown has a small diameter in the range of from several tens of nanometers to several hundreds of nanometers. in cases where the diameter is large in the range of from about 0.5 μm to several hundreds of micrometers, it becomes easier to grow the semiconductor core whose cross section is nearly hexagonal. for example, as shown in fig. 113 , a rod-like light-emitting device 370 includes a semiconductor core 371 made of n-type gan and having a rod shape whose cross section is nearly circular, and a semiconductor layer 372 made of p-type gan and formed to cover part of the semiconductor core 371 , and a transparent electrode 373 formed to cover the semiconductor layer 372 . the semiconductor core 371 has, at one end thereof, an exposed portion 371 a in which the outer peripheral surface of the semiconductor core 371 is exposed. a metal layer 374 made of al is formed on the transparent electrode 373 and on the side of a substrate 376 . the end surface of the other end of the semiconductor core 371 is covered with the semiconductor layer 372 and the transparent electrode 373 . as shown in fig. 114 , a rod-like light-emitting device 380 includes a semiconductor core 381 made of n-type gan and having a rod shape whose cross section is nearly circular, a quantum well layer 382 made of p-type ingan and formed to cover part of the semiconductor core 381 , a semiconductor layer 383 made of p-type gan and formed to cover the quantum well layer 382 , and a transparent electrode 384 formed to cover the semiconductor layer 383 . the semiconductor core 381 has, at one end thereof, an exposed portion 381 a in which the outer peripheral surface of the semiconductor core 381 is exposed. a metal layer 385 made of al is formed on the transparent electrode 384 and on the side of a substrate 386 . the end surface of the other end of the semiconductor core 381 is covered with the quantum well layer 382 , the semiconductor layer 383 and the transparent electrode 384 . (embodiment 45) fig. 115 is a side view of a light-emitting apparatus of embodiment 45 of this invention, and fig. 116 is a perspective view of the light-emitting apparatus. in this embodiment 45, any one of the rod-like light-emitting devices of the light-emitting apparatuses of embodiments 1 to 44 described above is used. fig. 116 shows a rod-like light-emitting device having the same configuration as the rod-like light-emitting device of the light-emitting apparatus of embodiment 40. the light-emitting apparatus of this embodiment 45, as shown in figs. 115 and 116 , includes an insulating substrate 450 on which metal electrodes 451 and 452 are formed on a mounting surface, and a rod-like light-emitting devices 460 mounted on the insulating substrate 450 such that the longitudinal direction of the rod-like light-emitting device 460 is parallel to a mounting surface of the insulating substrate 450 . the rod-like light-emitting device 460 , as shown in fig. 116 , includes a semiconductor core 471 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 472 made of p-type ingan and formed to cover part of the semiconductor core 471 , and a semiconductor layer 473 made of p-type gan and formed to cover the quantum well layer 472 . in the semiconductor core 471 , an exposed portion 471 a is formed. in the exposed portion 471 a , the outer peripheral surface of the semiconductor core 471 is exposed. the end surface of the other end of the semiconductor core 471 is covered with the quantum well layer 472 and the semiconductor layer 473 . as shown in fig. 115 and fig. 116 , the exposed portion 471 a on one side of the rod-like light-emitting device 460 is connected to the metal electrode 451 , and the semiconductor layer 473 on the other side of the rod-like light-emitting device 460 is connected to the metal electrode 452 . here, in the rod-like light-emitting device 460 , its central portion is deformed to come in contact with the insulating substrate 450 . this deformation is caused by stiction that occurs when a droplet contracts in a clearance between the substrate surface and the rod-like light-emitting device because of vaporization during drying of an ipa aqueous solution. next, a backlight, an illuminating device and a display device including light-emitting apparatuses in which the rod-like light-emitting devices 460 are aligned on the insulating substrate 450 are described. the rod-like light-emitting devices are aligned using a technique according to an invention entitled “method for aligning microscopic structures and substrate having microscopic structures aligned, as well as integrated circuit apparatus and display element”, for which japanese patent application no. 2007-102848 (as published under jp 2008-260073 a) was filed by the assignee of the present invention. fig. 117 is a plan view of an insulating substrate for use in a backlight, an illuminating device and a display device of this embodiment 45. as shown in fig. 117 , metal electrodes 451 and 452 are formed on the surface of an insulating substrate 450 . the insulating substrate 450 may be formed of an insulator, such as glass, ceramic, aluminum oxide or resin, or may be a substrate wherein a silicon oxide film is formed on a surface of a semiconductor such as silicon so that the surface of the substrate has insulating properties. in the case of using a glass substrate, it is desirable that an underlying insulating film such as a silicon oxide film or a silicon nitride film be formed on the surface of the substrate. the metal electrodes 451 and 452 are formed in desired electrode shapes utilizing a printing technique. note that the metal electrodes 451 and 452 may be formed by depositing a metal film and a photosensitive film over the substrate, then exposing the photosensitive film in a desired electrode pattern, and etching the films. pads, which are omitted in fig. 117 , are formed for the metal electrodes 451 and 452 so that potentials can be provided from the outside. the rod-like light-emitting devices are aligned in portions where the metal electrodes 451 and 452 face each other (alignment regions). while 2 by 2 alignment regions in which the rod-like light-emitting devices are to be aligned are shown in fig. 117 , any number of regions may be arranged. fig. 118 is a schematic cross-sectional view as taken along the line 118 - 118 in fig. 117 . first, as shown in fig. 118 , isopropyl alcohol (ipa) 161 containing the rod-like light-emitting devices 460 is thinly applied onto the insulating substrate 450 . instead of the ipa 361 , ethylene glycol, propylene glycol, methanol, ethanol and acetone or a mixture thereof may be used. alternatively, instead of the ipa 361 , a liquid made of another organic substance, water and the like can be used. however, if a large current flows between the metal electrodes 451 and 452 through the liquid, a desired voltage difference cannot be applied across the metal electrodes 451 and 452 . in such a case, the whole surface of the insulating substrate 450 may be coated with an insulating film of from about 10 to 30 nm so that the metal electrodes 451 and 452 are covered. the thickness at which the ipa 161 containing the rod-like light-emitting devices 460 is applied is a thickness that allows movement of the rod-like light-emitting devices 460 in the liquid so that the rod-like light-emitting devices 460 can be aligned in the subsequent step of aligning the rod-like light-emitting devices 460 . accordingly, the thickness of the applied ipa 161 is equal to or larger than the thickness of the rod-like light-emitting device 460 , and ranges, for example, from several micrometers to several millimeters. in cases where the thickness of the applied ipa is too small, it becomes difficult for the rod-like light-emitting devices 460 to move, whereas in cases where the thickness is too large, time for drying the liquid becomes long. the amount of the rod-like light-emitting device 460 relative to the amount of ipa is preferably in the range of from 1×10 4 /cm 3 to 1×10 7 /cm 3 . in order to apply the ipa 161 containing the rod-like light-emitting devices 460 , a frame is formed in the outer periphery of the metal electrodes where the rod-like light-emitting devices 460 are to be aligned, and the frame may be filled with the ipa 161 containing the rod-like light-emitting devices 460 so that the applied ipa has a desired thickness. however, in cases where the ipa 161 containing the rod-like light-emitting devices 460 has viscosity, the ipa 161 can be applied to a desired thickness without requiring the frame. it is desirable for the aligning step for the rod-like light-emitting devices 460 that a liquid such as ipa, ethylene glycol, propylene glycol, . . . , or a mixture thereof, or a liquid made of another organic substance or water have a viscosity as low as possible, and be likely to be evaporated by heat. next, a potential difference is applied across the metal electrodes 451 and 452 . in this embodiment 38, a potential difference of 1 v is appropriate. a potential difference in the range of from 0.1 to 10 v may be applied across the metal electrodes 451 and 452 . however, in the case of a potential difference of 0.1 v or less, the alignment of rod-like light-emitting devices 460 is poor. in the case of a potential difference of 10 v or more, insulation between the metal electrodes becomes problematic. accordingly, the potential difference is preferably in the range of from 1 v to 5 v, and more preferably about 1 v. fig. 119 shows the principle of aligning the rod-like light-emitting devices 460 on the metal electrodes 451 and 452 . as shown in fig. 119 , when a potential v l is applied to the metal electrode 451 , and a potential v r (v l <v r ) is applied to the metal electrode 452 , negative charge is induced on the metal electrode 451 , and positive charge is induced on the metal electrode 452 . as the rod-like light-emitting device 460 approaches the electrodes, positive charge is induced on a side close to the metal electrode 451 of the rod-like light-emitting device 460 , and negative charge is induced on a side close to the metal electrode 2352 of the rod-like light-emitting device 460 . this induction of charges in the rod-like light-emitting device 2360 is due to electrostatic induction. that is, in the rod-like light-emitting device 460 placed in an electric field, charges are induced on its surface until the electric field inside the device is zero. as a result, attraction due to the electrostatic force acts between the electrodes and the rod-like light-emitting devices 460 , and therefore the rod-like light-emitting devices 460 are aligned along the line of electric force between the metal electrodes 451 and 452 . charges induced on the rod-like light-emitting devices 460 are nearly the same, and therefore the rod-like light-emitting devices 460 are regularly aligned in a fixed direction at nearly regular intervals because of repulsive forces due to charges. however, regarding the rod-like light-emitting devices shown in fig. 106 of embodiment 39, for example, the orientations of the exposed portions 311 a of the semiconductor cores 311 are not fixed, but in a random fashion (this is true with the rod-like light-emitting devices in other embodiments and modifications). as described above, charges are generated in the rod-like light-emitting device 2360 by an external electric field generated between the metal electrodes 2351 and 2352 , and the force of attraction of charges causes the rod-like light-emitting device 2360 to be adsorbed to the metal electrodes 2351 and 2352 . therefore, the size of the rod-like light-emitting device 2360 need be large enough to allow the rod-like light-emitting device 2360 to move or migrate in the liquid. accordingly, the size of the rod-like light-emitting device 2360 should be selected in accordance with the amount (thickness) of the applied liquid. in cases where the amount of applied liquid is small, the rod-like light-emitting device 2360 needs to have a size in the order of nanometers. in contrast, in cases where the amount of applied liquid is large, the rod-like light-emitting device 2360 may have a size of the order of micrometers. in cases where the rod-like light-emitting devices 460 are not electrically neutral but positively or negatively charged, just applying a static potential difference (dc) across the metal electrodes 451 and 452 would not make it possible to stably align the rod-like light-emitting devices 460 . for example, in cases where the rod-like light-emitting devices 460 are positively charged as a whole, attraction between the devices and the metal electrode 2352 on which positive charge is induced becomes relatively weak. therefore, the alignment of the rod-like light-emitting devices 460 becomes asymmetrical. in such a case, as shown in fig. 120 , it is preferable that an ac voltage be applied across the metal electrodes 451 and 452 . in fig. 120 , a reference potential is applied to the metal electrode 451 , and an alternating current (ac) voltage with an amplitude of v ppl /2 is applied to the metal electrode 452 . in this way, even in cases where the rod-like light-emitting devices 460 are charged, the alignment can be kept symmetrical. note that the frequency of the ac voltage applied to the metal electrode 452 in this case is preferably in the range of from 10 hz to 1 mhz, and more preferably in the range of from 50 hz to 1 khz in which the alignment is most stable. moreover, the ac voltage applied across the metal electrodes 2351 and 2352 is not limited to being a sine wave, and may be a periodically varying wave, such as a rectangular wave, a triangular wave or a saw wave. note that v ppl is preferably about 1 v. next, the rod-like light-emitting devices 460 are aligned and arranged on the metal electrodes 451 and 452 , and then the insulating substrate 450 is heated, so that the liquid is evaporated and dried. the rod-like light-emitting devices 460 are aligned and arranged and adhered along the lines of electric force between the metal electrodes 451 and 452 at regular intervals. according to the above-described method of manufacturing a light-emitting apparatus, the insulating substrate 450 is produced where an alignment region are formed having as a unit the two electrode 451 and 452 to which independent potentials are respectively to be provided, and a liquid containing the rod-like light-emitting devices 460 in a size of the order of nanometers or micrometers is applied on the insulating substrate 450 . thereafter, independent voltages are respectively applied to the two electrodes 451 and 452 to align the microscopic rod-like light-emitting devices 460 at positions defined by the two electrodes 451 and 452 . thus, the rod-like light-emitting devices 460 can be easily aligned on the predetermined insulating substrate 450 . with the above-described method of manufacturing a light-emitting apparatus, the amount of semiconductors used can be decreased, and a light-emitting apparatus whose thickness and weight can be reduced can be manufactured. in the rod-like light-emitting device 460 , light is emitted from the whole periphery of the semiconductor core covered with the semiconductor layer to result in expansion of the light emitting region. therefore, a light-emitting apparatus that has a high light-emitting efficiency, achieves low power consumption, and has a good heat dissipation can be implemented. fig. 121 is a plan view of the insulating substrate 450 on which the rod-like light-emitting devices 460 are aligned. the insulating substrate 450 on which the rod-like light-emitting devices 460 are aligned is used for a backlight of a liquid crystal display device or the like. this makes it possible to implement a backlight whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. also, using as an illuminating device the insulating substrate 450 having the rod-like light-emitting devices 460 aligned thereon makes it possible to implement an illuminating device whose thickness and weight can be reduced and that has a high light emitting efficiency and achieves low power consumption. fig. 122 is a plan view of a display device that uses an insulating substrate on which the rod-like light-emitting devices 460 are aligned. as shown in fig. 122 , a display device 3300 has a display unit 2301 , a logic circuit unit 3302 , a logic circuit unit 3303 , a logic circuit unit 3304 and a logic circuit unit 3305 which are formed on the insulating substrate 3310 . in the display unit 3301 , the rod-like light-emitting devices 460 are aligned at pixels arranged in a matrix. fig. 123 is a circuit diagram of a main part of the display unit 3301 of the display device 3300 . the display unit 3301 of the display device 3300 , as shown in fig. 123 , includes a plurality of scanning signal lines gl (just one line of which is shown in fig. 123 ) intersecting with a plurality of data signal lines sl (just one line of which is shown in fig. 123 ). the pixels are arranged in a matrix form, with one pixel placed in a portion enclosed by two adjacent scanning signal lines gl and two adjacent data signal lines sl. the pixel includes a switching element q 1 whose gate is connected to a scanning signal line gl and whose source is connected to a data signal line sl, a switching element q 2 whose gate is connected to the drain of the switching element q 1 , a pixel capacitor c of which one end is connected to the gate of the switching element q 2 , and a plurality of light emitting diodes d 1 to dn (rod-like light-emitting devices 460 ) driven by the switching element q 2 . polarities of p and n of the rod-like light-emitting devices 460 are not aligned, but arranged at random. therefore, at the time of driving, the rod-like light-emitting devices 460 with different polarities alternately emit light when driven by an ac voltage. (embodiment 46) fig. 124 is a side view of a light-emitting apparatus of embodiment 46 of this invention, and fig. 125 is a perspective view of the light-emitting apparatus. in this embodiment 46, any one of the rod-like light-emitting devices of the light-emitting apparatuses of embodiments 39 to 45 described above is used. fig. 125 shows a rod-like light-emitting device having the same configuration as the rod-like light-emitting device of the light-emitting apparatus of embodiment 40. the light-emitting apparatus of this embodiment 46, as shown in fig. 124 and fig. 125 , includes an insulating substrate 450 having metal electrodes 461 and 462 formed on a mounting surface thereof, and a rod-like light-emitting device 460 mounted on the insulating substrate 450 such that the longitudinal direction of the rod-like light-emitting device 460 is parallel to a mounting surface of the insulating substrate 450 . on the insulating substrate 450 , a third metal electrode 463 , as one example of the metal portion, is formed between the metal electrodes 461 and 462 on the insulating substrate 450 and below the rod-like light-emitting device 460 . fig. 125 shows only parts of the metal electrodes 461 , 462 and 463 . the rod-like light-emitting device 460 , as shown in fig. 125 , includes a semiconductor core 471 made of n-type gan and having a rod shape whose cross section is nearly hexagonal, a quantum well layer 472 made of p-type ingan and formed to cover part of the semiconductor core 471 , and a semiconductor layer 473 made of p-type gan and formed to cover the quantum well layer 472 . in the semiconductor core 471 , an exposed portion 471 a is formed. in the exposed portion 471 a , the outer peripheral surface of the semiconductor core 471 is exposed. the end surface of the other end of the semiconductor core 471 is covered with the quantum well layer 472 and the semiconductor layer 473 . as shown in fig. 124 and fig. 125 , the exposed portion 471 a on one side of the rod-like light-emitting device 460 is connected to the metal electrode 461 , and the semiconductor layer 473 on the other side of the rod-like light-emitting device 460 is connected to the metal electrode 462 . here, a central portion of the rod-like light-emitting device 460 is connected to the metal electrode 463 . both ends of the rod-like light-emitting device 460 are connected to the metal electrodes 461 and 462 that are formed with a predetermined spacing therebetween on the insulating substrate 450 , and the metal portion is formed between the metal electrodes 461 and 462 and below the rod-like light-emitting device 460 on the insulating substrate 450 , so that the central side of the rod-like light-emitting device 460 whose both ends are connected to the metal electrodes 461 and 462 is supported by bringing the central side into contact with the surface of the third metal electrode 463 . as a result, the rod-like light-emitting device 460 , which is connected at both ends, is supported by the metal electrode 463 , without being deformed, and heat generated in the rod-like light-emitting device 460 can be dissipated with a good efficiency from the semiconductor layer 473 through the metal electrode 463 to the insulating substrate 450 . note that, as shown in fig. 126 , the metal electrodes 461 and 462 have base portions 461 a and 462 a that are nearly parallel to each other with a predetermined spacing therebetween, and a plurality of electrode portions 461 b and 462 b extending between the base portions 461 a and 462 a from positions facing each other of the base portions 461 a and 462 a , respectively. one rod-like light-emitting device 460 is aligned with the electrode portion 461 b of the metal electrode 461 and the electrode portion 462 b of the metal electrode 462 opposite thereto. between the electrode portion 461 b of the metal electrode 461 and the electrode portion 462 b of the metal electrode 462 opposite thereto, the third metal electrode 463 in the shape of a butterfly whose central portion is narrow is formed on the insulating substrate 450 . the third metal electrodes 463 adjacent to one another are electrically separated. as shown in fig. 126 , even in the case where the orientations of the rod-like light-emitting devices 460 adjacent to each other are reversed, the metal electrode 461 and the metal electrode 462 can be prevented from becoming short-circuited to each other through the metal electrode 463 . in embodiments 39 to 46 described above, descriptions have been given of the rod-like light-emitting devices having the exposed portions 311 a , 321 a , 331 a , 341 a , 351 a , 361 a , 371 a , 381 a and 471 a where the outer peripheral surfaces on one side of the semiconductor cores 311 , 321 , 331 , 341 , 351 , 361 , 371 , 381 and 471 are exposed. however, the rod-like light-emitting device is not limited to these devices, and may have an exposed portion where the outer peripheral surfaces on both ends of a semiconductor core are exposed, and may have an exposed portion where the outer peripheral surface of a central portion of the semiconductor core is exposed. in embodiments 39 to 46 described above, semiconductors whose base materials are gan are used for the semiconductor cores 311 , 321 , 331 , 341 , 351 , 361 , 371 , 381 and 471 and the semiconductor layers 312 , 323 , 332 , 343 , 352 , 363 , 372 , 383 and 473 . however, this invention may be applied to light-emitting devices that use semiconductors whose base materials are gaas, algaas, gaasp, ingan, algan, gap, znse, algainp and the like. while the semiconductor core is of n type and the semiconductor layer is of p type, this invention may be applied to a rod-like light-emitting device in which the conductivity types are reversed. in embodiments 39 to 42 described above, the rod-like light-emitting device with the size of the order of micrometers in which the diameter is 1 μm and the length is 20 μm is used. however, there may be a device with the size of the order of nanometers in which at least the diameter of the diameter and the length is less than 1 μm. the diameter of the semiconductor core of the above rod-like light-emitting device is preferably 500 nm or more and 50 μm or less, which enables variations in diameter of the semiconductor core to be reduced compared to a rod-like light-emitting device having a semiconductor core whose diameter ranges from several tens of nanometers to several hundreds of nanometers. therefore, variations in the light emitting region, that is, variations in light emission characteristics can be decreased. this can lead to improvement in yields. in embodiments 39 to 46 described above, crystal growth of the semiconductor cores 311 , 321 , 331 , 341 , 351 , 361 , 371 , 381 and 471 is made using the mocvd device. however, the semiconductor cores may be formed using other crystal growth devices such as a molecular-beam epitaxy (mbe) device. the crystal growth of the semiconductor core is made on a substrate using a mask having a growth hole. alternatively, metal species may be placed on a substrate, and crystal growth of a semiconductor core may result from the metal species. in the above-described rod-like light-emitting devices 310 , 320 , 330 , 340 , 350 , 360 , 370 , 380 and 460 of embodiments 38 to 46, the semiconductor cores 311 , 321 , 331 , 341 , 351 , 361 , 371 , 381 and 471 covered with the semiconductor layers 312 , 323 , 332 , 343 , 352 , 363 , 372 , 383 and 473 are separated from the substrates using ultrasonic waves. however, the way of separation is not limited to this, and the semiconductor core may be separated from the substrate by mechanically bending the semiconductor core with a cutting tool. in this case, a plurality of microscopic rod-like light-emitting devices provided on the substrate can be separated by a simple way for a short time. in embodiment 45 described above, a potential difference is provided to the two metal electrodes 451 and 452 formed on the surface of the insulating substrate 450 to align the rod-like light-emitting devices 460 between the metal electrodes 451 and 452 . however, alignment is not limited to this. rod-like light-emitting devices may be aligned at positions defined by the electrodes by forming a third electrode as in embodiment 46 between two electrodes formed on the surface of the insulating substrate, and applying independent voltages to the three electrodes, respectively. in embodiment 45 described above, the backlight, the illuminating device and the display device each including the light-emitting apparatuses have been described. however, the invention is not limited to these and may be applied to other apparatuses. embodiments of the invention being thus described, it will be obvious that the same may be varied in many ways. such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. citation list patent literature patent literature 1: jp 2008-235443 apatent literature 2: jp 2006-332650 a
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043-749-529-106-767
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US
|
[
"US",
"WO",
"AU"
] |
H01Q1/38,H01Q9/27,H01Q13/10,H01Q13/16,H01Q13/18
| 2000-10-02T00:00:00 |
2000
|
[
"H01"
] |
slot spiral miniaturized antenna
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a slot spiral miniaturized antenna is described. the antenna includes a conductive layer formed on a first side of a dielectric substrate. a slot arranged in the form of a spiral curve and having a slow-wave structure is formed in the conductive layer. the antenna also includes a planar balun formed on a second side of the substrate. the balun is in the form of a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline. the conductive layer strip has a shape that replicates a pattern of the two neighboring parts of the slotline. the conductive layer strip provides a balanced feed to the slot at a feedpoint that is defined by a place wherein a projection of said conductive layer strip on the second side intercepts the slotline. electromagnetic coupling between the conductive layer strip and the slotline without electrical contact causes the exciting of the slotline. the antenna of the present invention is geometrically smaller than another antenna performing the same functions, but without such features as the slow-wave structure of the slotline and the replication of a pattern of the slotline shape by a conductive layer strip.
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1. a slot spiral antenna comprising: 2. the antenna of claim 1 wherein at least a part of said slow-wave structure is selected from a group including zigzag, meander line, sine and fractal. 3. the antenna of claim 2 wherein said zigzag is a modified zigzag. 4. the antenna of claim 3 wherein teeth of the zigzag in vertexes have an angle of about zero degree. 5. the antenna of claim 1 wherein said conductive layer strip has a sine wave configuration. 6. the antenna of claim 1 wherein said spiral curve being a slotted two arm spiral configured to radiate bidirectionally electromagnetic energy over a broad frequency band. 7. the antenna of claim 6 wherein said feedpoint being arranged at a bridge connecting the two arms of the slotted spiral. 8. the antenna of claim 1 wherein at least a portion of said spiral curve is selected from a group including rectangular, archimedean, logarithmic, acentric and non-symmetric form. 9. the antenna of claim 1 wherein the feedpoint being arranged at a center of an aperture of said antenna. 10. the antenna of claim 1 wherein the feedpoint being arranged at any place of an aperture of said antenna. 11. the antenna of claim 1 wherein the slotline having ends being terminated by an element preventing wave reflection. 12. the antenna of claim 11 wherein said element is selected from the group that includes a lossy material, tapered absorbing material, resistive layer, resistor cards, resistive paint and lumped element. 13. the antenna of claim 1 wherein the slotline having slotline ends, the slotline at the ends being configured for matching an impedance of the slotline to the impedance of a space surrounding the spiral curve. 14. the antenna of claim 1 further comprising a connector for connecting the balun to a source. 15. the antenna of claim 14 wherein an impedance of said conductive layer strip being matched to the impedance of the connector. 16. the antenna of claim 1 wherein said conductive layer strip continues after the feedpoint for providing wideband matching. 17. the antenna of claim 16 wherein said conductive layer strip continues after the feedpoint a distance equal to a multiple of one quarter wavelength of a desired frequency. 18. the antenna of claim 16 wherein said conductive layer strip is terminated after the feedpoint by an element preventing wave reflection, said element is selected from the group consisting of a high dielectric loss material, tapered absorbing material, resistive layer, resistor cards, resistive paint and lumped element. 19. the antenna of claim 1 wherein said conductive layer acts as a ground plane for said conductive layer strip. 20. the antenna of claim 1 further comprising a superstrate layer placed on the first and second sides of said dielectric substrate. 21. the antenna of claim 20 wherein said superstrate layer being a high permittivity and low dielectric loss material. 22. the antenna of claim 1 wherein a width of said conductive layer strip being at least three times less than the width of said section on the conductive layer defined by the area between two neighboring parts of the slotline. 23. the antenna of claim 1 further comprising a thin reflecting cavity facing said first side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to reflect the radiation emitted by said slotline so as to render said antenna unidirectional. 24. the antenna of claim 1 further comprising a thin reflecting cavity facing said second side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to reflect the radiation emitted by said slotline so as to render said antenna unidirectional. 25. the antenna of claim 23 wherein the cavity being filled with a high dielectric loss material. 26. the antenna of claim 23 wherein the cavity being filled with a low dielectric loss material. 27. the antenna of claim 24 wherein the cavity being filled with a high dielectric loss material. 28. the antenna of claim 24 wherein the cavity being filled with a low dielectric loss material. 29. the antenna of claim 23 wherein the cavity being filled with a multi-layer dielectric having different permittivity and dielectric losses for each layer. 30. the antenna of claim 24 wherein the cavity being filled with a multi-layer dielectric having different permittivity and dielectric losses for each layer. 31. the antenna of claim 1 further comprising a thin absorptive cavity facing said first side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to absorb the radiation emitted by said slotline so as to render said antenna unidirectional. 32. the antenna of claim 1 further comprising a thin absorptive cavity facing said second side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to absorb the radiation emitted by said slotline so as to render said antenna unidirectional. 33. the antenna of claim 26 further comprising a superstrate layer placed on said second side of said substrate, said superstrate layer having a dielectric loss higher than the dielectric loss of said low dielectric loss material. 34. the antenna of claim 28 further comprising a superstrate layer placed on said first side of said substrate, said superstrate layer having a dielectric loss higher than the dielectric loss of said low dielectric loss material. 35. the antenna of claim 1 wherein at least a part of said slow-wave structure having a zigzag shape, said antenna further comprising vias configured for minimizing a coupling between the slotline and said conductive layer strip. 36. the antenna of claim 35 wherein a plurality of teeth of said zigzag shape having an angle of about zero. 37. the antenna of claim 35 wherein a triple via arrangement being made around each tooth. 38. the antenna of claim 36 wherein a triple via arrangement being made around each tooth. 39. the antenna of claim 23 wherein said cavity backing surface being non-planar in shape. 40. the antenna of claim 24 wherein said cavity backing surface being non-planar in shape. 41. the antenna of claim 23 wherein said cavity backing surface acts as a ground plane. 42. the antenna of claim 24 wherein said cavity backing surface acts as a ground plane. 43. the antenna of claim 41 further comprising: 44. the antenna of claim 42 further comprising: 45. the antenna of claim 43 wherein said second ground plane having regions through which a full or partial transmission of electromagnetic field is enabled for combining a main radiation emitted from the slotline with the radiation emitted from the slotline's ends, thereby providing a further enhanced impedance match. 46. the antenna of claim 44 wherein said second ground plane having regions through which a full or partial transmission of electromagnetic field is enabled for combining a main radiation emitted from the slotline with the radiation emitted from the slotline's ends, thereby providing a further enhanced impedance match. 47. the antenna of claim 1 being conformed to complexly shaped surfaces and contours of a mounting platform. 48. the antenna of claim 47 wherein a mounting platform being a body of a hand-held communication device. 49. a slot spiral antenna comprising: wherein said antenna being fitted for use in a hand-held communication device. 50. the antenna of claim 48 wherein the mobile communication device being selected from the group including mobile phone, pda and remote control units. 51. a slot spiral antenna comprising: wherein said antenna being automatically configured to operate over at least one octave frequency band within the frequency range of about 800 mhz to 3 ghz. 52. a hand-held communication device comprising an antenna comprising: 53. the hand-held communication device of claim 52 being selected from the group that includes mobile phone, pda and remote control units. 54. the hand-held communication device of claim 52 wherein said antenna being automatically configured to operate over at least one octave frequency band within the frequency range of about 800 mhz to 3 ghz. 55. a method of fabricating a slot spiral antenna comprising: 56. the method of claim 55 wherein at least a part of said slow-wave structure is selected from a group including zigzag, meander line, sine and fractal. 57. the method of claim 56 wherein said zigzag is a modified zigzag. 58. the method of claim 55 wherein said conductive layer strip has a sine wave configuration. 59. the method of claim 55 wherein said feedpoint being arranged at a bridge connecting the two arms of the slotted spiral. 60. the method of claim 55 wherein at least a portion of said spiral curve is selected from a group including rectangular, archimedean, logarithmic, acentric and non-symmetric form. 61. the method of claim 55 wherein the slotline having ends being terminated by an element preventing wave reflection. 62. the method of claim 55 wherein said conductive layer strip continues after the feedpoint for providing wideband matching. 63. the method of claim 55 further comprising the step of placing a superstrate layer on the first and second sides of said dielectric substrate. 64. the method of claim 55 further comprising the step of providing a thin reflecting cavity facing said first side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to reflect the radiation emitted by said slotline so as to render said antenna unidirectional. 65. the method of claim 55 further comprising the step of providing a thin reflecting cavity facing said second side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to reflect the radiation emitted by said slotline so as to render said antenna unidirectional. 66. the method of claim 55 further comprising the step of providing a thin absorptive cavity facing said first side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to absorb the radiation emitted by said slotline so as to render said antenna unidirectional. 67. the method of claim 55 further comprising the step of providing a thin absorptive cavity facing said second side of the substrate, the cavity having a bottom, the bottom having a cavity backing surface configured to absorb the radiation emitted by said slotline so as to render said antenna unidirectional. 68. the method of claim 55 wherein at least a part of said slow-wave structure having a zigzag shape, said antenna further comprising vias configured for minimizing a coupling between the slotline and said conductive layer strip. 69. a slot spiral antenna comprising: thereby said antenna is geometrically smaller than another antenna performing the same functions as said antenna, but without said slow-wave structure of the pattern of said at least a portion of the slotline and without said shape of said conductive layer. 70. a slot spiral antenna comprising: wherein said antenna being automatically configured to operate over at least one octave frequency band.
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field of the invention the present invention relates generally to antennas, and in particular, to slot spiral, miniature antennas. background of the invention spiral antennas are well known in the art as means of providing circularly polarized radiation over a broad frequency band. the most popular configurations are the dual arm equiangular. archimedean and logarithmic spirals, in which the two arms are fed in antiphase at the center (see, for example, u.s. pat. nos. 3,781,898 and 3,969,732 both) to holloway). the lowest frequency of operation in such antennas is determined by the diameter of the spiral, where the outer circumference is equal to the longest wavelength. there are many applications in which the small size of the antennas is a desirable feature due to cosmetic, security, aerodynamic and other reasons. there are also applications in which surface conformability of the antennas or a possibility to mount an antenna on a platform, which is not flat or planar, is a desirable feature. for example, in mobile devices (e.g., cellular phones, pdas, laptops, etc), reducing antenna's size is required since the amount of space available for mounting an antenna is limited. for antennas mounted on airplanes, the protrusion of the antenna beyond the surface of the plane should be minimized in order to reduce the effect of the antenna on its aerodynamic properties. generally, a decrease in the size of the spiral antenna may be accomplished by the reduction of its aperture and/or thickness. various approaches are known in the art for gaining an aperture reduction of the antennas. for instance, the aperture reduction may be achieved by utilization of perimeter squared spiral configurations. further aperture reduction may also be accomplished by utilizing a square spiral with a zigzag track to produce a slow wave structure (see, for example, u.s. pat. no. 3,465,346 to patterson and reduced size spiral antenna, proc. 9-th european microwave conf., september. 1979, pages 181-185, by morgan). the slow-wave structure features a slower phase velocity and, consequently, a smaller radiation zone at the lowest operating frequency that, in turn, allows the diameter of the slow-wave antenna to be reduced significantly. the reduction in size is proportional to the degree of slowing of the slow-wave, as measured by the slow-wave factor, which is defined as the ratio of the phase a velocity of the propagating wave in the traveling wave structure to the speed of light in a vacuum. various approaches for aperture reduction were implemented by implementation of multi-arms antennas. for example, u.s. pat. no. 6,023,250 to cronyn discloses an antenna having a plurality of exponential-spiral shaped antenna arms in which each of the arms includes an antenna clement having a sinuous portion. since a spiral in the antennas radiates bidirectionally, backed metallic and absorbing cavities are generally used (see, for example, morgan, reduced size spiral antenna, proc. 9-th european microwave conf., september. 1979, pages 181-185). the backed cavity is employed to redirect half of the energy constructively to form a main beam. theoretically, the optimum cavity depth is a quarter of the wavelength . if the frequency approaches the value /2, then the reflected energy is in antiphase with the forward radiation, that results in beam splitting and a degraded match. therefore, many conventional spiral antennas employ absorbing cavities that absorb the energy within the cavity, thereby preventing it from reflecting destructively and providing broadband operation. despite the technical advantages, adding a cavity to the spiral antenna may significantly increase its thickness to the overall antenna structure, that contradicts the small size requirements. a slot spiral antenna with an integrated planar balun and feed is described in u.s. pat. no. 5,815,122 to numberger, et al. the slot spiral antenna is produced by using standard printed circuit techniques. a conducting layer of the material substrate is etched to form a radiating spiral slot. the balun structure includes a microstrip line that winds toward the center of the slot spiral. at the center of the slot spiral, the feed is executed by breaking the ground plane of the microstrip line with the spiral slot. the technique disclosed in u.s. pat. no. 5,815,122 substantially reduces the size of the conventional spiral antennas, such that the antenna may be suitable for incorporating into the skin of some mobile devisees. however, the diameter of this antenna is still big in order to fit the external surface of a mobile phone. thus, there is still a need for further improvement in order to provide an antenna that might include the broad band performance, surface conformability, uni-directionality and reduced aperture and thickness (e.g.. suitable for flush mounting with the external surface of a mobile phone), all the features in a single package. summary of the invention the present invention satisfies the aforementioned need by providing a slot spiral antenna that is geometrically smaller than another antenna performing the same functions. the antenna includes a conductive layer formed on a first side of a dielectric substrate. a slot arranged along a spiral curve is formed in the conductive layer by using conventional printed circuit techniques. a slotline of the slot has a slow-wave structure, e.g. zigzag, meander line, sine, fractal, etc. the antenna also includes a planar balun formed on a second side of the substrate. the balun is in the form of a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline. the conductive layer strip bas a shape that replicates a pattern of the two neighboring parts of the slotline. for example, when a slotline of the slot has a zigzag shape, the shape of the conductive layer strip may resemble a sine pattern. the conductive layer strip provides a balanced feed to the slot at a feedpoint that is defined by a place wherein a projection of said conductive layer strip on the second side intercepts the slotline. electromagnetic coupling between the conductive layer strip and the slotline without electrical contact causes the exciting of the slotline. in order to limit the radiation to one direction, a thin cavity may be included. the cavity may face either the first or second side of the substrate. the cavity may be filled with high dielectric loss material, low dielectric loss material or a combination thereof. if it is necessary to decrease the coupling between the slotline and the conductive layer strip, then the antenna may include vias made near singularity points of the slow wave structure, e.g., near zigzag vertexes. according to one embodiment of the present invention, in vertexes of the zigzag, an angle of the teeth may have a magnitude of about zero degrees. the antenna of the present invention is geometrically smaller than another antenna performing the same functions, but without such features as the slow-wave structure of the slotline and the replication of a pattern of the slotline shape by a conductive layer strip. the antenna of the present invention has many of the advantages of the prior art techniques, while simultaneously overcoming some of the disadvantages normally associated therewith. the antenna according to the present invention may be mounted flush with the surface of a mounting platform. the antenna according to the present invention may be relatively thin in order to be inset in the skin of a mounting platform without creating a deep cavity therein. the antenna according to the present invention may be readily conformed to complexly shaped surfaces and contours of a mounting platform. the antenna according to the present invention may be easily and efficiently manufactured. the antenna according to the present invention is of durable and reliable construction. the antenna according to the present invention may have a low manufacturing cost. in summary, according to one broad aspect of the present invention, there is provided a slot spiral antenna comprising: a dielectric substrate of a predetermined form having a first surface and a second surface, a conductive layer on said first side of the substrate said conductive layer including at least one slot defined by a slotline arranged in the form of a spiral curve, at least a portion of the slotline having a pattern corresponding to a slow-wave structure; a planar balun formed on said second side of the substrate, the balun being a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline, each neighboring part having a pattern; said conductive layer strip having a shape substantially replicating the pattern of said two neighboring parts of the slotline, said conductive layer strip configured to provide a balanced feed to said at least one slot at a feedpoint defined by a place wherein a projection of said conductive layer strip on said second side intercepts the slotline, thereby exciting the slotline by causing electromagnetic coupling between said conductive layer strip and slotline without electrical contact. according to another broad aspect of the present invention there is provided a a slot spiral antenna comprising: a dielectric substrate of a predetermined form having a first surface and a second surface, a conductive layer on said first side of the substrate, said conductive layer including at least one slot defined by a slotline arranged in the form of a spiral curve, at least a portion of the slotline having a pattern corresponding to a slow-wave structure; a planar balun formed on said second side of the substrate, the balun being a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline, each neighboring part having a pattern; said conductive layer strip having a shape substantially replicating the pattern of said two neighboring parts of the slotline, said conductive layer strip configured to provide a balanced feed to said at least one slot at a feedpoint defined by a place wherein a projection of said conductive layer strip on said second side intercepts the slotline, thereby exciting the slotline by causing electromagnetic coupling between said conductive layer strip and slotline without electrical contact, wherein said antenna being fitted for use in a hand-held communication device. according to yet another broad aspect of the present invention, there is provided a slot spiral antenna comprising: a dielectric substrate of a predetermined form having a first surface and a second surface, a conductive layer on said fast side of the substrate, said conductive layer including at least one slot defined by a slotline arranged in the forms of a spiral curve, at least a portion of the slotline having a pattern corresponding to a slow-wave structure; a planar balun formed on said second side of the substrate, the balun being a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline, each neighboring part having a pattern; said conductive layer strip having a shape substantially replicating the pattern of said two neighboring parts of the slotline, said conductive layer strip configured to provide a balanced feed to said at least one slot at a feedpoint defined by a place wherein a projection of said conductive layer strip on said second side intercepts the slotline, thereby exciting the slotline by causing electromagnetic coupling between said conductive layer strip and slotline without electrical contact, wherein said antenna being automatically configured to operate over at least one octave frequency band. according to still another broad aspect of the present invention, there is provided a hand-held communication device comprising an antenna comprising: a dielectric substrate of a predetermined form having a first surface and a second surface, a conductive layer on said first side of the substrate, said conductive layer including at least one slot defined by a slotline arranged in the form of a spiral curve, at least a portion of the slotline having a pattern corresponding to a slow-wave structure; a planar balun formed on said second side of the substrate, the balun being a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline, each neighboring part having a pattern; said conductive layer strip having a shape substantially replicating the pattern of said two neighboring parts of the slotline, said conductive layer strip configured to provide a balanced feed to said at least one slot at a feedpoint defined by a place wherein a projection of said conductive layer strip on said second side intercepts the slotline, thereby exciting the slotline by causing electromagnetic coupling between said conductive layer strip and slotline without electrical contact. according to yet another broad aspect of the present invention, there is provided a hand-held communication device comprising a slot spiral antenna including a balun, wherein the antenna is adapted to provide a mutual operation of least three communication services operating in non-overlapping frequency bands. according to yet another broad aspect of the present invention, there is provided a hand-held communication device comprising a slot spiral antenna including a balun, wherein said antenna being automatically configured to operate over at least one octave frequency band within the frequency range of about 800 mhz to 3 ghz. according to yet another broad aspect of the present invention, there is provided a method for fabricating a slot spiral antenna comprising: providing a dielectric substrate of a predetermined form having a first surface and a second surface; forming a conductive layer on said first side of the substrate, said conductive layer including at least one slot defined by a slotline arranged in the form of a spiral curve, at least a portion of the slotline having a pattern corresponding to a slow-wave structure; forming a planar balun on said second side of the substrate, the balun being a conductive layer strip positioned beneath a section on the conductive layer defined by an area between two neighboring parts of the slotline, each neighboring part having a pattern; said conductive layer strip having a shape substantially replicating the pattern of said two neighboring parts of the slotline, said conductive layer strip configured to provide a balanced feed to said at least one slot at a feedpoint defined by a place wherein a projection of said conductive layer strip on said second side intercepts the slotline, thereby exciting the slotline by causing electromagnetic coupling between said conductive layer strip and slotline without electrical contact. according to still another broad aspect of the present invention, there is provided a conductive layer antenna comprising a dielectric substrate of a predetermined form having a microstrip on one side of the substrate arranged in the form of a spiral curve, at least a portion of the microstrip having a pattern of zigzag; the zigzag having a reversed s-type shape. there has thus been outlined, rather broadly, the more important features of the invention so that the detailed description thereof that follows hereinafter may be better understood, and the present contribution to the art may be better appreciated. additional details and advantages of the invention will be set fort in the detailed description. brief description of the drawings in order to understand the invention and to see how it may be carried out in practice, a preferred embodiment will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which: fig. 1 is a schematic view of the slot spiral antenna and balun according to one embodiment of the present invention; fig. 2 is a schematic view of a cross-section of a portion of the antenna, according to one embodiment of the present invention taken along a-a in fig. 1 ; fig. 3 is a schematic view of a cross-section of a portion of the antenna according to another embodiment of the present invention; fig. 4 a is a schematic view of a conventional zigzag; fig. 4 b is a schematic view of a modified zigzag, according to one embodiment of the present invention; fig. 5 is a table illustrating the values of slow-wave factor for the conventional zigzag and the corresponding values of slow-wave factor for the modified zigzags, according to one embodiment of the present invention; fig. 6 is a schematic view of a modified zigzag illustrating the differences between the modified zigzag and the conventional zigzag; fig. 7 a is a schematic view of a conventional zigzag with vias, according to one embodiment of the present invention; fig. 7 b is a schematic view of a modified zigzag with vias, according to another embodiment of the present invention; fig. 8 a is a schematic view of a cross-section of a portion of the antenna including a cavity, according to one embodiment of the present invention; fig. 8 b is a schematic view of a cross-section of a portion of the antenna including a cavity, according to another embodiment of the present invention; fig. 9 is a schematic view of a cross-section of a portion of the antenna including a cavity having a second ground plane, according to one embodiment of the present invention; fig. 10 is a schematic view of a mobile communication device including an antenna of the present invention; and fig. 11 is a schematic view of a spiral antenna having a modified zigzag implemented on a conductive layer exciting element, according to another general aspect of the present invention. detailed description of specific embodiments the principles and operation of a slot spiral antenna according to the present invention may be better understood with reference to the drawings and the accompanying description. it being understood that these drawings are given for illustrative purposes only and are not meant to be limiting. referring now to the drawings wherein like reference numerals designate corresponding parts throughout the several views, fig. 1 and fig. 2 illustrate a schematic view of the slot spiral antenna 10 according to one embodiment of the present invention. the antenna 10 includes a dielectric substrate 11 having a first surface 12 and a second surface 13 . the first surface 12 is covered by a conductive layer 14 . a portion of the conductive layer 14 is removed to produce a slot 15 defined by a slotline 16 having a pattern corresponding to a slow-wave structure, e.g., zigzag, meander line, sine, fractal, etc. the slotline 16 is arranged in the form of a spiral curve to form a two arm slotted spiral. it should be appreciated that the spiral curve of the slotline 16 may be in any form, e.g., rectangular, archimedean, logarithmic, etc. it should be appreciated that the slotline 16 may also have an acentric and non-symmetric form that is a combination of various forms. the spiral may be of any size, have any number and density of turns and growth rates. the density of the turns may be non-uniform, i.e. may depend on the spiral rotation angle and a location of a feed point 23 . the second surface 13 is also covered by a conductive layer (not shown). a portion of the layer is removed to produce a planar infinite balun 17 . the procedures used to remove the portions of the conducting layers on the first and second surfaces may be any one of the common techniques used to produce printed circuit boards such as etching, milling or other standard printed circuit techniques. the balun 17 is in the form of a conductive layer strip 18 positioned beneath a section 19 on the conductive layer defined by an area between two neighboring parts 20 and 21 of the slotline 16 . preferably, but not mandatory, that the width of the conductive layer strip 18 between strip ends 26 and 27 be at least three times narrower than the width of the section 19 . in order to improve the ratio between these widths, the distance between the two neighboring parts 20 and 21 (encompassing the conductive layer strip 18 ) may be made wider than the distance between the next two neighboring parts, such as 21 and 22 , which do not encompass the conductive layer strip 18 . the conductive layer strip 18 has a shape that substantially replicates a pattern of the two neighboring parts 20 and 21 of the slotline 16 . according to one non-limiting example, when a slotline of the slot has zigzag shape, the shape of the conductive layer strip may resemble a sine pattern. the conductive layer 14 acts as a ground plane for the conductive layer strip 18 . as shown in fig. 1 , the conductive layer strip 18 is wound toward the feedpoint 23 and provides a balanced feed to the slot at the feedpoint 23 that is defined by the place wherein the projection of said conductive layer strip 18 on the second side intercepts the slotline 16 . according to one embodiment of the present invention, the feedpoint 23 is arranged at a center of an aperture of the antenna. according to another embodiment of the present invention, the feedpoint 23 is arranged at any place of an aperture of the antenna. electromagnetic coupling between the conductive layer strip 18 and the slotline 16 at the feedpoint 23 without electrical contact causes the exciting of the slotline 16 . the excited slotline 16 may radiate electromagnetic energy bidirectionally over a relatively broad frequency band. the antenna, according to this embodiment of the present invention, is geometrically smaller than another antenna performing the same functions, but without such features as the slow-wave structure of the slotline 16 and the replication of a pattern of the slotline shape by a conductive layer strip 18 . according to one non-limiting example, the feedpoint 23 is arranged at the center of an aperture of the antenna. the center may include a bridge 24 connecting the two arms of the slotted spiral, and the feedpoint 23 is arranged at the bridge 24 . in order to accomplish maximum energy transfer in broadband operation, the conductive layer strip 18 at the feedpoint 23 is configured to have an impedance substantially equal to one-half of the impedance of the slotline. to achieve this impedance match, a width of the conductive layer strip 18 and/or the spiral slotline 16 can be adjusted to given values. after the feedpoint 23 , the conductive layer strip 18 continues and winds back out from the feedpoint 23 . it can extend any multiple of a desired quarter wavelength at a desired frequency. alternatively, it may continue to wind out to the end 27 of the conductive layer strip 18 , where it may be resistively terminated. still, alternatively, other reactive or lossy termination may be implemented by utilizing a high dielectric loss material, tapered absorbing material, resistive layer, resistor cards, resistive paint, lumped element or any combination of materials and methods performing the reactive or lossy termination functions. to prevent wave reflection from ends 25 of the slotline 16 , the outer ends of the slotline spiral may be configured for matching an impedance of the slotline to the impedance of a space surrounding the spiral curve. according to one non-limiting example, in order to accomplish the matching, the slot width is modified. according to another non-limiting example, the ends are loaded with electromagnetic absorbing element, as shown in fig. 2 , such as a dielectric loss material 28 . tapering of the material 28 thickness, as shown in fig. 2 , can improve its effectiveness by making a change in the volume of the terminating material to be more gradual. alternatively, the outer slot arms may be terminated by using deposition various lossy materials, resistive layers, resistive points, resistor cards, other similar materials, lumped element or any combination of materials and methods performing the reactive or lossy termination functions. in order to enhance the performance of the antenna, superstrate layers 32 and 34 are placed on the first and/or second side, as shown in fig. 3 . preferably, but not necessarily, the material of superstrate layers 32 and 34 has high permittivity and low dielectric loss values. the selection of such material may extend the operation frequency of the antenna in the low limit of the frequency band, without a noticeable deterioration in the antenna's performance. the antenna 10 may be fed using any conventional manner, and in a manner compatible with the corresponding external electronic unit (source or receiver) for which the antenna is employed. for example, the external unit may be connected to the balun 17 by attaching a connector (not shown) at the end ( 26 in fig. 1 ) of the conductive layer strip 18 , and fastening a coax cable or any other transmission line (not shown) between this connection and the external unit. turning to fig. 4 a and fig. 4 b , a conventional zigzag 42 and a modified zigzag 44 are shown, according to one embodiment of the present invention. the conventional zigzag 42 has straight-line teeth 43 , while the modified zigzag 44 has a reversed s-type shape 45 . using various configurations, e.g., the configurations 45 through 47 of the modified zigzag, it is possible to further increase the length of the slotline ( 16 in fig. 1 ), when compared with using the length 43 of the conventional zigzag 42 . as a consequence of the increase in the zigzag length, the slow-wave factor of the configuration decreases, and the low frequency limit of the antennas' operation is extended without changes of the overall antenna geometry in the position and number of the zigzag's teeth. a slow wave factor f _{ con } of the conventional zigzag 42 as compared to a straight-line slotline (i.e. a slotline without any zigzag) may be obtained by f con = a a 2 + b 2 ( 1 ) wherein the parameters a and b are shown in fig. 4 a. an upper limit value of the length of a side of the zigzag's tooth is ab. this limit may be achieved by approaching dotted lines 48 and 49 by the consequent consideration of the modified zigzags 45 , 46 , 47 , etc. a slow wave factor f _{ lim } of the limiting zigzag as compared with the conventional zigzag may be obtained by f lim = a 2 + b 2 a + b ( 2 ) wherein the parameters a and b are shown in fig. 4 b. an overall improvement of the slow-wave factor of the limiting modified zigzag as compared with straight-line slotline may be obtained by f ov = f con f lim = a a + b ( 3 ) the values of slow-wave factors for the conventional zigzags (calculated by using eq. (1)) and the corresponding values for the limiting modified zigzags having various configurations (calculated by using eq. (3)) are shown in the table in fig. 5 . the zigzags are characterized by a slop of the teeth. each row in the table corresponds to the same value of the slop. as it can be seen from the table, the value of the slow-wave factor for a modified zigzag is always less than the value for a corresponding conventional zigzag. thus the modified zigzag may increase the operating band of the antenna (better than on 20%) with respect to the low frequency limit of an antenna with a conventional zigzag without changes of the overall antenna geometry in the position and number of the zigzag's teeth. as it may be seen in fig. 6 , in vertexes 61 of the zigzags, angles 62 of the teeth of the modified zigzag 44 always have less magnitude than angles 64 of the conventional zigzag 42 . in the limit, the modified zigzag may have an angle of the teeth of about zero that may also improve the radiation of the antenna. it may be appreciated by a person versed in the art that when the slotline ( 16 in fig. 1 ) has the shape of modified zigzag 44 , it provides many additional advantages, when compared with the shape of conventional zigzag 42 . for instance, the increase of the slow-wave factor for the modified zigzags results in the widening of the antenna's frequency band. additionally, the distance 65 (for the modified zigzag 44 ) between two neighboring parts 67 and 68 of the slotline is larger than the distance 66 (for the modified zigzag 44 ) between two neighboring parts 69 and 70 , resulting in less influence of the slotline on the balun 71 . yet, additionally, a decrease in the magnitude of the teeth angle results in better radiation performance of the slotline. referring now to fig. 7 a and fig. 7 b , two embodiments of the present invention are illustrated implemented for minimizing a coupling between a conventional zigzag slotline ( 101 in fig. 7 a ) and a conductive layer strip 102 , and a modified zigzag slotline ( 103 in fig. 7 a ) and a conductive layer strip 102 , respectively. according to these embodiments, vias 105 are arranged in the vicinity of zigzag vertexes. for example, the vias 105 may be in the form of a set of empty bores having a conductive cover on the internal surface of the bores. according to another example, the bores may be filled with a conductive material, e.g. with metal pins. preferably, but not mandatory, that a triple via arrangement (as shown in fig. 7 a and fig. 7 b ) is made around each tooth of the zigzags. referring now to fig. 8 a and fig. 8 b , two embodiments of the present invention are illustrated, in which the antenna 10 further includes a cavity 72 that is configured to limit the radiation of the antenna to one direction. the cavity 72 may face either the send surface 13 (as illustrated in fig. 8 a ) or the first surface 12 (as illustrated in fig. 8 b ). the cavity 72 may have an absorbing or reflective bottom 74 and walls (not shown in figs. 8 a and 8 b ). the bottom 74 may be planar, conical or may be shaped in another manner. magnetic currents running along the spiral slot 15 provide a bi-directional radiation of the slot antenna 10 . when the bottom 74 is absorbing bottom, the wave radiated into the cavity 72 will be absorbed and the antenna's radiation will be limited to one direction. on the other hand, when the bottom 74 is reflective, the wave radiated into the cavity 72 may be reflected by a backing surface 78 that operates as a ground plane. thus, the antenna including the cavity 72 with the reflective bottom 74 , may have an enhanced gain, when compared with the gain of the antenna without the reflective bottom. since the slot 15 may be considered as a shunt element, the cavity 72 may be a very thin cavity (lesser than a {fraction (1/10)}th of a wavelength) maintaining the antenna broadband performance and reflecting the wave by backing surface 78 approximately in phase with the corresponding outward radiating wave. this is an important characteristic of the design, because it enables the antenna as a whole to be very thin. thus, the thin antenna of this embodiment of the present invention may be mounted flush with the surface of the mounting platform (e.g., a communicating device) or may be inset in the outer skin of the mounting platform. according to one embodiment of the present invention, the cavity 72 is empty. according to another embodiment of the present invention, the cavity 72 is filled with a material 76 . it may include any combination and number of layers of material fillings. in particular, the filling of the cavity with a dielectric material may serve to shift the antenna operation to lower frequencies and this is equivalent to reducing the aperture dimension. according to one embodiment, the material 76 may be a high dielectric loss material. this configuration may be utilized in conjunction with absorbing bottom 74 . according to another embodiment, when the bottom 74 is reflective, the material 76 may be a low dielectric loss material. it should be appreciated that the antenna 10 with the cavity 72 may further include superstrate layers 78 and 79 . the superstrate layers 78 may be placed on the first side 12 of the substrate 11 (as shown in fig. 8 a ) or on the second side 13 , (as shown in fig. 8 b ). preferably, but not mandatory, the material of superstrate layers 78 and 79 has high permittivity and low dielectric loss values. the selection of such material may further extend the operation frequency of the antenna in the low limit of the frequency band, without noticeable deterioration of the antenna's performance. however, it should be appreciated that a number of various materials and material compositions may be used upon the antenna's design and requirements. it should be further appreciated that the antenna 10 with the cavity 72 may further include a vias arrangement as described above with reference to fig. 7 a and fig. 7 b. further embodiment of the present invention is shown in fig. 9 , a modified cavity 81 is shown that further includes a second ground plane 82 . the second ground plane 82 is in the form of a conductive plate mounted between the dielectric substrate 11 and the cavity backing surface 78 . the second ground plane 82 divides the cavity 81 into sections 85 and 86 . the modified cavity 81 further includes re-radiating cavity edges 83 attached to the conductive layer 14 . the second ground plane 82 and re-radiating cavity edges 83 are provided for redirecting a wave radiated from ends 84 of the slotline ( 16 in fig. 1 ) to the section 86 (between the second ground plane 82 and said cavity backing surface 78 ). preferably, but not mandatory, the section 86 is filled with a high dielectric loss material. in particular, the described above configuration of the modified cavity 81 may provide an extension of termination of the slotline's ends 84 to the section 86 for providing an enhanced impedance match. it should be appreciated that the modified cavity 81 may face either the first surface 12 (as in fig. 9 ) or the second surface 13 (the figure is not shown). according to yet further embodiment of the present invention, the second ground plane 82 may have regions through which a full or partial transmission of electromagnetic field is enabled, for example, by providing a plurality of bores in the second ground plane 82 . this feature is provided for a possibility to combine a main radiation emitted from the slotline ( 16 in fig. 1 ) together with the radiation emitted from the slotline's ends 84 , and thereby provide a further enhanced impedance match and overall antenna performance. as such, those skilled in the art to which the present invention pertains, can appreciate that while the present invention has been described in terms of preferred embodiments, the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures systems and processes for carrying out the several purposes of the present invention. it is apparent that the antenna of the present invention is not bound to the examples of the symmetric and planar antennas. if necessary, the form and shape of the antenna may be defined by the form and shape of the mounting platform. it can be appreciated by a man of the art that the slot spiral miniaturized antenna of the present invention may have numerous applications. the list of applications includes, but is not limited to, various portable devices operating in the frequency band of about 800 mhz to 3 ghz. in particular, the antenna of the present invention would be operative with various hand-held mobile communication devices, e.g., mobile phones, pdas. remote control units, etc. the term hand-held means that the communication device is small in size and comparable with the size of a palm. it should be appreciated that this term includes also ear-piece and head-mounted devices. employment of the antenna of the present invention for operating a mobile phone may eliminate one of the drawbacks pertinent to most conventional mobile phones, i.e., the omnidirectional transmission of electromagnetic radiation from such apparatuses. when using a mobile phone, the user holds the mobile phone in close proximity to the biological tissue of the user's head. the phone transmits microwave electromagnetic radiation in all directions, therefore part of the energy is absorbed by the head tissues. it is believed in certain communities that the radiation absorbed by the head may cause cancer or create other health risks or hazards to the user talking over such devices. in addition, the energy absorbed by the head reduces the strength of the radiation signal emitted from the conventional antenna for communication and decreases the efficiency of the mobile phone. fig. 10 schematically illustrates an antenna 110 of the present invention mounted on a back surface 120 of a mobile communication device 100 . when the antenna 110 includes a backed cavity (not shown), it radiates uni-directionally. such implementation of the antenna eliminates the aforementioned drawback of conventional antennas, since the radiation directed towards the user (not shown) will be significantly decreased, when compared with the bi-directional radiation of the conventional communication devices. additionally, the antenna of the present invention may allow reducing the development effort required for connectivity between different communication devices associated with different communication services and operating in various frequency bands. typically, the modern communication devices operate in different non-overlapping frequency bands distributed over a wide frequency range of about 800 mhz to 3 ghz. the antennas utilized in these devices are typically constructed for operation with a specific frequency band, reserved by a specific communication service. for example, the frequency band utilized by apms (advanced mobile phone service) is 824 mhz-894 mhz, while the band utilized by pcs (personal communication service) is 1850 mhz-1990 mhz. therefore, if a user wants to change the communication service, he has to change the communication device, that may be inconvenient for the user. the antenna of the present invention may be utilized for operating over a wide frequency range of about 800 mhz to 3 ghz that may cover many applications by using only a single communication device. accordingly, the antenna of the present invention may allow utilizing a single cellular phone for communicating over different cellular services. according to one non-limiting example, the antenna of the present invention may be automatically configured to provide mutual operation of at least three communication services. according to another non-limiting example, the antenna of the present invention may be automatically configured to operate over at least one octave frequency band within the frequency range of about 800 mhz to 3 ghz. the antenna of the present invention may be utilized in internet phones, bluetooth applications, tag systems, remote control units, video wireless phone, communications between internet and cellular phones, etc. the antenna may also be utilized in various intersystems, e.g., in communication within the computer wireless lan (local area network), pcn (personal communication network) and ism (industrial, scientific, medical network) systems. the antenna may also be utilized in communications between the lan and cellular phone network, gps (global positioning system) or gsm (global system for mobile communication). referring now to fig. 11 that schematically illustrates a spiral conductive layer antenna 200 according to another general aspect of the invention. the antenna 200 includes a dielectric substrate 202 on which a microstrip spiral 204 having a pattern of a reversed s-type zigzag ( 44 in fig. 4 b ) is fabricated by any conventional printed circuit technique. it should be appreciated that the spiral may be in any form, e.g., rectangular, archimedean, logarithmic, acentric, non-symmetric form and a combination thereof. according to one non-limiting example, the spiral has a two-arm configuration (as shown in fig. 11 ). according to another non-limiting example, the spiral has a multi-arm configuration (not shown). the antenna 200 may further include a backed cavity (not shown in fig. 11 ) arranged in any conventional manner, e.g., as described in the paper titled: reduced size spiral antenna, proc. 9-th european microwave conf., september. 1979, pages 181-185, by morgan (incorporated herein by reference). the antenna 200 may be fed by a source in any conventional manner. therefore, it will not be expounded hereinbelow. it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting. it is important, therefore, that the scope of the invention is not construed as being limited by the illustrative embodiments set forth herein. other variations are possible within the scope of the present invention as defined in the appended claims.
|
044-039-031-128-205
|
US
|
[
"CA",
"US"
] |
E01D22/00
| 1999-06-07T00:00:00 |
1999
|
[
"E01"
] |
process for demolishing a bridge structure
|
a process for demolishing a bridge deck by means of a truck assembly equipped with a a receptacle comprised of a right side and a left side and a first wing rotatably connected to the right side of the receptacle. the process includes the steps of: (a) disposing the truck assembly beneath the bridge deck, (b) rotating the first wing upwardly and outwardly from the right side of the receptacle to a first position, (c) supporting the first wing in its first position by means a support contiguous with the first wing, (d) demolishing the bridge deck and causing debris to fall therefrom, (d) receiving debris from the bridge deck within the receptacle, (e) ceasing supporting the first wing in its first position and moving it downwardly and inwardly towards the right side of the receptacle, (f) moving the trunk assembly, and (g) removing debris from the receptacle.
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1. a process for demolishing a bridge deck by means of a truck assembly equipped with a receptacle comprised of a right side and a left side, a first wing rotatably connected to said right side of said receptacle, comprising the steps of: (a) disposing said truck assembly beneath said bridge deck, (b) rotating said first wing upwardly and outwardly from said right side of said receptacle to a first position, (c) supporting said first wing in said first position by means of a support contiguous with said first wing, (d) demolishing said bridge deck and causing debris to fall therefrom, (d) receiving said debris from said bridge deck within said receptacle, (e) ceasing supporting said first wing in said first position and moving said first wing downwardly and inwardly towards said right side of said receptacle, (f) moving said truck assembly, and (g) removing said debris from said receptacle. 2. the process as recited in claim 1, wherein said truck assembly is comprised of a second wing rotatably connected to said left side of said receptacle. 3. the process as recited in claim 2, wherein said means of support is comprised of a first hydraulic cylinder assembly comprised of a first hydraulic cylinder, a second hydraulic cylinder disposed within said first hydraulic cylinder, and a first rod disposed within said second hydraulic cylinder. 4. the process as recited in claim 3, wherein said first hydraulic cylinder assembly is contiguous with said first wing. 5. the process as recited in claim 4, wherein said means of support is comprised of a second hydraulic cylinder assembly comprised of a third hydraulic cylinder, a fourth hydraulic cylinder disposed within said third hydraulic cylinder, and a second rod disposed within said fourth hydraulic cylinder. 6. the process as recited in claim 5, wherein said second hydraulic cylinder assembly is contiguous with said second wing. 7. the process as recited in claim 6, comprising the step of supporting said first wing by means of said first hydraulic cylinder assembly. 8. the process as recited in claim 7, comprising the step of supporting said second wing by means of said second hydraulic cylinder assembly. 9. the process as recited in claim 8, comprising the step of extending said second hydraulic cylinder away from said first hydraulic cylinder, thereby rotating said first wing upwardly and outwardly from said right side of said receptacle. 10. the process as recited in claim 9, comprising the step of extending said fourth hydraulic cylinder away from said third hydraulic cylinder, thereby rotating said second wing upwardly and outwardly from said left side of said receptacle. 11. the process as recited in claim 10, comprising the step of extending said first rod away from said second hydraulic cylinder, thereby rotating said first wing upwardly and outwardly from said right side of said receptacle. 12. the process as recited in claim 11, comprising the step of extending said second rod away from said fourth hydraulic cylinder, thereby rotating said second wing upwardly and outwardly from said left side of said receptacle. 13. the process as recited in claim 12, comprising the step of moving said first rod towards said second hydraulic cylinder, thereby rotating said first wing downwardly and inwardly towards said right side of said receptacle. 14. the process as recited in claim 13, comprising the step of moving said second rod towards said fourth hydraulic cylinder, thereby rotating said second wing downwardly and inwardly towards said left side of said receptacle. 15. the process as recited in claim 14, comprising the step of moving said second hydraulic cylinder towards said first hydraulic cylinder, thereby rotating said first wing downwardly and inwardly towards said right side of said receptacle. 16. the process as recited in claim 15, comprising the step of moving said fourth hydraulic cylinder towards said third hydraulic cylinder, thereby rotating said second wing downwardly and inwardly towards said left side of said receptacle.
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field of the invention a process for demolishing a bridge structure in which a truck with a receptacle and a movable wing connected to the receptacle is disposed under a bridge structure and the bridge structure is thereafter demolished. background of the invention u.s. pat. no. 4,955,972 of roy e. labounty discloses a container for catching falling debris from bridge deck demolitions. in the process described in this patent, a crane is disposed near a bridge deck and suspends a receptacle by means of a support arm connected to the receptacle. thereafter, by means of a cable connected to the receptacle and the crane, the receptacle is tilted so that crushed, collected concrete slides off of an open end of the receptacle and into a dump truck. this process is rather cumbersome and complicated, requiring a crane, a multiplicity of cables, a receptacle, and a dump truck. furthermore, because of the manner in which the receptacle is supported by the crane and tilted by the crane, the receptacle can only be placed under a portion of the bridge; the device of this patent effectively only can work at the edges of the bridge deck and, after they are demolished, at the new edges so formed; it is not capable of working in the middle of the bridge deck. thus, multiple cycles involving the steps of placing the receptacle at a specified location, filling the receptacle, moving and unloading the receptacle, moving the crane, repositioning the receptacle, and refilling it, are required. it is an object of this invention to provide a process for demolishing a bridge structure in which a receptacle for receiving debris from the demolished bridge structure may be located underneath the bridge structure. summary of the invention in accordance with this invention, there is provided a process for demolishing a bridge deck. in the first step of this process, a truck with a receptacle and a movable wing connected to the receptacle is disposed beneath a first portion of a bridge deck so that a substantial portion of the width of the bridge deck is disposed over the receptacle. thereafter, the movable wing is raised towards the bottom of the bridge deck, the bridge deck is demolished, debris from the bridge deck is received in the receptacle, and the truck is moved away from the first portion of the bridge deck. brief description of the drawings the claimed invention will be described by reference to the specification and to the enclosed drawings, in which like numerals refer to like elements, and in which: fig. 1 is a perspective view of one preferred truck with a dump trailer which can be used in the process of this invention; fig. 2 is a schematic view illustrating how two of the trucks of fig. 1 may be used in the process of the invention; fig. 3 is a back view of the truck of fig. 1 fig. 4 is a perspective view of another preferred truck with a dump trailer which can be used in the process of this invention; fig. 5 is a front view of a connector which may be used to connect one or more wings to the dump trailer depicted in fig. 4; fig. 6 is a side view of the connector of fig. 5; fig. 7 is a schematic illustration of one preferred means for supporting the wings of the truck of fig. 4; fig. 8 is sectional view of a bridge structure to which is connected an overhang bracket assembly; fig. 9 is an exploded view of the overhang bracket assembly of fig. 8; fig. 10 is a schematic representation of disposing the overhang bracket assembler in a desired position; and fig. 11 is a flow diagram of one preferred process of the invention. description of the preferred embodiments fig. 1 illustrates a preferred winged tractor trailer 10 which may be used in the process of the invention. referring to fig. 1, it will be seen that winged tractor trailer 10 is comprised of a truck 12 attached by conventional means to a rear dump trailer 14. as is known to those skilled in the art, a rear dump trailer is a receptacle with means for removably connecting the trailer to a tractor (such as a truck), a multiplicity of wheels attached to the trailer, and means for removing debris contained in the dump trailer by tilting the trailer up and away from the trailer bed at an angle greater than about 30 degrees and removing the debris from the rear of the trailer. these and similar dump trailers are well known to those skilled in the art and are described, e.g., in u.s. pat. nos. 5,782,538 (end dump trailer), 5,681,095 (dump body for a vehicle), 5,662,374 (dump body), 5,482,356 (rear dump trailer), 4,968,096 (dump trailer with lifting mechanism), 4,659,147 (dump trailer), 4,616,879, and the like. the entire description of each of these united states patents is hereby incorporated by reference into this specification. in one embodiment, not shown, a dump truck is used instead of the dump trailer assembly 14. such dump trucks are well known to those skilled in the art and are described, e.g., in u.s. pat. nos. 5,588,712, 5,452,942, 5,407,251, 4,955,972, 3,881,764, 3,601,447, and the like. the disclosure of each of these united states patents is hereby incorporated by reference into this specification. fig. 3 illustrates wing 18 in its initial position 36. after it is raised by means of two-stage hydraulic cylinder 24, it will be seen that wing 18 will have moved upwardly and outwardly in the direction of arrow 38 to the position 40 depicted in dotted line outline in fig. 3. the angle 42 between the initial position 36 of wing 18 and its final position 40 is generally from about 10 to about 180 degrees. it is generally preferred that angle 42 be from about 60 to about 150 degrees and, even more preferably, from about 100 to about 150 degrees. it one preferred embodiment, the top surfaces, 42 and 44, of wings 18 and 16 actually touch the bottom 46 of the bridge structure being worked on. referring again to fig. 3, it will be seen that wings 16 and 18 are preferably rotatably attached to trailer 14 by means of bracket 15, which is preferably integrally joined to trailer 14 by conventional means, such as welding. the bracket 15 is also connected to the wings 16 and 18 by conventional fasteners, such as, e.g., a solid pin. the two-stage hydraulic cylinder assemblies 24 and 22 are attached to trailer 14 by means of, e.g., brackets 17, each of which also is preferably integrally connected to trailer 14 by welding. fig. 2 illustrates one aspect of applicants' claimed process. in this embodiment, a bridge deck 48 is being demolished. as is known to those skilled in the art, a bridge deck is the surface of the bridge upon which vehicular traffic rides and can be comprised of or consist of concrete, steel, wood, etc. in one preferred embodiment, the bridge deck 48 consists essentially of reinforced concrete supported by steel girders 50. reinforced concrete bridge decks are well known to those skilled in the art and are described, e.g., in u.s. pat. nos. 5.579,361, 5,664,378, 5,639,358, 5,595,034, 5,509,243, 5,449,563, 5,427,819, and the like. the entire disclosure of each of these united states patents is hereby incorporated by reference into this specification. referring again to fig. 1, it will be seen that dump trailer 14 is connected to wings 16 and 18. these wings 16 and 18 may be raised and/or lowered by a hydraulic lift system comprised of hydraulic cylinder assemblies 20, 22 (see fig. 1), and 24 (see fig. 3). the hydraulic lift system is preferably a two-stage hydraulic lift system. thus, referring to fig. 3, it will be seen that hydraulic cylinder assembly 22 is comprised of hydraulic cylinder 26 within which is disposed hydraulic cylinder 28 within which is disposed rod 30. thus, the two stage hydraulic lift system operates by first extending cylinder 28 by means of hydraulic pressure, and thereafter extending rod 30 by means of hydraulic pressure. two stage hydraulic cylinder assemblies, and means for controlling them, are well known to those skilled in the art and are described, e.g., in 5,829,947 (two stage hydraulic lift cylinder), 5,649,424 (two stage pressure cylinder), 5,551,391 (control system for two stage hydraulic lift cylinder), 5,467,754, 5,341,837, 5,241,935, 4,852,464 (two stage telescoping hydraulic cylinder), 4,172,612 (two stage telescopic hydraulic cylinder), and the like. the entire disclosure of each of these united states patents is hereby incorporated by reference into this specification. thus, in the process of the invention, hydraulic cylinder 28 is first raised, and then rod 30 is then raised. conversely, when hydraulic pressure has been removed, rod 30 is first retracted and lowered, and then hydraulic cylinder 28 is then retracted and lowered. referring again to fig. 1, and in the preferred embodiment depicted therein, it will be seen that means for locking hydraulic cylinders 20, 22, et seq. are provided. in the preferred embodiment illustrated, manual hydraulic shut off valves 32 are provided, preferably one for each hydraulic cylinder assembly. these shut off valves 32, or similar structure, may be used to lock each such hydraulic cylinder assembly in place once it has reached the desired position. each of wings 16 and 18 preferably each have a width 34 of from about 4 to about 8 feet. it is preferred that the lengths of the wings be substantially equal to the lengths of the trailer 14 and/or the dump truck (not shown) to which the wings are connected. fig. 2 illustrates one preferred embodiment in which two winged tractor trailers 10 are used. in this embodiment, an excavator 51 equipped with a hydraulic hoe ram 52 is used to demolish the bridge deck 48. one may use other demolition means such as, e.g., those described in u.s. pat. nos. 5,014,381, 4,955,972, 4,641,581 (use of explosive charges), 4,633,975, and the like. the disclosure of each of these united states patents is hereby incorporated by reference into this specification. in one embodiment, not shown, concrete slab saws are used to cut the bridge deck. these concrete slab saws are well known and are described, e.g., in u.s. pat. nos. 4,945,356, 4,938,201, 4,928,662, 4,889,675, 4,769,201, 4,310,198, and the like. the entire disclosure of each of these united states patents is hereby incorporated by reference into this specification. in one aspect of this embodiment, the bridge deck 48 is cut into substantially rectangular slabs with a width of from about 5 to about 9 feet and a length of from about 6 to about 19 feet; it is preferred that each such slab be supported, at least in part, by one or more steel girders 50. thereafter, each such slab is then hoisted off of the bridge by means of a hydraulic excavator 51 and/or a crane (not shown). in another embodiment, the bridge deck 48 is cut into the aforementioned slabs by means of hydraulic excavator 51/hoe ram 52 (see fig. 2) and thereafter, hoisted off the bridge, preferably by means of excavator 51. in this embodiment, it is preferred to cut the slab by means of the hoe ram 52, and thereafter support the cut slab with the hoe ram 52 while cutting the reinforcement bars on the left and right sides of the slab by means of a torch (such as an oxyacetylene torch), and thereafter fold the slab back towards the excavator 5 1, and thereafter cut the reinforcement bars on the back side of the slab. referring to fig. 2, rear dump trailers 14 is completely disposed under the bridge deck 48. with wings 16 and 18 extended, the effective width 54 if presented to the deck is from about 9 to about 24 feet. inasmuch as rear dump trailers 14 may be from about 16 to about 40 feet in length, the cross-sectional area provided by the winged receptacles to deck 48 is substantial. in general, an effective cross-sectional area of at least 500 square feet is provided to catch debris from deck 48. it is preferred that the effective cross-sectional area be from about 600 to about 800 square feet. in one embodiment, not shown in fig. 2, the wings 16 and 18 contact the bottom 46 of the bridge 56. in this embodiment, the receptacles formed by the bottom of the bridge 46, the upstanding wings 16 and 18, and the trailer 14, effectively protect vehicular traffic and/or persons near bridge from flying debris. fig. 4 is a perspective view of a dump trailer 14 equipped with wings 16 and 18 wherein the wings are supported by means of arms 60 and brackets 62. fig. 5 is a front view of a preferred bracket 62. referring to fig. 5, and in the preferred embodiment depicted, it will be seen that leg 64 is preferably longer than leg 66. the bracket 62 is preferably connected to wing 16 by means of pin 71. as will be apparent, the pin 70 allows the wing 16 to swivel upwardly and outwardly. thus, referring again to fig. 4, wings 16 and 18 may be swiveled upwardly and outwardly in the direction of arrow 38 and, when it has reached its desired position, be held in place by stiff legs 60. one may use one-piece stiff legs 60 with a specified length. alternatively, or additionally, one may use adjustable stiff legs with variable lengths. as will be apparent, brackets 62 may be removably mounted on trailer 14, and/or they may be integrally and permanently affixed to the trailer by conventional means. a novel overhang bracket fig. 2 shows that, in the process depicted therein, in addition to using two winged tractor trailers 10 to catch failing debris, one may also use one or more overhang brackets 70 to catch debris in areas where the tractor-trailer assemblies 10 are not located. these overhang brackets 70 also serve to protect vehicular and pedestrian traffic under the bridge 56 while work is in progress. one preferred embodiment of overhang bracket 70 is illustrated in fig. 9. referring to fig. 9, it will be seen that bracket 70 is comprised of an bracket frame 72 and bracket deck 74 integrally connected to each other by conventional means such as, e.g., welding. the bracket frame 72, in the embodiment depicted, is comprised of triangular braces 76. in the embodiment depicted, three such triangular braces are present. in general, it is preferred to use from about 2 to 4 such triangular braces. the bracket deck 74 is preferably made from formed sheet metal to which are connected a multiplicity of post supports 78 preferably made from box tubing. three such post supports are illustrated in fig. 9, but from about 2 to about 4 such post supports 78 may be used. as is illustrated in fig. 9, removably connected to the bracket deck 74 is a splatter guard 80 which is comprised of a multiplicity of box tubing inserts 82 adapted to be received within post supports 78. the splatter guard 80 is preferably constructed from sheet metal or plywood. referring again to fig. 9, it will be seen that the bracket frame 72/bracket deck 74 assembly, after the two pieces have been integrally connected to each other, may be joined to bridge girder 50 by means of connectors (not shown) disposed in orifices 82. in the embodiment depicted in fig. 10, the orifices 82 (see fig. 9) are lined up by means of crane or hydraulic excavator (not shown) from which cables 86 and 88 are suspended. the cables move an installation/removal bracket 90 into place so that, when moved in the direction of arrow 92 tube 94 may be inserted into orifice 96 of bracket frame 72 (see fig. 9). after such insertion, the bracket frame 72/bracket deck 74 may be hoisted into a position appropriate to align orifices 82 (see fig. 9). a preferred process of the invention fig. 11 illustrates one preferred process of the instant invention. in step 100 of this process, one or more of tractor-trailers 10 is disposed under the bridge deck 48. in this step, it is preferred to so dispose the tractor-trailers 10 so that at least about 600 square feet of cross-sectional area is disposed above each such tractor trailer. in one embodiment, not shown, the overhang bracket 70 is installed on the bridge deck prior to moving the tractor-trailer(s) 10 in place. in another embodiment, not shown, the overhang bracket 70 is installed on the bridge deck just after moving the tractor trailers 10 in place. in step 102 of this process, wing 16 is initially raised upwardly and outwardly by means of a first hydraulic cylinder. thereafter, in step 104 of this process, wing 16 is raised upwardly and outwardly by means of a rod. once the wing 16 has been raised to the desired position, it is preferably locked in place with shut off valves 32 in step 106. thereafter, in step 108, the bridge deck 48 is demolished by conventional means. it is preferred, after a section of bridge deck 48 has been demolished and/or after al truck a receptacle has been completely filled, to lower the wing 16. thus, in this preferred embodiment, in step 110, the wing 16 is preferably unlocked and, thereafter, in step 112, the wing 16 is moved downwardly and inwardly by retracting rod 30. thereafter, in step 114 the wing 16 is further moved downwardly and inwardly by retracting hydraulic cylinder 28. thereafter, in step 116, the tractor trailer 10 is driven away from the bride deck 48, preferably to a disposal area into shown) where the debris may be dumped or removed by other conventional means. it is to be understood that the aforementioned description is illustrative only and that changes can be made in the apparatus, in the ingredients and their proportions, and in the sequence of combinations and process steps, as well as in other aspects of the invention discussed herein, without departing from the scope of the invention as defined in the following claims.
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044-138-331-412-623
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EP
|
[
"EP",
"US",
"WO",
"CN"
] |
C11D3/386,C11D11/00
| 2018-10-11T00:00:00 |
2018
|
[
"C11"
] |
cleaning compositions and uses thereof
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the present invention relates to compositions such as cleaning compositions comprising a mix of enzymes. the invention further relates, use of compositions comprising such enzymes in cleaning processes.
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1 . a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component. 2 . a cleaning composition according to claim 1 , wherein the alpha-mannan degrading enzyme is of the gh family gh76, gh92 or gh99. 3 . a cleaning composition according to claim 1 , wherein the alpha-mannan degrading enzyme is a gh76 glycosyl hydrolase. 4 . a cleaning composition according to claim 3 , wherein the alpha-mannan degrading enzyme has at least 60%, sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 89, 90, 91, 92, 93, 94, 95, 96 and 97. 5 . a cleaning composition according to claim 1 , wherein the alpha-mannan degrading enzyme is a gh92 glycosyl hydrolase. 6 . a cleaning composition according to claim 5 , wherein the alpha-mannan degrading enzyme has at least 60%, sequence identity to the amino acid sequence shown in seq id no: 87. 7 . a cleaning composition according to claim 1 , wherein the alpha-mannan degrading enzyme is a gh99 glycosyl hydrolase. 8 . a cleaning composition according to claim 7 , wherein the alpha-mannan degrading enzyme has at least 60%, sequence identity to the amino acid sequence shown in seq id no: 88. 9 . a cleaning composition according to claim 1 , wherein the dnase is obtained from bacteria or fungi. 10 . a cleaning composition according to claim 1 , wherein the dnase is obtained from bacillus. 11 . a cleaning composition according to claim 1 , wherein the dnase comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). 12 . a cleaning composition according claim 9 , wherein the dnase has at least 60% sequence identity to the amino acid sequence shown in seq id no: 13. 13 . a cleaning composition according to claim 9 , sequence identity to the amino acid sequence shown in seq id no: 65. 14 . a cleaning composition according to claim 9 , wherein the dnase has at least 60% sequence identity to the amino acid sequence shown in seq id no: 66. 15 . a cleaning composition according to claim 9 , wherein the dnase sequence identity to the amino acid sequence shown in seq id no: 67. 16 . a cleaning composition according to claim 9 , wherein the dnase sequence identity to the amino acid sequence shown in seq id no: 68. 17 . a cleaning composition according to claim 1 , wherein the amount of dnase in the composition is from 0.01 to 1000 ppm and the amount of alpha-mannan degrading enzyme is from 0.01 to 1000 ppm. 18 . a cleaning composition according to claim 1 , wherein the cleaning component is selected from surfactants, builders and bleach components. 19 . (canceled) 20 . a method of cleaning of an item, comprising the steps of: a) contacting the item with a cleaning composition according to claim 1 ; and b) optionally rinsing the item, wherein the item is preferably a textile.
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reference to a sequence listing this application contains a sequence listing in computer readable form, which is incorporated herein by reference. background of the invention the present invention relates to compositions such as cleaning compositions comprising a mix of enzymes. the invention further relates to the use of compositions comprising such enzymes in cleaning processes and/or for deep cleaning of organic stains and to methods for removal or reduction of components of organic matter. description of the related art enzymes have been used in detergents for decades. usually a cocktail of various enzymes is added to detergent compositions. the enzyme cocktail often comprises various enzymes, wherein each enzyme targets it specific substrate e.g. amylases are active towards starch stains, proteases on protein stains and so forth. textile and hard surfaces, such as dishes or the inner space of a laundry machine enduring a number of wash cycles, become soiled with many different types of soiling which may compose of proteins, grease, starch etc. one type of stains may be poly-organic such as stains from body soiling e.g. skin cell debris, sebum, sweat, and biofilm, eps, etc. poly-organic stains composes different organic molecules such as polysaccharides, extracellular dna (exdna), mannan, starch and proteins. some biofilm eps in particular from fungi may comprise polysaccharide constituents such as α-mannan, β-1,6 glucan, and β-1,3 glucan. some organic matter may be sticky or glueing, which when present on textile, attracts soils and may course redeposition or backstaining of soil resulting in a greying of the textile. additionally, polymeric substances such as eps often cause malodor issue as various malodor molecules can be adhered by the polysaccharides, extracellular dna (exdna), and proteins in the complex extracellular matrix and be slowly released to cause consumer noticeable malodor issue. there is still a need for cleaning compositions, which effectively prevent, reduce or remove stains. the present invention provides new compositions fulfilling such need. summary of the invention a first aspect of the present invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component. a second aspect of the invention relates to the use of a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component for deep cleaning of an item, wherein the item is a textile or a surface. a third aspect of the invention relates to a method of cleaning of an item, comprising the steps of: a) contacting the item with a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component; andb) optionally rinsing the item, wherein the item is preferably a textile. detailed description of the invention various enzymes are applied in cleaning processes each targeting specific types of stains such as protein, starch and grease stains. enzymes are now standard ingredients in detergents for laundry and dish wash. the effectiveness of these commercial enzymes provides detergents which removes much of the soiling. however, components of organic matters such as body soils, e.g. dead skin cells, cell debris, sweat, biofilm eps (extracellular polymeric substance) components and pollution components constitute a challenging type of staining due to the complex nature of such organic stains. none of the commercially available cleaning compositions effectively remove or reduce such complex stains. polysaccharides, mannan and macromolecules such as dna are difficult to remove with the traditional cleaning compositions, when all mixed in a poly organic stain. the poly-organic comprising polysaccharides and dna may also have glue effects when such stains stick to e.g. laundry textile as well as coursing malodor. a poly-organic stain is in the context of the present invention a stain comprising more than one organic component such as stains from body soiling e.g. skin cell debris, sebum, sweat, and biofilm, eps, etc. which comprises several organic molecules such as polysaccharides, extracellular dna (exdna), mannan e.g. α-mannan, starch and proteins. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and effectively reduce or remove organic components, such as mannan and dna from surfaces such as textiles and hard surfaces e.g. dishes. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and effectively reduce or limit redeposition when applied in e.g. laundry process. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and effectively reduce or limit malodor of e.g. textiles or hard surfaces such as dishes. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and improve whiteness of textile. a composition of the invention is preferably a cleaning composition, the composition of the invention comprises at least one dnase and at least one alpha-mannan degrading enzyme. examples of useful dnases and alpha-mannan degrading enzymes are mentioned below in the sections “polypeptides having dnase activity” and “polypeptides having alpha-mannan degrading enzyme activity” respectively. polypeptides having dnase activity the term “dnase” means a polypeptide with dnase (deoxyribonuclease) activity that catalyzes the hydrolytic cleavage of phosphodiester linkages in a dna backbone, thus degrading dna. exodeoxyribonuclease cut or cleaves residues at the end of the dna back bone where endo-deoxyribonucleases cleaves or cut within the dna backbone. a dnase may cleave only double-stranded dna or may cleave double stranded and single stranded dna. the term “dnases” and the expression “a polypeptide with dnase activity” may be used interchangeably throughout the application. for purposes of the present invention, dnase activity is determined according to the procedure described in the assay i or ii. preferably the dnase is selected from any of the enzyme classes e.c.3.1, preferably e.c.3.1.21, e.g. such as e.c.3.1.21.x, where x=1, 2, 3, 4, 5, 6, 7, 8 or 9, or e.g. deoxyribonuclease 1, deoxyribonuclease iv, type i site-specific deoxyribonuclease, type ii site-specific deoxyribonuclease, type iii site-specific deoxyribonuclease, cc-preferring endo-deoxyribonuclease, deoxyribonuclease v, t(4) deoxyribonuclease ii, t(4) deoxyribonuclease iv or e.c. 3.1.22.y where y=1, 2, 4 or 5, e.g. deoxyribonuclease ii, aspergillus deoxyribonuclease k(1), crossover junction endo-deoxyribonuclease, deoxyribonuclease x. preferably, the polypeptide having dnase activity is obtained from a microorganism and the dnase is a microbial enzyme. the dnase is preferably of fungal or bacterial origin. the dnase may be obtainable from bacillus e.g. such as a bacillus licheniformis, bacillus subtilis, bacillus horikoshii, bacillus horneckiae, bacillus cibi, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi, bacillus luciferensis. the dnase may also be obtained from any of the following pyrenochaetopsis sp., vibrissea flavovirens, setosphaeria rostrate, endophragmiella valdina, corynespora cassiicola, paraphoma sp., monilinia fructicola, curvularia lunata, penicillium reticulisporum, penicillium quercetorum, setophaeosphaeria sp., alternaria, alternaria sp., trichoderma reesei, chaetomium thermophilum, scytalidium thermophilum, metapochonia suchlasporia, daldinia fissa, acremonium sp., acremonium dichromosporum, sarocladium sp., metarhizium sp., isaria tenuipes scytalidium circinatum, metarhizium lepidiotae, thermobispora bispora, sporormia fimetaria, pycnidiophora cf. dispera, clavicipitaceae sp., westerdykella sp., humicolopsis cephalosporioides, neosartorya massa, roussoella intermedia, pleosporales, phaeosphaeria or didymosphaeria futilis. in one embodiment the dnases to be used in a composition of the invention preferable belong to the nuc1 group of dnases. the nuc1 group of dnases comprises polypeptides which in addition to having dnase activity, may comprise one or more of the motifs [t/d/s][g/n]pql (seq id no: 69), [f/l/y/i]a[n/r]d[l/i/p/v] (seq id no: 70), or c[d/n]t[a/r] (seq id no: 71). one embodiment of the invention relates to a composition comprising an alpha-mannan degrading enzyme and a polypeptide having dnase activity, wherein the polypeptide comprises one or more of the motifs [t/d/s][g/n]pql (seq id no: 69), [f/l/y/i]a[n/r]d[l/i/p/v] (seq id no: 70) and/or c[d/n]t[a/r] (seq id no: 71). the dnases preferably comprise a nuc1_a domain [d/q][i/v]dh (seq id no: 72). in addition to comprising any of the domain motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v] or c[d/n]t[a/r] the polypeptides having dnase activity, to be used in a composition of the invention, may comprise the nuc1_a domain and may share the common motif [d/q][i/v]dh (seq id no: 72). one embodiment the invention relates to compositions comprising an alpha-mannan degrading enzyme and polypeptides, which comprises one or more motifs selected from the motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v], c[d/n]t[a/r] and [d/q][i/v]dh, wherein the polypeptides have dnase activity. the dnases to be added to a composition of the invention preferably belong to the group of dnases comprised in the gys-clade, which are group of dnases on the same branch of a phylogenetic tree having both structural and functional similarities. these dnases which may be defined as nuc1 and/or nuc1_a dnases comprise the conservative motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74) and share similar structural and functional properties. the dnases of the gys-clade are preferably obtained from bacillus genus. one embodiment of the invention relates to a composition comprising an alpha-mannan degrading enzyme and a polypeptide of the gys clade having dnase activity, optionally wherein the polypeptide comprises one or both of the motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73), asxnrskg (seq id no: 74) and wherein the polypeptide is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 1,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 2,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 3,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 4,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 5,f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 6,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 7,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 8,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 9,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 10,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 11,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 12,m) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 13,n) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 14,o) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 15,p) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 16,q) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 17,r) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 18,s) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 19,t) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 20,u) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 21,v) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 22,w) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 23,x) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 24, andy) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 25. polypeptides having dnase activity and which comprise the gys-clade motifs have shown particularly good deep cleaning properties e.g. the dnases are particularly effective in removing or reducing components of organic matter, such as dna, from an item such as a textile or a hard surface. in addition, these dnases are particularly effective in removing or reducing malodor, from an item such as a textile or a hard surface. further, the gys-clade dnases are particularly effective in preventing redeposition when laundering an item such as textile. in one embodiment the dnases to be added in a composition of the invention preferably belong to the group of dnases comprised in the nawk-clade, which may be defined as nuc1 and nuc1_a dnases, which may further comprise the conservative motifs [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76). one embodiment of the invention relates to a composition comprising an alpha-mannan degrading enzyme and a polypeptide of the nawk-clade having dnase activity, optionally wherein the polypeptide comprises one or both of the motifs [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76) and wherein the polypeptide is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 26,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 27,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 28,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 29,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 30,f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 31,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 32,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 33,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 34,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 35,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 36,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 37, andm) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 38. polypeptides having dnase activity and which comprise the nawk-clade motifs have shown particularly good deep cleaning properties e.g. the dnases are particularly effective in removing or reducing components of organic matter, such as dna, from an item such as a textile or a hard surface. in addition, these dnases are particularly effective in removing or reducing malodor, from an item such as a textile or a hard surface. further, the nawk-clade dnases are particularly effective in preventing redeposition when laundering an item such as textile. the dnases to be added in a composition of the invention preferably belong to the group of dnases comprised in the knaw-clade, which may be defined as nuc1 and nuc1_a dnases which may further comprise the conservative motifs p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78). one embodiment of the invention relates to a composition comprising an alpha-mannan degrading enzyme and a polypeptide of the knaw clade having dnase activity, optionally wherein the polypeptide comprises one or both of the motifs p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78), and wherein the polypeptide is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 39,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 40,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 41,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 42,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 43f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 44,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 45,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 46,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 47,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 48,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 49,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 50, andm) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75% at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 51. polypeptides having dnase activity and which comprise the knaw-clade motifs have shown particularly good deep cleaning properties e.g. the dnases are particularly effective in removing or reducing components of organic matter, such as dna, from an item such as a textile or a hard surface. in addition, these dnases are particularly effective in removing or reducing malodor, from an item such as a textile or a hard surface. further, the knaw-clade dnases are particularly effective in preventing redeposition when laundering an item such as textile. the dnases of the gys, nawk and knaw-clades are also described in wo2017/060475 (novozymes a/s). in some embodiments, the present invention relates compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 1 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 1. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus horikoshii , having a sequence identity to the polypeptide shown in seq id no: 2 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 2. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 3 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 3. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 4 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 4. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus horikoshii , having a sequence identity to the polypeptide shown in seq id no: 5 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 5. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus horikoshii , having a sequence identity to the polypeptide shown in seq id no: 6 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 6. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 7 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 7. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 8 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 8. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 9 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 9. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 10 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 10. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus horneckiae, having a sequence identity to the polypeptide shown in seq id no: 11 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 11. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 12 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 12. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus cibi , having a sequence identity to the polypeptide shown in seq id no: 13 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 13. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 14 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 14. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus idriensis, having a sequence identity to the polypeptide shown in seq id no: 15 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 15. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus algicola , having a sequence identity to the polypeptide shown in seq id no: 16 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 16. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide having a sequence identity to the polypeptide shown in seq id no: 17 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 17. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus vietnamensis , having a sequence identity to the polypeptide shown in seq id no: 18 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 18. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus hwajinpoensis, having a sequence identity to the polypeptide shown in seq id no: 19 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 19. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from paenibacillus mucilaginosus , having a sequence identity to the polypeptide shown in seq id no: 20 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 20. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus indicus , having a sequence identity to the polypeptide shown in seq id no: 21 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 21. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus marisflavi , having a sequence identity to the polypeptide shown in seq id no: 22 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 22. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus luciferensis , having a sequence identity to the polypeptide shown in seq id no: 23 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 23. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus marisflavi , having a sequence identity to the polypeptide shown in seq id no: 24 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 24. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide preferably obtainable from bacillus , having a sequence identity to the polypeptide shown in seq id no: 25 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 25. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from pyrenochaetopsis sp., having a sequence identity to the polypeptide shown in seq id no: 26 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 26. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from vibrissea flavovirens , having a sequence identity to the polypeptide shown in seq id no: 27 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 27. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from setosphaeria rostrate, having a sequence identity to the polypeptide shown in seq id no: 28 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 28. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from endophragmiella valdina , having a sequence identity to the polypeptide shown in seq id no: 29 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 29. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from corynespora cassiicola , having a sequence identity to the polypeptide shown in seq id no: 30 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 30. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from paraphoma sp. xz1965, having a sequence identity to the polypeptide shown in seq id no: 31 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 31. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from monilinia fructicola , having a sequence identity to the polypeptide shown in seq id no: 32 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 32. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from curvularia lunata , having a sequence identity to the polypeptide shown in seq id no: 33 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 33. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from penicillium reticulisporum , having a sequence identity to the polypeptide shown in seq id no: 34 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 34. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from penicillium quercetorum , having a sequence identity to the polypeptide shown in seq id no: 35 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 35. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from setophaeosphaeria sp., having a sequence identity to the polypeptide shown in seq id no: 36 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 36. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from alternaria sp., having a sequence identity to the polypeptide shown in seq id no: 37 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 37. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from alternaria , having a sequence identity to the polypeptide shown in seq id no: 38 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 38. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from trichoderma reesei , having a sequence identity to the polypeptide shown in seq id no: 39 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 39. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from chaetomium thermophilum , having a sequence identity to the polypeptide shown in seq id no: 40 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 40. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from scytalidium thermophilum , having a sequence identity to the polypeptide shown in seq id no: 41 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 41. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from metapochonia suchlasporia , having a sequence identity to the polypeptide shown in seq id no: 42 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 42. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from daldinia fissa , having a sequence identity to the polypeptide shown in seq id no: 43 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 43. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from acremonium sp., having a sequence identity to the polypeptide shown in seq id no: 44 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 44. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from acremonium dichromosporum , having a sequence identity to the polypeptide shown in seq id no: 45 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 45. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from sarocladium sp., having a sequence identity to the polypeptide shown in seq id no: 46 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 46. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from metarhizium sp., having a sequence identity to the polypeptide shown in seq id no: 47 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 47. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from acremonium sp., having a sequence identity to the polypeptide shown in seq id no: 48 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 48. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from isaria tenuipes , having a sequence identity to the polypeptide shown in seq id no: 49 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 49. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from scytalidium circinatum , having a sequence identity to the polypeptide shown in seq id no: 50 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 50. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from metarhizium lepidiotae , having a sequence identity to the polypeptide shown in seq id no: 51 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 51. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from thermobispora bispora , having a sequence identity to the polypeptide shown in seq id no: 52 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 52. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from sporormia fimetaria , having a sequence identity to the polypeptide shown in seq id no: 53 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 53. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from pycnidiophora cf. dispera, having a sequence identity to the polypeptide shown in seq id no: 54 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 54. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, having a sequence identity to the polypeptide shown in seq id no: 55 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 55. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, having a sequence identity to the polypeptide shown in seq id no: 56 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 56. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from clavicipitaceae, having a sequence identity to the polypeptide shown in seq id no: 57 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 57. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from westerdykella sp., having a sequence identity to the polypeptide shown in seq id no: 58 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 58. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from humicolopsis cephalosporioides , having a sequence identity to the polypeptide shown in seq id no: 59 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 59. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferable obtainable from neosartorya massa , having a sequence identity to the polypeptide shown in seq id no: 60 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 60. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from roussoella intermedia , having a sequence identity to the polypeptide shown in seq id no: 61 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 61. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from pleosporales, having a sequence identity to the polypeptide shown in seq id no: 62 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 62. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from phaeosphaeria , having a sequence identity to the polypeptide shown in seq id no: 63 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 63. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from didymosphaeria futilis , having a sequence identity to the polypeptide shown in seq id no: 64 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 64. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus licheniformis , having a sequence identity to the polypeptide shown in seq id no: 65 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 65. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from bacillus e.g. obtainable from bacillus subtilis , having a sequence identity to the polypeptide shown in seq id no: 66 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 66. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from aspergillus e.g. obtainable from aspergillus oryzae , having a sequence identity to the polypeptide shown in seq id no: 67 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 67. in some embodiments, the present invention relates to compositions comprising an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and a polypeptide, preferably obtainable from trichoderma e.g. obtainable from trichoderma harzianum , having a sequence identity to the polypeptide shown in seq id no: 68 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity. in one aspect, the polypeptides differ by up to 10 amino acids, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, from the mature polypeptide shown in seq id no: 68. polypeptides having alpha-mannan degrading enzyme activity the term “alpha-mannan degrading enzyme” or “polypeptide having alpha-mannan degrading activity” or alpha-mannanases means an enzyme having hydrolase activity on alpha-mannan. for purposes of the present invention, alpha-mannanase activity is determined according to the procedure described in the assay ill. relevant are enzymes having alpha-mannanase and/or alpha-mannosidase activity. in particular, the polypeptide having alpha-mannan degrading activity includes glycoside hydrolase domains gh76, gh92, or gh99, as defined in cazy (available at cazy.org, and as described in lombard v, et al. 2014, nucleic acids res 42:d490-d495). these can include enzyme activities such as alpha-1,6-mannanase (ec 3.2.1.101), alpha-1,2-mannase; mannosyl-oligosaccharide alpha-1,2-mannosidase (ec 3.2.1.113); mannosyl-oligosaccharide alpha-1,3-mannosidase (ec 3.2.1.-); mannosyl-oligosaccharide alpha-1,6-mannosidase (ec 3.2.1.-); alpha-mannosidase (ec 3.2.1.24); alpha-1,2-mannosidase (ec 3.2.1.-); alpha-1,3-mannosidase (ec 3.2.1.-); alpha-1,4-mannosidase (ec 3.2.1.-); mannosyl-1-phosphodiester alpha-1,p-mannosidase (ec 3.2.1.-); glycoprotein endo-alpha-1,2-mannosidase (ec 3.2.1.130); and/or mannan endo-1,2-alpha-mannanase (3.2.1.-) activities. according to the online carbohydrate-active enzyme (“cazy”) database (available at cazy.org), alpha-mannan degrading enzymes have been found in glycoside hydrolase families including 76, 92, and 99. the present invention provides compositions comprising a polypeptide having dnase activity and polypeptides having alpha-mannanase activity. polypeptides having alpha-mannan degrading activity or alpha-mannan degrading enzymes are enzymes having hydrolase activity on alpha-mannan. in particular, the polypeptide having alpha-mannan degrading activity includes enzymes from glycoside hydrolase domains gh76, gh92, and gh99, which are enzymes having alpha-mannanase and/or alpha-mannosidase activity. in one embodiment, the polypeptide belongs to gh family 76. in one embodiment, the polypeptide belongs to gh family 92. in one embodiment, the polypeptide belongs to gh family 99. also contemplated are compositions comprising dnase with blends of polypeptides having alpha-mannan degrading activity, including, for example, combinations of polypeptides having two or more different gh classifications according to the cazy naming system. in an embodiment are provided compositions comprising a dnase and any of the blends selected from the group consisting of: i. a polypeptide belonging to gh family 76 and a polypeptide belonging to gh family 92;ii. a polypeptide belonging to gh family 76 and a polypeptide belonging to gh family 99; andiii. a polypeptide belonging to gh family 92 and a polypeptide belonging to gh family 99. also contemplated are blends of three or more different gh classifications according to the cazy naming system, including blends comprising a polypeptide belonging to gh family 76, a polypeptide belonging to gh family 92, and a polypeptide belonging to gh family 99. in some embodiments, the present invention relates compositions e.g. cleaning compositions, comprising a dnase and a polypeptide selected from the group consisting of: (a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 79 or a fragment thereof having alpha-mannan degrading activity;(b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 80 or a fragment thereof having alpha-mannan degrading activity;(c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 81 or a fragment thereof having alpha-mannan degrading activity;(d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 82 or a fragment thereof having alpha-mannan degrading activity;(e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 83 or a fragment thereof having alpha-mannan degrading activity;(f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 84 or a fragment thereof having alpha-mannan degrading activity;(g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 85 or a fragment thereof having alpha-mannan degrading activity;(h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 86 or a fragment thereof having alpha-mannan degrading activity;(i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 87 or a fragment thereof having alpha-mannan degrading activity;(j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 88 or a fragment thereof having alpha-mannan degrading activity;(k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 89 or a fragment thereof having alpha-mannan degrading activity;(l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 90 or a fragment thereof having alpha-mannan degrading activity;(m) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 91 or a fragment thereof having alpha-mannan degrading activity;(n) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 92 or a fragment thereof having alpha-mannan degrading activity;(o) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 93 or a fragment thereof having alpha-mannan degrading activity;(p) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 94 or a fragment thereof having alpha-mannan degrading activity;(q) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 95 or a fragment thereof having alpha-mannan degrading activity;(r) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 96 or a fragment thereof having alpha-mannan degrading activity, and(s) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 97 or a fragment thereof having alpha-mannan degrading activity. cleaning compositions the invention relates to cleaning compositions comprising a dnase and an alpha-mannan degrading enzyme in combination with one or more additional cleaning composition components. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component. the alpha-mannan degrading enzyme may be any of the alpha-mannan degrading enzymes mentioned under the heading “polypeptides having alpha-mannan degrading enzyme activity”. preferably the alpha-mannan degrading enzyme is of (belongs to) the glycosyl hydrolase family gh76, gh92 or gh99. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is of the gh family gh76, gh92 or gh99. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh76 glycosyl hydrolase. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh92 glycosyl hydrolase. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh99 glycosyl hydrolase. the most relevant alpha-mannan degrading enzymes for cleaning are those belonging to the glycosyl hydrolase families gh76, gh92 or gh99, such alpha-mannan degrading enzymes have shown to be active in detergents and to effectively remove mannan. further, the alpha-mannan degrading enzymes acts synergistically with the dnase in poly-organic stains e.g. in reduction, and removal of biofilm or components hereof e.g. dna and/or mannan. biofilm eps is a complex structure comprising e.g. polysaccharides and dna, the target substrate e.g. the dna may be embedded in the biofilm structure and it's believed that when the dnases and alpha-mannan degrading enzymes are acting together, the dna and mannan components are more effectively removed. it is thus advantageous to formulate dnases with alpha-mannan degrading enzymes in cleaning compositions e.g. for laundry. one aspect of the invention relates to a method of formulating a cleaning composition comprising adding a dnase, an alpha-mannan degrading enzyme and at least one cleaning component. the invention further relates to a kit intended for deep cleaning, wherein the kit comprises a solution of an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme. the most relevant mannan degrading enzymes used in the cleaning industry today are beta mannanases e.g. of the gh5 or gh26 glycosyl hydrolase families. in contrast, the enzymes of the invention are alpha-mannan degrading enzymes, which have shown to be useful together with the dnases. this is surprising as glycosyl hydrolases degrading alpha mannan are not know for use in cleaning compositions for e.g. laundry and dish wash. alpha-mannan degrading enzymes suitable for combining with the dnases in the cleaning composition of the invention are preferably glycosyl hydrolases of the gh76, gh92 or gh99 families, which are suitable for cleaning and which has high stain removal capacity under cleaning conditions e.g. in the presence of surfactants, builders or other cleaning components. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequences shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 79. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 80. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 81. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 82. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 83. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 84. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 85. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 86. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 87. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 88. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 89. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 90. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 91. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 92. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 93. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 94. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 95. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 96. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 97. as mentioned the alpha-mannan degrading enzyme should be compatible with cleaning components and likewise, the dnases to be formulated together with the alpha-mannan degrading enzyme or to be used together with the alpha-mannan degrading enzyme should also be compatible with cleaning components. dnases as well as alpha mannanases are at present not standard ingredients in cleaning compositions. however, the applicant has identified dnases suitable for use in cleaning compositions e.g. in wo2017/060475, wo2014/087011, wo2015/155350 and wo2015/155351. enzymes, such as dnases should not only be compatible with the cleaning components the dnases should also be compatible with other enzymes which may be present in a typical cleaning composition. the inventors have found that the alpha mannan degrading enzymes are compatible with the dnases and preferably are even acting synergistically to remove or reduce complex organic stains (poly-organic stains) or components hereof e.g. extracellular polymeric substances, biofilm, body soils such as skin debris and pollution particles. particularly useful dnases may be those of microbial origin. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase is microbial, preferably obtained from bacteria or fungi. in one embodiment, the cleaning composition comprise a dnase from bacteria. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase is obtained from bacillus , preferably bacillus cibi, bacillus horikoshii, bacillus licheniformis, bacillus subtilis, bacillus horneckiae, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi or bacillus luciferensis . one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase is obtained from aspergillus , preferably aspergillus oryzae. as mentioned above the dnases to be used in a composition of the invention preferable belong to the nuc1 group of dnases. the nuc1 group of dnases may comprise one or more of the motifs [t/d/s][g/n]pql (seq id no: 69), [f/l/y/i]a[n/r]d[l/i/p/v] (seq id no: 70), or c[d/n]t[a/r] (seq id no: 71). one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises one or more of the motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v] or c[d/n]t[a/r]. the dnases preferably additionally comprise a nuc1_a domain [d/q][i/v]dh (seq id no: 72). one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises one or more motifs selected from the motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v], c[d/n]t[a/r] and [d/q][i/v]dh. one preferred embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises two or more motifs selected from the motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v], c[d/n]t[a/r] and [d/q][iv]dh. one preferred embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises three or more motifs selected from the motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v], c[d/n]t[a/r] and [d/q][iv]dh. one preferred embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises all four motifs [t/d/s][g/n]pql, [f/l/y/i]a[n/r]d[l/i/p/v], c[d/n]t[a/r] and [d/q][i/v]dh. the dnases to be added to a composition of the invention preferably belong to the group of dnases comprised in the gys-clade, which may be defined as nuc1 and nuc1_a dnases further comprising the conservative motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74) and which share similar structural and functional properties. the dnases of the gys-clade are preferably obtained from bacillus genus. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). in a particularly preferred embodiment the bacillus dnase comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). in another particularly preferred embodiment the dnase comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74) and is obtained from bacillus cibi . in yet another preferred embodiment the dnase comprises the amino acid sequence shown in seq id no: 13 or dnases closely related hereto. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. other preferred dnases include those comprising the amino acid sequence shown in seq id no: 65 and 66. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. the dnase may also preferably be fungal. particularly preferred are dnases obtained from aspergillus in particular, aspergillus oryzae. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. other particularly preferred are dnases obtained from trichoderma in particular, trichoderma harzianum. one embodiment of the invention relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme, preferably of the glycosyl hydrolase family gh76, gh92 or gh99, and at least one cleaning component, wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. one embodiment relates to a cleaning composition comprising a bacillus dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh76 mannanase and wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 89, 90, 91, 92, 93, 94, 95, 96 and 97. one embodiment relates to a cleaning composition comprising a bacillus dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh92 mannanase and wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 87. one embodiment relates to a cleaning composition comprising a bacillus dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme is a gh99 mannanase and wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 88. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 13 and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 65 and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 66 and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 67 and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 68 and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the gys-clade and comprise one or both of the motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73), asxnrskg (seq id no: 74) and wherein the alpha-mannan degrading enzyme belongs to the gh76 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 89, 90, 91, 92, 93, 94, 95, 96 or 97, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the gys-clade and comprise one or both of the motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73), asxnrskg (seq id no: 74) and wherein the alpha-mannan degrading enzyme belongs to the gh92 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 87, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the gys-clade and comprise one or both of the motifs [d/m/l][s/t]gysr[d/n] (seq id no: 73), asxnrskg (seq id no: 74), and wherein the alpha-mannan degrading enzyme belongs to the gh99 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 88, and wherein the composition comprises at least one cleaning component. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 79 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 80 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id no: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 81 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id no: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 82 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 83 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 84 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 85 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 86 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 87 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 88 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 89 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 90 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 91 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 92 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 93 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 94 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 95 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 96 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 97 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the nawk-clade and comprise one or both of the motifs [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76), wherein the alpha-mannan degrading enzyme belongs to the gh76 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 89, 90, 91, 92, 93, 94, 95, 96 or 97, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the nawk-clade and comprise one or both of the motifs [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76), wherein the alpha-mannan degrading enzyme belongs to the gh92 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 87, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the nawk-clade and comprise one or both of the motifs [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76), wherein the alpha-mannan degrading enzyme belongs to the gh99 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 88, and wherein the composition comprises at least one cleaning component. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id nos: 79 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 80 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 81 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 82 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 83 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 84 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 85 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 86 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 87 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 88 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 89 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 90 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 91 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 92 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 93 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 94 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 95 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 96 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 97 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the knaw-clade and comprise one or both of the motifs p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78), wherein the alpha-mannan degrading enzyme belongs to the gh76 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 89, 90, 91, 92, 93, 94, 95, 96 or 97, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the knaw-clade and comprise one or both of the motifs p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78), wherein the alpha-mannan degrading enzyme belongs to the gh92 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 87, and wherein the composition comprises at least one cleaning component. one embodiment of the invention relates to a composition, preferably a cleaning composition, comprising an alpha-mannan degrading enzyme, a polypeptide having dnase activity, wherein the polypeptide belongs to the knaw-clade and comprise one or both of the motifs p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78), wherein the alpha-mannan degrading enzyme belongs to the gh99 glycosyl hydrolase family and preferably wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 88, and wherein the composition comprises at least one cleaning component. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 79 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 80 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 81 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 82 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 83 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 84 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 85 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 86 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 87 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 88 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 89 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 90 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 91 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 92 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 93 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 94 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 95 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 96 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 97 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 79 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 80 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 81 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 82 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 83 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 84 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 85 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 86 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 87 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 88 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 89 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 90 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 91 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 92 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 93 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 94 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 95 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 96 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the dnase comprises or consists of a polypeptide selected from the group of polypeptides comprising the amino acid sequence shown in seq id nos: 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 or 68 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto and wherein the alpha-mannan degrading enzyme comprises or consists of the polypeptide comprising the amino acid sequence shown in seq id no: 97 or a polypeptide having at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98% or 100% sequence identity hereto. the alpha-mannan degrading enzyme and dnase may be included in the cleaning composition of the present invention at a level of from 0.01 to 1000 ppm, from 1 ppm to 1000 ppm, from 10 ppm to 1000 ppm, from 50 ppm to 1000 ppm, from 100 ppm to 1000 ppm, from 150 ppm to 1000 ppm, from 200 ppm to 1000 ppm, from 250 ppm to 1000 ppm, from 250 ppm to 750 ppm, from 250 ppm to 500 ppm. the dnases above may be combined with alpha-mannan degrading enzymes to form a blend to be added to the wash liquor solution according to the invention. the concentration of the dnase in the wash liquor solution is typically in the range of wash liquor from 0.00001 ppm to 10 ppm, from 0.00002 ppm to 10 ppm, from 0.0001 ppm to 10 ppm, from 0.0002 ppm to 10 ppm, from 0.001 ppm to 10 ppm, from 0.002 ppm to 10 ppm, from 0.01 ppm to 10 ppm, from 0.02 ppm to 10 ppm, 0.1 ppm to 10 ppm, from 0.2 ppm to 10 ppm, from 0.5 ppm to 5 ppm. the concentration of the alpha-mannan degrading enzyme in the wash liquor solution is typically in the range of wash liquor from 0.00001 ppm to 10 ppm, from 0.00002 ppm to 10 ppm, from 0.0001 ppm to 10 ppm, from 0.0002 ppm to 10 ppm, from 0.001 ppm to 10 ppm, from 0.002 ppm to 10 ppm, from 0.01 ppm to 10 ppm, from 0.02 ppm to 10 ppm, 0.1 ppm to 10 ppm, from 0.2 ppm to 10 ppm, from 0.5 ppm to 5 ppm. the dnases may be combined with any of the alpha-mannan degrading enzymes below to form a blend to be added to a composition according to the invention. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the amount of dnase in the composition is from 0.01 to 1000 ppm and the amount of alpha-mannan degrading enzyme is from 0.01 to 1000 ppm. in addition to the alpha-mannan degrading enzyme and dnase the cleaning composition further comprises one or more cleaning component. one embodiment relates to a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component, wherein the cleaning component is selected from surfactants, preferably anionic and/or nonionic, builders and bleach components. the choice of cleaning components may include, for textile care, the consideration of the type of textile to be cleaned, the type and/or degree of soiling, the temperature at which cleaning is to take place, and the formulation of the detergent product. although components mentioned below are categorized by general header according to a particular functionality, this is not to be construed as a limitation, as a component may comprise additional functionalities as will be appreciated by the skilled artisan. surfactants the cleaning composition may comprise one or more surfactants, which may be anionic and/or cationic and/or non-ionic and/or semi-polar and/or zwitterionic, or a mixture thereof. in a particular embodiment, the detergent composition includes a mixture of one or more nonionic surfactants and one or more anionic surfactants. the surfactant(s) is typically present at a level of from about 0.1% to 60% by weight, such as about 1% to about 40%, or about 3% to about 20%, or about 0.1% to about 15% or about 3% to about 10%. the surfactant(s) is chosen based on the desired cleaning application, and may include any conventional surfactant(s) known in the art. when included therein the detergent will usually contain from about 1% to about 40% by weight of an anionic surfactant, such as from about 5% to about 30%, including from about 5% to about 15%, or from about 15% to about 20%, or from about 20% to about 25% of an anionic surfactant. non-limiting examples of anionic surfactants include sulfates and sulfonates, in particular, linear alkylbenzenesulfonates (las), isomers of las, branched alkylbenzenesulfonates (babs), phenylalkanesulfonates, alpha-olefinsulfonates (aos), olefin sulfonates, alkene sulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonates and disulfonates, alkyl sulfates (as) such as sodium dodecyl sulfate (sds), fatty alcohol sulfates (fas), primary alcohol sulfates (pas), alcohol ethersulfates (aes or aeos or fes, also known as alcohol ethoxysulfates or fatty alcohol ether sulfates), secondary alkanesulfonates (sas), paraffin sulfonates (ps), ester sulfonates, sulfonated fatty acid glycerol esters, alpha-sulfo fatty acid methyl esters (alpha-sfme or ses) including methyl ester sulfonate (mes), alkyl- or alkenylsuccinic acid, dodecenyl/tetradecenyl succinic acid (dtsa), fatty acid derivatives of amino acids, diesters and monoesters of sulfo-succinic acid or salt of fatty acids (soap), and combinations thereof. when included therein the detergent will usually contain from about 1% to about 40% by weigh of a cationic surfactant, for example from about 0.5% to about 30%, in particular from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12% or from about 10% to about 12%. non-limiting examples of cationic surfactants include alkyldimethylethanolamine quat (admeaq), cetyltrimethylammonium bromide (ctab), dimethyldistearylammonium chloride (dsdmac), and alkylbenzyldimethylammonium, alkyl quaternary ammonium compounds, alkoxylated quaternary ammonium (aqa) compounds, ester quats, and combinations thereof. when included therein the detergent will usually contain from about 0.2% to about 40% by weight of a nonionic surfactant, for example from about 0.5% to about 30%, in particular from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12%, or from about 10% to about 12%. non-limiting examples of nonionic surfactants include alcohol ethoxylates (ae or aeo), alcohol propoxylates, propoxylated fatty alcohols (pfa), alkoxylated fatty acid alkyl esters, such as ethoxylated and/or propoxylated fatty acid alkyl esters, alkylphenol ethoxylates (ape), nonylphenol ethoxylates (npe), alkylpolyglycosides (apg), alkoxylated amines, fatty acid monoethanolamides (fam), fatty acid diethanolamides (fada), ethoxylated fatty acid monoethanolamides (efam), propoxylated fatty acid monoethanolamides (pfam), polyhydroxyalkyl fatty acid amides, or n-acyl n-alkyl derivatives of glucosamine (glucamides, ga, or fatty acid glucamides, faga), as well as products available under the trade names span and tween, and combinations thereof. when included therein the detergent will usually contain from about 0.01 to about 10% by weight of a semipolar surfactant. non-limiting examples of semipolar surfactants include amine oxides (ao) such as alkyldimethylamineoxide, n-(coco alkyl)-n,n-dimethylamine oxide and n-(tallow-alkyl)-n,n-bis(2-hydroxyethyl)amine oxide, and combinations thereof. when included therein the detergent will usually contain from about 0.01% to about 10% by weight of a zwitterionic surfactant. non-limiting examples of zwitterionic surfactants include betaines such as alkyldimethylbetaines, sulfobetaines, and combinations thereof. builders and co-builders the cleaning composition may contain about 0-65% by weight, such as about 5% to about 50%, such as about 0.5% to about 20% of a detergent builder or co-builder, or a mixture thereof. in a dish wash detergent, the level of builder is typically 40-65%, particularly 50-65%. the builder and/or co-builder may particularly be a chelating agent that forms water-soluble complexes with ca and mg. any builder and/or co-builder known in the art for use in cleaning detergents may be utilized. non-limiting examples of builders include zeolites, diphosphates (pyrophosphates), triphosphates such as sodium triphosphate (stp or stpp), carbonates such as sodium carbonate, soluble silicates such as sodium metasilicate, layered silicates (e.g., sks-6 from hoechst), ethanolamines such as 2-aminoethan-1-ol (mea), diethanolamine (dea, also known as 2,2′-iminodiethan-1-ol), triethanolamine (tea, also known as 2,2′,2″-nitrilotriethan-1-ol), and (carboxymethyl)inulin (cmi), and combinations thereof. the detergent composition may also contain 0-50% by weight, such as about 5% to about 30%, of a detergent co-builder. the detergent composition may include a co-builder alone, or in combination with a builder, for example a zeolite builder. non-limiting examples of co-builders include homopolymers of polyacrylates or copolymers thereof, such as poly(acrylic acid) (paa) or copoly(acrylic acid/maleic acid) (paa/pma). further non-limiting examples include citrate, chelators such as aminocarboxylates, aminopolycarboxylates and phosphonates, and alkyl- or alkenylsuccinic acid. additional specific examples include 2,2′,2″-nitrilotriacetic acid (nta), ethylenediaminetetraacetic acid (edta), diethylenetriaminepentaacetic acid (dtpa), iminodisuccinic acid (ids), ethylenediamine-n,n′-disuccinic acid (edds), methylglycinediacetic acid (mgda), glutamic acid-n,n-diacetic acid (glda), 1-hydroxyethane-1,1-diphosphonic acid (hedp), ethylenediaminetetra(methylenephosphonic acid) (edtmpa), diethylenetriaminepentakis(methylenephosphonic acid) (dtmpa or dtpmpa), n-(2-hydroxyethyl)iminodiacetic acid (edg), aspartic acid-n-monoacetic acid (asma), aspartic acid-n,n-diacetic acid (asda), aspartic acid-n-monopropionic acid (asmp), iminodisuccinic acid (ida), n-(2-sulfomethyl)-aspartic acid (smas), n-(2-sulfoethyl)-aspartic acid (seas), n-(2-sulfomethyl)-glutamic acid (smgl), n-(2-sulfoethyl)-glutamic acid (segl), n-methyliminodiacetic acid (mida), α-alanine-n,n-diacetic acid (α-alda), serine-n,n-diacetic acid (seda), isoserine-n,n-diacetic acid (isda), phenylalanine-n,n-diacetic acid (phda), anthranilic acid-n,n-diacetic acid (anda), sulfanilic acid-n,n-diacetic acid (slda), taurine-n,n-diacetic acid (tuda) and sulfomethyl-n,n-diacetic acid (smda), n-(2-hydroxyethyl)ethylenediamine-n,n′,n″-triacetic acid (hedta), diethanolglycine (deg), diethylenetriamine penta(methylenephosphonic acid) (dtpmp), aminotris(methylenephosphonic acid) (atmp), and combinations and salts thereof. further exemplary builders and/or co-builders are described in, e.g., wo 09/102854, u.s. pat. no. 5,977,053 bleaching systems the cleaning composition may contain 0-30% by weight, such as about 1% to about 20%, such as about 0.01% to about 10% of a bleaching system. any bleaching system comprising components known in the art for use in cleaning detergents may be utilized. suitable bleaching system components include sources of hydrogen peroxide; sources of peracids; and bleach catalysts or boosters. sources of hydrogen peroxide: suitable sources of hydrogen peroxide are inorganic persalts, including alkali metal salts such as sodium percarbonate and sodium perborates (usually mono- or tetrahydrate), and hydrogen peroxide—urea (1/1). sources of peracids: peracids may be (a) incorporated directly as preformed peracids or (b) formed in situ in the wash liquor from hydrogen peroxide and a bleach activator (perhydrolysis) or (c) formed in situ in the wash liquor from hydrogen peroxide and a perhydrolase and a suitable substrate for the latter, e.g., an ester. a) suitable preformed peracids include, but are not limited to, peroxycarboxylic acids such as peroxybenzoic acid and its ring-substituted derivatives, peroxy-α-naphthoic acid, peroxyphthalic acid, peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthalimidoperoxyhexanoic acid (pap)], and o-carboxybenzamidoperoxycaproic acid; aliphatic and aromatic diperoxydicarboxylic acids such as diperoxydodecanedioic acid, diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, 2-decyldiperoxybutanedioic acid, and diperoxyphthalic, -isophthalic and -terephthalic acids; perimidic acids; peroxymonosulfuric acid; peroxydisulfuric acid; peroxyphosphoric acid; peroxysilicic acid; and mixtures of said compounds. it is understood that the peracids mentioned may in some cases be best added as suitable salts, such as alkali metal salts (e.g., oxone®) or alkaline earth-metal salts. b) suitable bleach activators include those belonging to the class of esters, amides, imides, nitriles or anhydrides and, where applicable, salts thereof. suitable examples are tetraacetylethylenediamine (taed), sodium 4-[(3,5,5-trimethylhexanoyl)oxy]benzene-1-sulfonate (isonobs), sodium 4-(dodecanoyloxy)benzene-1-sulfonate (lobs), sodium 4-(decanoyloxy)benzene-1-sulfonate, 4-(decanoyloxy)benzoic acid (doba), sodium 4-(nonanoyloxy)benzene-1-sulfonate (nobs), and/or those disclosed in wo98/17767. a particular family of bleach activators of interest was disclosed in ep624154 and particularly preferred in that family is acetyl triethyl citrate (atc). atc or a short chain triglyceride like triacetin has the advantage that they are environmentally friendly. furthermore, acetyl triethyl citrate and triacetin have good hydrolytical stability in the product upon storage and are efficient bleach activators. finally, atc is multifunctional, as the citrate released in the perhydrolysis reaction may function as a builder. bleach catalysts and boosters the bleaching system may also include a bleach catalyst or booster. some non-limiting examples of bleach catalysts that may be used in the compositions of the present invention include manganese oxalate, manganese acetate, manganese-collagen, cobalt-amine catalysts and manganese triazacyclononane (mntacn) catalysts; particularly preferred are complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (me3-tacn) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (me4-tacn), in particular me3-tacn, such as the dinuclear manganese complex [(me3-tacn)mn(o)3mn(me3-tacn)](pf6)2, and [2,2′,2″-nitrilotris(ethane-1,2-diylazanylylidene-kn-methanylylidene)triphenolato-κ3o]manganese(iii). the bleach catalysts may also be other metal compounds; such as iron or cobalt complexes. in some embodiments, where a source of a peracid is included, an organic bleach catalyst or bleach booster may be used having one of the following formulae: (iii) and mixtures thereof; wherein each r1 is independently a branched alkyl group containing from 9 to 24 carbons or linear alkyl group containing from 11 to 24 carbons, preferably each r1 is independently a branched alkyl group containing from 9 to 18 carbons or linear alkyl group containing from 11 to 18 carbons, more preferably each r1 is independently selected from the group consisting of 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isononyl, isodecyl, isotridecyl and isopentadecyl. other exemplary bleaching systems are described, e.g. in wo2007/087258, wo2007/087244, wo2007/087259, ep1867708 (vitamin k) and wo2007/087242. suitable photobleaches may for example be sulfonated zinc or aluminium phthalocyanines. metal care agents metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of metals, including aluminium, stainless steel and non-ferrous metals, such as silver and copper. suitable examples include one or more of the following: (a) benzatriazoles, including benzotriazole or bis-benzotriazole and substituted derivatives thereof. benzotriazole derivatives are those compounds in which the available substitution sites on the aromatic ring are partially or completely substituted. suitable substituents include linear or branch-chain ci-c20-alkyl groups (e.g., c1-c20-alkyl groups) and hydroxyl, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine. (b) metal salts and complexes chosen from the group consisting of zinc, manganese, titanium, zirconium, hafnium, vanadium, cobalt, gallium and cerium salts and/or complexes, the metals being in one of the oxidation states ii, iii, iv, v or vi. in one aspect, suitable metal salts and/or metal complexes may be chosen from the group consisting of mn(ii) sulphate, mn(ii) citrate, mn(ii) stearate, mn(ii) acetylacetonate, k{circumflex over ( )}tif6 (e.g., k2tif6), k{circumflex over ( )}zrf6 (e.g., k2zrf6), coso4, co(nos)2 and ce(nos)3, zinc salts, for example zinc sulphate, hydrozincite or zinc acetate; (c) silicates, including sodium or potassium silicate, sodium disilicate, sodium metasilicate, crystalline phyllosilicate and mixtures thereof. further suitable organic and inorganic redox-active substances that act as silver/copper corrosion inhibitors are disclosed in wo 94/26860 and wo 94/26859. preferably the composition of the invention comprises from 0.1 to 5% by weight of the composition of a metal care agent, preferably the metal care agent is a zinc salt. hydrotropes the cleaning composition may contain 0-10% by weight, for example 0-5% by weight, such as about 0.5 to about 5%, or about 3% to about 5%, of a hydrotrope. any hydrotrope known in the art for use in detergents may be utilized. non-limiting examples of hydrotropes include sodium benzenesulfonate, sodium p-toluene sulfonate (sts), sodium xylene sulfonate (sxs), sodium cumene sulfonate (scs), sodium cymene sulfonate, amine oxides, alcohols and polyglycolethers, sodium hydroxynaphthoate, sodium hydroxynaphthalene sulfonate, sodium ethylhexyl sulfate, and combinations thereof. polymers the cleaning composition may contain 0-10% by weight, such as 0.5-5%, 2-5%, 0.5-2% or 0.2-1% of a polymer. any polymer known in the art for use in detergents may be utilized. the polymer may function as a co-builder as mentioned above, or may provide antiredeposition, fiber protection, soil release, dye transfer inhibition, grease cleaning and/or anti-foaming properties. some polymers may have more than one of the above-mentioned properties and/or more than one of the below-mentioned motifs. exemplary polymers include (carboxymethyl)cellulose (cmc), poly(vinyl alcohol) (pva), poly(vinylpyrrolidone) (pvp), poly(ethyleneglycol) or poly(ethylene oxide) (peg), ethoxylated poly(ethyleneimine), carboxymethyl inulin (cmi), and polycarboxylates such as paa, paa/pma, poly-aspartic acid, and lauryl methacrylate/acrylic acid copolymers, hydrophobically modified cmc (hm-cmc) and silicones, copolymers of terephthalic acid and oligomeric glycols, copolymers of poly(ethylene terephthalate) and poly(oxyethene terephthalate) (pet-poet), pvp, poly(vinylimidazole) (pvi), poly(vinylpyridine-n-oxide) (pvpo or pvpno) and polyvinylpyrrolidone-vinylimidazole (pvpvi). suitable examples include pvp-k15, pvp-k30, chromabond s-400, chromabond s-403e and chromabond s-100 from ashland aqualon, and sokalan® hp 165, sokalan® hp 50 (dispersing agent), sokalan® hp 53 (dispersing agent), sokalan® hp 59 (dispersing agent), sokalan® hp 56 (dye transfer inhibitor), sokalan® hp 66 k (dye transfer inhibitor) from basf. further exemplary polymers include sulfonated polycarboxylates, polyethylene oxide and polypropylene oxide (peo-ppo) and diquaternium ethoxy sulfate. other exemplary polymers are disclosed in, e.g., wo 2006/130575. salts of the above-mentioned polymers are also contemplated. particularly preferred polymer is ethoxylated homopolymer sokalan® hp 20 from basf, which helps to prevent redeposition of soil in the wash liquor. fabric hueing agents the cleaning compositions of the present invention may also include fabric hueing agents such as dyes or pigments, which when formulated in detergent compositions can deposit onto a fabric when said fabric is contacted with a wash liquor comprising said detergent compositions and thus altering the tint of said fabric through absorption/reflection of visible light. fluorescent whitening agents emit at least some visible light. in contrast, fabric hueing agents alter the tint of a surface as they absorb at least a portion of the visible light spectrum. suitable fabric hueing agents include dyes and dye-clay conjugates, and may also include pigments. suitable dyes include small molecule dyes and polymeric dyes. suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the colour index (c.i.) classifications of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet and basic red, or mixtures thereof, for example as described in wo2005/03274, wo2005/03275, wo2005/03276 and ep1876226 (hereby incorporated by reference). the detergent composition preferably comprises from about 0.00003 wt % to about 0.2 wt %, from about 0.00008 wt % to about 0.05 wt %, or even from about 0.0001 wt % to about 0.04 wt % fabric hueing agent. the composition may comprise from 0.0001 wt % to 0.2 wt % fabric hueing agent, this may be especially preferred when the composition is in the form of a unit dose pouch. suitable hueing agents are also disclosed in, e.g. wo 2007/087257 and wo2007/087243. enzymes the cleaning composition may comprise one or more additional enzymes such as one or more lipase, cutinase, an amylase, carbohydrase, cellulase, pectinase, mannanase, arabinase, galactanase, xylanase, oxidase, e.g., a laccase, and/or peroxidase. in general, the properties of the selected enzyme(s) should be compatible with the selected detergent, (i.e., ph-optimum, compatibility with other enzymatic and non-enzymatic ingredients, etc.), and the enzyme(s) should be present in effective amounts. cellulases suitable cellulases include those of bacterial or fungal origin. chemically modified or protein engineered mutants are included. suitable cellulases include cellulases from the genera bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium , e.g., the fungal cellulases produced from humicola insolens, myceliophthora thermophila and fusarium oxysporum disclosed in u.s. pat. nos. 4,435,307, 5,648,263, 5,691,178, 5,776,757 and wo 89/09259. especially suitable cellulases are the alkaline or neutral cellulases having colour care benefits. examples of such cellulases are cellulases described in ep 0 495 257, ep 0 531 372, wo 96/11262, wo 96/29397, wo 98/08940. other examples are cellulase variants such as those described in wo 94/07998, ep 0 531 315, u.s. pat. nos. 5,457,046, 5,686,593, 5,763,254, wo 95/24471, wo 98/12307 and wo99/001544. other cellulases are endo-beta-1,4-glucanase enzyme having a sequence of at least 97% identity to the amino acid sequence of position 1 to position 773 of seq id no:2 of wo 2002/099091 or a family 44 xyloglucanase, which a xyloglucanase enzyme having a sequence of at least 60% identity to positions 40-559 of seq id no: 2 of wo 2001/062903. commercially available cellulases include celluzyme™, and carezyme™ (novozymes a/s) carezyme premium™ (novozymes a/s), celluclean™ (novozymes a/s), celluclean classic™ (novozymes a/s), cellusoft™ (novozymes a/s), whitezyme™ (novozymes a/s), clazinase™, and puradax ha™ (genencor international inc.), and kac-500(b)™ (kao corporation). lipases and cutinases suitable lipases and cutinases include those of bacterial or fungal origin. chemically modified or protein engineered mutant enzymes are included. examples include lipase from thermomyces , e.g. from t. lanuginosus (previously named humicola lanuginosa ) as described in ep258068 and ep305216, cutinase from humicola , e.g. h. insolens (wo96/13580), lipase from strains of pseudomonas (some of these now renamed to burkholderia ), e.g. p. alcaligenes or p. pseudoalcaligenes (ep218272), p. cepacia (ep331376), p. sp. strain sd705 (wo95/06720 & wo96/27002), p. wisconsinensis (wo96/12012), gdsl-type streptomyces lipases (wo10/065455), cutinase from magnaporthe grisea (wo10/107560), cutinase from pseudomonas mendocina (u.s. pat. no. 5,389,536), lipase from thermobifida fusca (wo11/084412), geobacillus stearothermophilus lipase (wo11/084417), lipase from bacillus subtilis (wo11/084599), and lipase from streptomyces griseus (wo11/150157) and s. pristinaespiralis (wo12/137147). other examples are lipase variants such as those described in ep407225, wo92/05249, wo94/01541, wo94/25578, wo95/14783, wo95/30744, wo95/35381, wo95/22615, wo96/00292, wo97/04079, wo97/07202, wo00/34450, wo00/60063, wo01/92502, wo07/87508 and wo09/109500. preferred commercial lipase products include lipolase™, lipex™; lipolex™ and lipoclean™ (novozymes a/s), lumafast (originally from genencor) and lipomax (originally from gist-brocades). still other examples are lipases sometimes referred to as acyltransferases or perhydrolases, e.g. acyltransferases with homology to candida antarctica lipase a (wo10/111143), acyltransferase from mycobacterium smegmatis (wo05/56782), perhydrolases from the ce 7 family (wo09/67279), and variants of the m. smegmatis perhydrolase in particular the s54v variant used in the commercial product gentle power bleach from huntsman textile effects pte ltd (wo10/100028). amylases suitable amylases include alpha-amylases and/or a glucoamylases and may be of bacterial or fungal origin. chemically modified or protein engineered mutants are included. amylases include, for example, alpha-amylases obtained from bacillus , e.g., a special strain of bacillus licheniformis , described in more detail in gb 1,296,839. suitable amylases include amylases having seq id no: 2 in wo 95/10603 or variants having 90% sequence identity to seq id no: 3 thereof. preferred variants are described in wo 94/02597, wo 94/18314, wo 97/43424 and seq id no: 4 of wo 99/019467, such as variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 178, 179, 181, 188, 190, 197, 201, 202, 207, 208, 209, 211, 243, 264, 304, 305, 391, 408, and 444. different suitable amylases include amylases having seq id no: 6 in wo 02/010355 or variants thereof having 90% sequence identity to seq id no: 6. preferred variants of seq id no: 6 are those having a deletion in positions 181 and 182 and a substitution in position 193. other amylases which are suitable are hybrid alpha-amylase comprising residues 1-33 of the alpha-amylase derived from b. amyloliquefaciens shown in seq id no: 6 of wo 2006/066594 and residues 36-483 of the b. licheniformis alpha-amylase shown in seq id no: 4 of wo 2006/066594 or variants having 90% sequence identity thereof. preferred variants of this hybrid alpha-amylase are those having a substitution, a deletion or an insertion in one of more of the following positions: g48, t49, g107, h156, a181, n190, m197, i201, a209 and q264. most preferred variants of the hybrid alpha-amylase comprising residues 1-33 of the alpha-amylase derived from b. amyloliquefaciens shown in seq id no: 6 of wo 2006/066594 and residues 36-483 of seq id no: 4 are those having the substitutions: m197t; h156y+a181t+n190f+a209v+q264s; or g48a+t491+g107a+h156y+a181t+n190f+i201f+a209v+q264s. further amylases which are suitable are amylases having seq id no: 6 in wo 99/019467 or variants thereof having 90% sequence identity to seq id no: 6. preferred variants of seq id no: 6 are those having a substitution, a deletion or an insertion in one or more of the following positions: r181, g182, h183, g184, n195, 1206, e212, e216 and k269. particularly preferred amylases are those having deletion in positions r181 and g182, or positions h183 and g184. additional amylases which can be used are those having seq id no: 1, seq id no: 3, seq id no: 2 or seq id no: 7 of wo 96/023873 or variants thereof having 90% sequence identity to seq id no: 1, seq id no: 2, seq id no: 3 or seq id no: 7. preferred variants of seq id no: 1, seq id no: 2, seq id no: 3 or seq id no: 7 are those having a substitution, a deletion or an insertion in one or more of the following positions: 140, 181, 182, 183, 184, 195, 206, 212, 243, 260, 269, 304 and 476, using seq id 2 of wo 96/023873 for numbering. more preferred variants are those having a deletion in two positions selected from 181, 182, 183 and 184, such as 181 and 182, 182 and 183, or positions 183 and 184. most preferred amylase variants of seq id no: 1, seq id no: 2 or seq id no: 7 are those having a deletion in positions 183 and 184 and a substitution in one or more of positions 140, 195, 206, 243, 260, 304 and 476. other amylases which can be used are amylases having seq id no: 2 of wo 08/153815, seq id no: 10 in wo 01/66712 or variants thereof having 90% sequence identity to seq id no: 2 of wo 08/153815 or 90% sequence identity to seq id no: 10 in wo 01/66712. preferred variants of seq id no: 10 in wo 01/66712 are those having a substitution, a deletion or an insertion in one of more of the following positions: 176, 177, 178, 179, 190, 201, 207, 211 and 264. further suitable amylases are amylases having seq id no: 2 of wo 09/061380 or variants having 90% sequence identity to seq id no: 2 thereof. preferred variants of seq id no: 2 are those having a truncation of the c-terminus and/or a substitution, a deletion or an insertion in one of more of the following positions: q87, q98, s125, n128, t131, t165, k178, r180, s181, t182, g183, m201, f202, n225, s243, n272, n282, y305, r309, d319, q320, q359, k444 and g475. more preferred variants of seq id no: 2 are those having the substitution in one of more of the following positions: q87e,r, q98r, s125a, n128c, t131i, t165i, k178l, t182g, m201l, f202y, n225e,r, n272e,r, s243q,a,e,d, y305r, r309a, q320r, q359e, k444e and g475k and/or deletion in position r180 and/or s181 or of t182 and/or g183. most preferred amylase variants of seq id no: 2 are those having the substitutions: n128c+k178l+t182g+y305r+g475k; n128c+k178l+t182g+f202y+y305r+d319t+g475k; s125a+n128c+k178l+t182g+y305r+g475k; or s125a+n128c+t131i+t165+k178l+t182g+y305r+g475k wherein the variants are c-terminally truncated and optionally further comprises a substitution at position 243 and/or a deletion at position 180 and/or position 181. further suitable amylases are amylases having seq id no: 1 of wo13184577 or variants having 90% sequence identity to seq id no: 1 thereof. preferred variants of seq id no: 1 are those having a substitution, a deletion or an insertion in one of more of the following positions: k176, r178, g179, t180, g181, e187, n192, m199, 1203, s241, r458, t459, d460, g476 and g477. more preferred variants of seq id no: 1 are those having the substitution in one of more of the following positions: k176l, e187p, n192fyh, m199l, i203yf, s241qadn, r458n, t459s, d460t, g476k and g477k and/or deletion in position r178 and/or s179 or of t180 and/or g181. most preferred amylase variants of seq id no: 1 are those having the substitutions: e187p+i203y+g476k e187p+i203y+r458n+t459s+d460t+g476k wherein the variants optionally further comprise a substitution at position 241 and/or a deletion at position 178 and/or position 179. further suitable amylases are amylases having seq id no: 1 of wo10104675 or variants having 90% sequence identity to seq id no: 1 thereof. preferred variants of seq id no: 1 are those having a substitution, a deletion or an insertion in one of more of the following positions: n21, d97, v128 k177, r179, s180, i181, g182, m200, l204, e242, g477 and g478. more preferred variants of seq id no: 1 are those having the substitution in one of more of the following positions: n21d, d97n, v128i k177l, m200l, l204yf, e242qa, g477k and g478k and/or deletion in position r179 and/or s180 or of i181 and/or g182. most preferred amylase variants of seq id no: 1 are those having the substitutions: n21d+d97n+v128i wherein the variants optionally further comprise a substitution at position 200 and/or a deletion at position 180 and/or position 181. other suitable amylases are the alpha-amylase having seq id no: 12 in wo01/66712 or a variant having at least 90% sequence identity to seq id no: 12. preferred amylase variants are those having a substitution, a deletion or an insertion in one of more of the following positions of seq id no: 12 in wo01/66712: r28, r118, n174; r181, g182, d183, g184, g186, w189, n195, m202, y298, n299, k302, s303, n306, r310, n314; r320, h324, e345, y396, r400, w439, r444, n445, k446, q449, r458, n471, n484. particular preferred amylases include variants having a deletion of d183 and g184 and having the substitutions r118k, n195f, r320k and r458k, and a variant additionally having substitutions in one or more position selected from the group: m9, g149, g182, g186, m202, t257, y295, n299, m323, e345 and a339, most preferred a variant that additionally has substitutions in all these positions. other examples are amylase variants such as those described in wo2011/098531, wo2013/001078 and wo2013/001087. commercially available amylases are duramyl™, termamyl™, fungamyl™, stainzyme™ stainzyme plus™, natalase™, liquozyme x and ban™ (from novozymes a/s), and rapidase™, purast™/effectenz™, powerase, preferenz s1000, preferenz s100 and preferenz s110 (from genencor international inc./dupont). peroxidases/oxidases a peroxidase may be an enzyme comprised by the enzyme classification ec 1.11.1.7, as set out by the nomenclature committee of the international union of biochemistry and molecular biology (iubmb), or any fragment derived therefrom, exhibiting peroxidase activity. suitable peroxidases include those of plant, bacterial or fungal origin. chemically modified or protein engineered mutants are included. examples of useful peroxidases include peroxidases from coprinopsis , e.g., from c. cinerea (ep 179,486), and variants thereof as those described in wo 93/24618, wo 95/10602, and wo 98/15257. a suitable peroxidase includes a haloperoxidase enzyme, such as chloroperoxidase, bromoperoxidase and compounds exhibiting chloroperoxidase or bromoperoxidase activity. haloperoxidases are classified according to their specificity for halide ions. chloroperoxidases (e.c. 1.11.1.10) catalyze formation of hypochlorite from chloride ions. preferably, the haloperoxidase is a vanadium haloperoxidase, i.e., a vanadate-containing haloperoxidase. haloperoxidases have been isolated from many different fungi, in particular from the fungus group dematiaceous hyphomycetes, such as caldariomyces , e.g., c. fumago, alternaria, curvularia , e.g., c. verruculosa and c. inaequalis, drechslera, ulocladium and botrytis. haloperoxidases have also been isolated from bacteria such as pseudomonas , e.g., p. pyrrocinia and streptomyces , e.g., s. aureofaciens . a suitable oxidase includes in particular, any laccase enzyme comprised by the enzyme classification ec 1.10.3.2, or any fragment derived therefrom exhibiting laccase activity, or a compound exhibiting a similar activity, such as a catechol oxidase (ec 1.10.3.1), an o-aminophenol oxidase (ec 1.10.3.4), or a bilirubin oxidase (ec 1.3.3.5). preferred laccase enzymes are enzymes of microbial origin. the enzymes may be derived from plants, bacteria or fungi (including filamentous fungi and yeasts). suitable examples from fungi include a laccase derivable from a strain of aspergillus, neurospora , e.g., n. crassa, podospora, botrytis, collybia, fomes, lentinus, pleurotus, trametes , e.g., t. villosa and t. versicolor, rhizoctonia , e.g., r. solani, coprinopsis , e.g., c. cinerea, c. comatus, c. friesii , and c. plicatilis, psathyrella , e.g., p. condelleana, panaeolus , e.g., p. papilionaceus, myceliophthora , e.g., m. thermophila, schytalidium , e.g., s. thermophilum, polyporus , e.g., p. pinsitus, phlebia , e.g., p. radiata (wo 92/01046), or coriolus , e.g., c. hirsutus (jp 2238885). suitable examples from bacteria include a laccase derivable from a strain of bacillus . a laccase derived from coprinopsis or myceliophthora is preferred; in particular, a laccase derived from coprinopsis cinerea , as disclosed in wo 97/08325; or from myceliophthora thermophila , as disclosed in wo 95/33836. proteases suitable proteases include those of bacterial, fungal, plant, viral or animal origin e.g. vegetable or microbial origin. microbial origin is preferred. chemically modified or protein engineered mutants are included. the protease may be an alkaline protease, such as a serine protease. a serine protease may for example be of the s1 family, such as trypsin, or the s8 family such as subtilisin. a metalloprotease protease may for example be a thermolysin from e.g. family m4 or other metalloprotease such as those from m5, m7 or m8 families. the term “subtilases” refers to a sub-group of serine protease according to siezen et al., protein engng. 4 (1991) 719-737 and siezen et al. protein science 6 (1997) 501-523. serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. the subtilases may be divided into 6 sub-divisions, i.e. the subtilisin family, the thermitase family, the proteinase k family, the lantibiotic peptidase family, the kexin family and the pyrolysin family. examples of subtilases are those derived from bacillus such as bacillus lentus, bacillus alkalophilus, bacillus subtilis, bacillus amyloliquefaciens, bacillus pumilus and bacillus gibsonii described in; u.s. pat. no. 7,262,042 and wo09/021867, and subtilisin lentus, subtilisin novo, subtilisin carlsberg, bacillus licheniformis , subtilisin bpn′, subtilisin 309, subtilisin 147 and subtilisin 168 and e.g. protease pd138 described in (wo93/18140). other useful proteases may be those described in wo01/016285 and wo02/016547. examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the fusarium protease described in wo94/25583 and wo05/040372, and the chymotrypsin proteases derived from cellumonas described in wo05/052161 and wo05/052146. further preferred protease is the alkaline protease from bacillus lentus dsm 5483, as described for example in wo95/23221, and variants thereof which are described in wo92/21760, wo95/23221, ep1921147 and ep1921148. examples of metalloproteases are the neutral metalloprotease as described in wo07/044993 (proctor & gamble/genencor int.) such as those derived from bacillus amyloliquefaciens. examples of useful proteases are the variants described in: wo89/06279 wo92/19729, wo96/034946, wo98/20115, wo98/20116, wo99/011768, wo01/44452, wo03/006602, wo04/03186, wo04/041979, wo07/006305, wo11/036263, wo11/036264, especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 24, 27, 42, 55, 59, 60, 66, 74, 85, 96, 97, 98, 99, 100, 101, 102, 104, 116, 118, 121, 126, 127, 128, 154, 156, 157, 158, 161, 164, 176, 179, 182, 185, 188, 189, 193, 198, 199, 200, 203, 206, 211, 212, 216, 218, 226, 229, 230, 239, 246, 255, 256, 268 and 269, wherein the positions correspond to the positions of the bacillus lentus protease shown in seq id no: 1 of wo 2016/001449. more preferred the protease variants may comprise one or more of the mutations selected from the group consisting of: s3t, v41, s9r, s9e, a15t, s24g, s24r, k27r, n42r, s55p, g59e, g59d, n60d, n60e, v66a, n74d, s85r, a96s, s97g, s97d, s97a, s97sd, s99e, s99d, s99g, s99m, s99n, s99r, s99h, s101a, v102i, v102y, v102n, s104a, g116v, g116r, h118d, h118n, a120s, s126l, p127q, s128a, s154d, a156e, g157d, g157p, s158e, y161a, r164s, q176e, n179e, s182e, q185n, a188p, g189e, v193m, n198d, v1991, y203w, s206g, l211q, l211d, n212d, n212s, m216s, a226v, k229l, q230h, q239r, n246k, n255w, n255d, n255e, l256e, l256d t268a and r269h. the protease variants are preferably variants of the bacillus lentus protease shown in seq id no: 1 of wo2016/001449, the bacillus amylolichenifaciens protease (bpn′) shown in seq id no: 2 of wo2016/001449. the protease variants preferably have at least 80% sequence identity to seq id no: 1 or seq id no: 2 of wo 2016/001449. a protease variant comprising a substitution at one or more positions corresponding to positions 171, 173, 175, 179, or 180 of seq id no: 1 of wo2004/067737, wherein said protease variant has a sequence identity of at least 75% but less than 100% to seq id no: 1 of wo2004/067737. suitable commercially available protease enzymes include those sold under the trade names alcalase®, duralase™, durazym™, relase®, relase® ultra, savinase®, savinase® ultra, primase®, polarzyme®, kannase®, liquanase®, liquanase® ultra, ovozyme®, coronase®, coronase® ultra, blaze®, blaze evity® 100t, blaze evity® 125t, blaze evity® 150t, neutrase®, everlase® and esperase® (novozymes a/s), those sold under the tradename maxatase®, maxacal®, maxapem®, purafect ox®, purafect oxp®, puramax®, fn2®, fn3®, fn4®, excellase®, excellenz p1000™, excellenz p1250™, eraser®, preferenz p100™ purafect prime®, preferenz p110™, effectenz p1000™ purafect™, effectenz p1050™ purafect ox®™, effectenz p2000™ purafast®, properase®, opticlean® and optimase® (danisco/dupont), axapem™ (gist-brocases n.v.), blap (sequence shown in fig. 29 of u.s. pat. no. 5,352,604) and variants hereof (henkel ag) and kap ( bacillus alkalophilus subtilisin) from kao. dispersants the cleaning compositions of the present invention can also contain dispersants. in particular, powdered detergents may comprise dispersants. suitable water-soluble organic materials include the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. suitable dispersants are for example described in powdered detergents, surfactant science series volume 71, marcel dekker, inc. dye transfer inhibiting agents the cleaning compositions of the present invention may also include one or more dye transfer inhibiting agents. suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine n-oxide polymers, copolymers of n-vinylpyrrolidone and n-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. when present in a subject composition, the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the composition. fluorescent whitening agent the cleaning compositions of the present invention will preferably also contain additional components that may tint articles being cleaned, such as fluorescent whitening agent or optical brighteners. where present the brightener is preferably at a level of about 0.01% to about 0.5%. any fluorescent whitening agent suitable for use in a laundry detergent composition may be used in the composition of the present invention. the most commonly used fluorescent whitening agents are those belonging to the classes of diaminostilbene-sulfonic acid derivatives, diarylpyrazoline derivatives and bisphenyl-distyryl derivatives. examples of the diaminostilbene-sulfonic acid derivative type of fluorescent whitening agents include the sodium salts of: 4,4′-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2′-disulfonate, 4,4′-bis-(2,4-dianilino-s-triazin-6-ylamino) stilbene-2.2′-disulfonate, 4,4′-bis-(2-anilino-4-(n-methyl-n-2-hydroxy-ethylamino)-s-triazin-6-ylamino) stilbene-2,2′-disulfonate, 4,4′-bis-(4-phenyl-1,2,3-triazol-2-yl)stilbene-2,2′-disulfonate and sodium 5-(2h-naphtho[1,2-d][1,2,3]triazol-2-yl)-2-[(e)-2-phenylvinyl]benzenesulfonate. preferred fluorescent whitening agents are tinopal dms and tinopal cbs available from ciba-geigy ag, basel, switzerland. tinopal dms is the disodium salt of 4,4′-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2,2′-disulfonate. tinopal cbs is the disodium salt of 2,2′-bis-(phenyl-styryl)-disulfonate. also preferred are fluorescent whitening agents is the commercially available parawhite kx, supplied by paramount minerals and chemicals, mumbai, india. other fluorescers suitable for use in the invention include the 1-3-diaryl pyrazolines and the 7-alkylaminocoumarins. suitable fluorescent brightener levels include lower levels of from about 0.01, from 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %. soil release polymers the cleaning compositions of the present invention may also include one or more soil release polymers which aid the removal of soils from fabrics such as cotton and polyester based fabrics, in particular the removal of hydrophobic soils from polyester based fabrics. the soil release polymers may for example be nonionic or anionic terephthalte based polymers, polyvinyl caprolactam and related copolymers, vinyl graft copolymers, polyester polyamides see for example chapter 7 in powdered detergents, surfactant science series volume 71, marcel dekker, inc. another type of soil release polymers is amphiphilic alkoxylated grease cleaning polymers comprising a core structure and a plurality of alkoxylate groups attached to that core structure. the core structure may comprise a polyalkylenimine structure or a polyalkanolamine structure as described in detail in wo 2009/087523 (hereby incorporated by reference). furthermore, random graft co-polymers are suitable soil release polymers. suitable graft co-polymers are described in more detail in wo 2007/138054, wo 2006/108856 and wo 2006/113314 (hereby incorporated by reference). suitable polyethylene glycol polymers include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) side chain(s) selected from the group consisting of: c4-c25 alkyl group, polypropylene, polybutylene, vinyl ester of a saturated c1-c6 mono-carboxylic acid, ci-c 6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof. suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains. the average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 da to 20,000 da, or from 4,000 da to 8,000 da. the molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2. the average number of graft sites per ethylene oxide units can be less than 1, or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4. a suitable polyethylene glycol polymer is sokalan hp22. other soil release polymers are substituted polysaccharide structures especially substituted cellulosic structures such as modified cellulose deriviatives such as those described in ep 1867808 or wo 2003/040279 (both are hereby incorporated by reference). suitable cellulosic polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides and mixtures thereof. suitable cellulosic polymers include anionically modified cellulose, nonionically modified cellulose, cationically modified cellulose, zwitterionically modified cellulose, and mixtures thereof. suitable cellulosic polymers include methyl cellulose, carboxy methyl cellulose, ethyl cellulose, hydroxyl ethyl cellulose, hydroxyl propyl methyl cellulose, ester carboxy methyl cellulose, and mixtures thereof. anti-redeposition agents the cleaning compositions of the present invention may also include one or more anti-redeposition agents such as carboxymethylcellulose (cmc), polyvinyl alcohol (pva), polyvinylpyrrolidone (pvp), polyoxyethylene and/or polyethyleneglycol (peg), homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and ethoxylated polyethyleneimines. the cellulose based polymers described under soil release polymers above may also function as anti-redeposition agents. rheology modifiers the cleaning compositions of the present invention may also include one or more rheology modifiers, structurants or thickeners, as distinct from viscosity reducing agents. the rheology modifiers are selected from the group consisting of non-polymeric crystalline, hydroxy-functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of a liquid detergent composition. the rheology and viscosity of the detergent can be modified and adjusted by methods known in the art, for example as shown in ep 2169040. other suitable cleaning composition components include, but are not limited to, anti-shrink agents, anti-wrinkling agents, bactericides, binders, carriers, dyes, enzyme stabilizers, fabric softeners, fillers, foam regulators, hydrotropes, perfumes, pigments, sod suppressors, solvents, and structurants for liquid detergents and/or structure elasticizing agents. formulation of detergent products the cleaning composition of the present invention may be formulated, for example, as a hand or machine laundry detergent composition including a laundry additive composition suitable for pre-treatment of stained fabrics and a rinse added fabric softener composition or be formulated as a detergent composition for use in general household hard surface cleaning operations or be formulated for hand or machine dishwashing operations. in a specific aspect, the present invention provides a detergent additive comprising one or more enzymes as described herein. the cleaning composition of the invention may be in any convenient form, e.g., a bar, a homogenous tablet, a tablet having two or more layers, a pouch having one or more compartments, a regular or compact powder, a granule, a paste, a gel, or a regular, compact or concentrated liquid. pouches can be configured as single or multicompartments. it can be of any form, shape and material which is suitable for hold the composition, e.g. without allowing the release of the composition to release of the composition from the pouch prior to water contact. the pouch is made from water soluble film which encloses an inner volume. said inner volume can be divided into compartments of the pouch. preferred films are polymeric materials preferably polymers which are formed into a film or sheet. preferred polymers, copolymers or derivates thereof are selected polyacrylates, and water soluble acrylate copolymers, methyl cellulose, carboxy methyl cellulose, sodium dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, malto dextrin, poly methacrylates, most preferably polyvinyl alcohol copolymers and, hydroxypropyl methyl cellulose (hpmc). preferably the level of polymer in the film for example pva is at least about 60%. preferred average molecular weight will typically be about 20,000 to about 150,000. films can also be of blended compositions comprising hydrolytically degradable and water soluble polymer blends such as polylactide and polyvinyl alcohol (known under the trade reference m8630 as sold by monosol llc, indiana, usa) plus plasticisers like glycerol, ethylene glycerol, propylene glycol, sorbitol and mixtures thereof. the pouches can comprise a solid laundry cleaning composition or part components and/or a liquid cleaning composition or part components separated by the water soluble film. the compartment for liquid components can be different in composition than compartments containing solids: us2009/0011970 a1. detergent ingredients can be separated physically from each other by compartments in water dissolvable pouches or in different layers of tablets. thereby negative storage interaction between components can be avoided. different dissolution profiles of each of the compartments can also give rise to delayed dissolution of selected components in the wash solution. a liquid or gel detergent, which is not unit dosed, may be aqueous, typically containing at least 20% by weight and up to 95% water, such as up to about 70% water, up to about 65% water, up to about 55% water, up to about 45% water, up to about 35% water. other types of liquids, including without limitation, alkanols, amines, diols, ethers and polyols may be included in an aqueous liquid or gel. an aqueous liquid or gel detergent may contain from 0-30% organic solvent. a liquid or gel detergent may be non-aqueous. granular cleaning formulations non-dusting granulates may be produced, e.g. as disclosed in u.s. pat. nos. 4,106,991 and 4,661,452 and may optionally be coated by methods known in the art. examples of waxy coating materials are poly(ethylene oxide) products (polyethyleneglycol, peg) with mean molar weights of 1000 to 20000; ethoxylated nonylphenols having from 16 to 50 ethylene oxide units; ethoxylated fatty alcohols in which the alcohol contains from 12 to 20 carbon atoms and in which there are 15 to 80 ethylene oxide units; fatty alcohols; fatty acids; and mono- and di- and triglycerides of fatty acids. examples of film-forming coating materials suitable for application by fluid bed techniques are given in gb 1483591. liquid enzyme preparations may, for instance, be stabilized by adding a polyol such as propylene glycol, a sugar or sugar alcohol, lactic acid or boric acid according to established methods. protected enzymes may be prepared according to the method disclosed in ep 238,216. the dnase and the alpha-mannan degrading enzyme may be formulated as a granule for example as a co-granule that combines one or more enzymes. each enzyme will then be present in more granules securing a more uniform distribution of enzymes in the detergent. this also reduces the physical segregation of different enzymes due to different particle sizes. methods for producing multi-enzyme co-granulate for the detergent industry is disclosed in the ip.com disclosure ipcom000200739d. another example of formulation of enzymes by the use of co-granulates are disclosed in wo 2013/188331, which relates to a detergent composition comprising (a) a multi-enzyme co-granule; (b) less than 10 wt zeolite (anhydrous basis); and (c) less than 10 wt phosphate salt (anhydrous basis), wherein said enzyme co-granule comprises from 10 to 98 wt % moisture sink component and the composition additionally comprises from 20 to 80 wt % detergent moisture sink component. the multi-enzyme co-granule may comprise an enzyme blend of the invention (alpha-mannanase and dnase) and one or more enzymes selected from the group consisting of alpha-mannan degrading enzymes, lipases, cellulases, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, laccases, hemicellulases, alpha-mannan degrading enzymes, cellulases, cellobiose dehydrogenases, xylanases, phospho lipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, ligninases, pullulanases, tannases, pentosanases, lichenases glucanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof. wo 2013/188331 also relates to a method of treating and/or cleaning a surface, preferably a fabric surface comprising the steps of (i) contacting said surface with the detergent composition as claimed and described herein in aqueous wash liquor, (ii) rinsing and/or drying the surface. an embodiment of the invention relates to an enzyme granule/particle comprising the dnase and alpha-mannan degrading enzyme. the granule is composed of a core, and optionally one or more coatings (outer layers) surrounding the core. typically, the granule/particle size, measured as equivalent spherical diameter (volume based average particle size), of the granule is 20-2000 μm, particularly 50-1500 μm, 100-1500 μm or 250-1200 μm. the core may include additional materials such as fillers, fibre materials (cellulose or synthetic fibres), stabilizing agents, solubilising agents, suspension agents, viscosity regulating agents, light spheres, plasticizers, salts, lubricants and fragrances. the core may include binders, such as synthetic polymer, wax, fat, or carbohydrate. the core may comprise a salt of a multivalent cation, a reducing agent, an antioxidant, a peroxide decomposing catalyst and/or an acidic buffer component, typically as a homogenous blend. the core may consist of an inert particle with the enzyme absorbed into it, or applied onto the surface, e.g., by fluid bed coating. the core may have a diameter of 20-2000 μm, particularly 50-1500 μm, 100-1500 μm or 250-1200 μm. the core can be prepared by granulating a blend of the ingredients, e.g., by a method comprising granulation techniques such as crystallization, precipitation, pan-coating, fluid bed coating, fluid bed agglomeration, rotary atomization, extrusion, prilling, spheronization, size reduction methods, drum granulation, and/or high shear granulation. methods for preparing the core can be found in handbook of powder technology; particle size enlargement by c. e. capes; volume 1; 1980; elsevier. the core of the enzyme granule/particle may be surrounded by at least one coating, e.g., to improve the storage stability, to reduce dust formation during handling, or for coloring the granule. the optional coating(s) may include a salt coating, or other suitable coating materials, such as polyethylene glycol (peg), methyl hydroxy-propyl cellulose (mhpc) and polyvinyl alcohol (pva). examples of enzyme granules with multiple coatings are shown in wo 93/07263 and wo 97/23606. the coating may be applied in an amount of at least 0.1% by weight of the core, e.g., at least 0.5%, 1% or 5%. the amount may be at most 100%, 70%, 50%, 40% or 30%. the coating is preferably at least 0.1 μm thick, particularly at least 0.5 μm, at least 1 μm or at least 5 μm. in a one embodiment, the thickness of the coating is below 100 μm. in another embodiment, the thickness of the coating is below 60 μm. in an even more particular embodiment the total thickness of the coating is below 40 μm. the coating should encapsulate the core unit by forming a substantially continuous layer. a substantially continuous layer is to be understood as a coating having few or no holes, so that the core unit it is encapsulating/enclosing has few or none uncoated areas. the layer or coating should be homogeneous in thickness. the coating can further contain other materials as known in the art, e.g., fillers, antisticking agents, pigments, dyes, plasticizers and/or binders, such as titanium dioxide, kaolin, calcium carbonate or talc. a salt coating may comprise at least 60% by weight w/w of a salt, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99% by weight w/w. the salt may be added from a salt solution where the salt is completely dissolved or from a salt suspension wherein the fine particles is less than 50 μm, such as less than 10 μm or less than 5 μm. the salt coating may comprise a single salt or a mixture of two or more salts. the salt may be water soluble and may have a solubility at least 0.1 grams in 100 g of water at 20° c., preferably at least 0.5 g per 100 g water, e.g., at least 1 g per 100 g water, e.g., at least 5 g per 100 g water. the salt may be an inorganic salt, e.g., salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of simple organic acids (less than 10 carbon atoms, e.g., 6 or less carbon atoms) such as citrate, malonate or acetate. examples of cations in these salts are alkali or earth alkali metal ions, the ammonium ion or metal ions of the first transition series, such as sodium, potassium, magnesium, calcium, zinc or aluminium. examples of anions include chloride, bromide, iodide, sulfate, sulfite, bisulfite, thiosulfate, phosphate, monobasic phosphate, dibasic phosphate, hypophosphite, dihydrogen pyrophosphate, tetraborate, borate, carbonate, bicarbonate, metasilicate, citrate, malate, maleate, malonate, succinate, lactate, formate, acetate, butyrate, propionate, benzoate, tartrate, ascorbate or gluconate. in particular alkali- or earth alkali metal salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of simple organic acids such as citrate, malonate or acetate may be used. the salt in the coating may have a constant humidity at 20° c. above 60%, particularly above 70%, above 80% or above 85%, or it may be another hydrate form of such a salt (e.g., anhydrate). the salt coating may be as described in wo 00/01793 or wo 2006/034710. specific examples of suitable salts are nacl (ch 2° c. =76%), na 2 co 3 (ch 20° c. =92%), nano 3 (ch 20° c. =73%), na 2 hpo 4 (ch 20° c. =95%), na 3 po 4 (ch 25° c. =92%), nh 4 cl (ch 20° c. =79.5%), (nh 4 ) 2 hpo 4 (ch 20° c. =93.0%), nh 4 h 2 po 4 (ch 20° c. =93.1%), (nh 4 ) 2 so 4 (ch 20° c. =81.1%), kcl (ch 20° c. =85%), k 2 hpo 4 (ch 20° c. =92%), kh 2 po 4 (ch 20° c. =96.5%), kno 3 (ch 20° c. =93.5%), na 2 so 4 (ch 20° c. =93%), k 2 so 4 (ch 20° c. =98%), khso 4 (ch 20° c. =86%), mgso 4 (ch 20° c. =90%), znso 4 (ch 20° c. =90%) and sodium citrate (ch 25° c. =86%). other examples include nah 2 po 4 , (nh 4 )h 2 po 4 , cuso 4 , mg(no 3 ) 2 and magnesium acetate. the salt may be in anhydrous form, or it may be a hydrated salt, i.e. a crystalline salt hydrate with bound water(s) of crystallization, such as described in wo 99/32595. specific examples include anhydrous sodium sulfate (na 2 so 4 ), anhydrous magnesium sulfate (mgso 4 ), magnesium sulfate heptahydrate (mgso 4 -7h 2 o), zinc sulfate heptahydrate (znso 4 -7h 2 o), sodium phosphate dibasic heptahydrate (na 2 hpo 4 -7h 2 o), magnesium nitrate hexahydrate (mg(no 3 ) 2 (6h 2 o)), sodium citrate dihydrate and magnesium acetate tetrahydrate. preferably the salt is applied as a solution of the salt, e.g., using a fluid bed. one embodiment of the present invention provides a granule, which comprises: (a) a core comprising a dnase and an alpha-mannan degrading enzyme, preferably selected from gh76, gh92 and gh99, and (b) optionally a coating consisting of one or more layer(s) surrounding the core. one embodiment of the invention relates to a granule, which comprises: (a) a core comprising a dnase and an alpha-mannan degrading enzyme wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to an amino acid sequence shown in seq id nos: and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13, and(b) optionally a coating consisting of one or more layer(s) surrounding the core. one embodiment of the invention relates to a granule, which comprises: (a) a core comprising a dnase and an alpha-mannan degrading enzyme wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65, and(b) optionally a coating consisting of one or more layer(s) surrounding the core. one embodiment of the invention relates to a granule, which comprises:(a) a core comprising a dnase and an alpha-mannan degrading enzyme wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66, and(b) optionally a coating consisting of one or more layer(s) surrounding the core. one embodiment of the invention relates to a granule, which comprises:(a) a core comprising a dnase and an alpha-mannan degrading enzyme wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67, and(b) optionally a coating consisting of one or more layer(s) surrounding the core. one embodiment of the invention relates to a granule, which comprises:(a) a core comprising a dnase and an alpha-mannan degrading enzyme wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68, and(b) optionally a coating consisting of one or more layer(s) surrounding the core. uses the present invention is also directed to methods for using the compositions thereof. laundry/textile/fabric (house hold laundry washing, industrial laundry washing). hard surface cleaning (adw, car wash, industrial surface). the cleaning e.g. detergent composition of the present invention may be formulated, for example, as a hand or machine laundry detergent composition including a laundry additive composition suitable for pre-treatment of stained fabrics and a rinse added fabric softener composition or be formulated as a detergent composition for use in general household hard surface cleaning operations or be formulated for hand or machine dishwashing operations. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and effectively reduce or remove organic components, such as polysaccharides and dna from surfaces such as textiles and hard surfaces e.g. dishes. one embodiment of the invention relates to the use of a composition comprising a dnase and alpha-mannan degrading enzyme for reduction of redeposition. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and alpha-mannan degrading enzyme for reduction of redeposition one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and alpha-mannan degrading enzyme for reduction of redeposition when the cleaning composition is applied in e.g. laundry process. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and alpha-mannan degrading enzyme for reduction of redeposition on an item e.g. textile. in one embodiment, the composition is an anti-redeposition composition. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus , preferably bacillus cibi, bacillus horikoshii, bacillus licheniformis, bacillus subtilis, bacillus horneckiae, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi or bacillus luciferensis. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 and 97 and wherein the dnase is obtained from bacillus and comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of redeposition, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. the compositions of the invention comprise a blend of dnase and an alpha-mannan degrading enzyme and effectively reduce or limit malodor of e.g. textiles or hard surfaces such as dishes. one embodiment of the invention relates to the use of a composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor when the cleaning composition is applied in e.g. laundry process. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor on an item e.g. textile. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus , preferably bacillus cibi, bacillus horikoshii, bacillus licheniformis, bacillus subtilis, bacillus horneckiae, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi or bacillus luciferensis. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus and comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction of malodor, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and improve whiteness of textile. one embodiment of the invention relates to the use of a composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness of an item e.g. a textile. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme improve whiteness when the cleaning composition is applied in e.g. laundry process. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme improve whiteness on an item e.g. textile. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos:79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus , preferably bacillus cibi, bacillus horikoshii, bacillus licheniformis, bacillus subtilis, bacillus horneckiae, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi or bacillus luciferensis. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus and comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for improve whiteness, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. the compositions of the invention comprise a blend of dnase and alpha-mannan degrading enzyme and effectively reduce or remove poly-organic stains comprising organic components, such as polysaccharides and dna from surfaces such as textiles and hard surfaces e.g. dishes. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component for reduction or removal of biofilm and components of biofilm, such as dna and polysaccharides, of an item, wherein the item is a textile or a hard surface. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase, an alpha-mannan degrading enzyme and at least one cleaning component for deep cleaning of an item, wherein the item is a textile or a surface. one embodiment of the invention relates to the use of a composition comprising a dnase and an alpha-mannan degrading enzyme for reduction or removal of biofilm compounds such as dna and polysaccharides of an item. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for reduction or removal of biofilm compounds such as dna and polysaccharides of an item such as textile. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep cleaning e.g. reduction or removal of biofilm compounds such as dna and polysaccharides when the cleaning composition is applied in e.g. laundry process. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus , preferably bacillus cibi, bacillus horikoshii, bacillus licheniformis, bacillus subtilis, bacillus horneckiae, bacillus idriensis, bacillus algicola, bacillus vietnamensis, bacillus hwajinpoensis, bacillus indicus, bacillus marisflavi or bacillus luciferensis. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the dnase is obtained from bacillus and comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment of the invention relates to the use of a cleaning composition comprising a dnase and an alpha-mannan degrading enzyme for deep clean of an item, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. the invention further relates to a method of deep cleaning an item, wherein the item may be textile or hard surface preferably is a textile, one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of: a) contacting the item with a cleaning composition according to the invention; andb) and optionally rinsing the item, wherein the item is preferably a textile. one embodiment of the invention relates to a method of cleaning on an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of: a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 13. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and a alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 65. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 66. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 67. one embodiment of the invention relates to a method of cleaning e.g. deep cleaning an item, comprising the steps of:a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 0.1 to 15 wt %, preferably 1 to 30 wt % or preferably 1 to 60 wt % of at least one a surfactant; 0.5 to 20 wt %, preferably 1 to 40 wt % of at least one builder; and 0.01 to 10 wt %, preferably 1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile, wherein the alpha-mannan degrading enzyme has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 98% sequence identity to the amino acid sequence shown in seq id nos: 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 or 97 and wherein the is dnase has at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the amino acid sequence shown in seq id no: 68. definitions biofilm is produced by any group of microorganisms in which cells stick to each other or stick to a surface, such as a textile, dishware or hard surface or another kind of surface. these adherent cells are frequently embedded within a self-produced matrix of extracellular polymeric substance (eps). biofilm eps is a polymeric conglomeration generally composed of extracellular dna, proteins, and polysaccharides. biofilms may form on living or non-living surfaces. the microbial cells growing in a biofilm are physiologically distinct from planktonic cells of the same organism, which, by contrast, are single-cells that may float or swim in a liquid medium. bacteria living in a biofilm usually have significantly different properties from planktonic bacteria of the same species, as the dense and protected environment of the film allows them to cooperate and interact in various ways. one benefit of this environment for the microorganisms is increased resistance to detergents and antibiotics, as the dense extracellular matrix and the outer layer of cells protect the interior of the community. on laundry biofilm producing bacteria can be found among the following species: acinetobacter sp., aeromicrobium sp., brevundimonas sp., microbacterium sp., micrococcus luteus, pseudomonas sp., staphylococcus epidermidis , and stenotrophomonas sp. on hard surfaces biofilm producing bacteria can be found among the following species: acinetobacter sp., aeromicrobium sp., brevundimonas sp., microbacterium sp., micrococcus luteus, pseudomonas sp., staphylococcus epidermidis, staphylococcus aureus and stenotrophomonas sp. in one aspect, the biofilm producing strain is brevundimonas sp. in one aspect, the biofilm producing strain is pseudomonas alcaliphila or pseudomonas fluorescens . in one aspect, the biofilm producing strain is staphylococcus aureus. by the term “deep cleaning” is meant reduction, disruption or removal of components which may be comprised in organic matter, e.g. biofilm, such as polysaccharides, proteins, dna, soil or other components present in the organic matter. in the context of the present invention organic matter is e.g. a poly-organic stain i.e. a stain comprising more than one organic component such as stains from body soiling e.g. skin cell debris, sebum, sweat, and biofilm, eps, etc. which comprises several organic molecules such as polysaccharides, extracellular dna (exdna), mannan e.g. α-mannan, starch and proteins. cleaning component: the cleaning component e.g. the detergent adjunct ingredient is different to the dnase and alpha-mannan degrading enzyme enzymes. the precise nature of these additional cleaning components e.g. adjunct components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. suitable cleaning components e.g. adjunct materials include, but are not limited to the components described below such as surfactants, builders, flocculating aid, chelating agents, dye transfer inhibitors, enzymes, enzyme stabilizers, enzyme inhibitors, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, builders and co-builders, fabric huing agents, anti-foaming agents, dispersants, processing aids, and/or pigments. cleaning composition: the term “cleaning composition” refers to compositions that find use in the removal of undesired compounds from items to be cleaned, such as textiles. the cleaning composition may be used to e.g. clean textiles for both household cleaning and industrial cleaning. the terms encompass any materials/compounds selected for the particular type of cleaning composition desired and the form of the product (e.g., liquid, gel, powder, granulate, paste, or spray compositions) and includes, but is not limited to, detergent compositions (e.g., liquid and/or solid laundry detergents and fine fabric detergents; fabric fresheners; fabric softeners; and textile and laundry pre-spotters/pretreatment). in addition to containing the enzymes, the cleaning composition may contain one or more additional enzymes (such as amylases, lipases, cutinases, cellulases, endoglucanases, xyloglucanases, pectinases, pectin lyases, xanthanases, peroxidases, haloperoxygenases, catalases and mannanases, or any mixture thereof), and/or cleaning components e.g. detergent adjunct ingredients such as surfactants, builders, chelators or chelating agents, bleach system or bleach components, polymers, fabric conditioners, foam boosters, suds suppressors, dyes, perfume, tannish inhibitors, optical brighteners, bactericides, fungicides, soil suspending agents, anti-corrosion agents, enzyme inhibitors or stabilizers, enzyme activators, transferase(s), hydrolytic enzymes, oxido reductases, bluing agents and fluorescent dyes, antioxidants, and solubilizers. the term “enzyme detergency benefit” is defined herein as the advantageous effect an enzyme may add to a detergent compared to the same detergent without the enzyme. important detergency benefits which can be provided by enzymes are stain removal with no or very little visible soils after washing and/or cleaning, prevention or reduction of redeposition of soils released in the washing process (an effect that also is termed anti-redeposition), restoring fully or partly the whiteness of textiles which originally were white but after repeated use and wash have obtained a greyish or yellowish appearance (an effect that also is termed whitening). textile care benefits, which are not directly related to catalytic stain removal or prevention of redeposition of soils, are also important for enzyme detergency benefits. examples of such textile care benefits are prevention or reduction of dye transfer from one fabric to another fabric or another part of the same fabric (an effect that is also termed dye transfer inhibition or anti-backstaining), removal of protruding or broken fibers from a fabric surface to decrease pilling tendencies or remove already existing pills or fuzz (an effect that also is termed anti-pilling), improvement of the fabric-softness, colour clarification of the fabric and removal of particulate soils which are trapped in the fibers of the fabric or garment. enzymatic bleaching is a further enzyme detergency benefit where the catalytic activity generally is used to catalyze the formation of bleaching components such as hydrogen peroxide or other peroxides. textile care benefits, which are not directly related to catalytic stain removal or prevention of redeposition of soils, are also important for enzyme detergency benefits. examples of such textile care benefits are prevention or reduction of dye transfer from one textile to another textile or another part of the same textile (an effect that is also termed dye transfer inhibition or anti-backstaining), removal of protruding or broken fibers from a textile surface to decrease pilling tendencies or remove already existing pills or fuzz (an effect that also is termed anti-pilling), improvement of the textile-softness, colour clarification of the textile and removal of particulate soils which are trapped in the fibers of the textile. enzymatic bleaching is a further enzyme detergency benefit where the catalytic activity generally is used to catalyze the formation of bleaching component such as hydrogen peroxide or other peroxides or other bleaching species.” the term “hard surface cleaning” is defined herein as cleaning of hard surfaces wherein hard surfaces may include floors, tables, walls, roofs etc. as well as surfaces of hard objects such as cars (car wash) and dishes (dish wash). dish washing includes but are not limited to cleaning of plates, cups, glasses, bowls, cutlery such as spoons, knives, forks, serving utensils, ceramics, plastics, metals, china, glass and acrylics. the term “wash performance” is used as an enzyme's ability to remove stains present on the object to be cleaned during e.g. wash or hard surface cleaning. the term “whiteness” is defined herein as a greying, yellowing of a textile. loss of whiteness may be due to removal of optical brighteners/hueing agents. greying and yellowing can be due to soil redeposition, body soils, colouring from e.g. iron and copper ions or dye transfer. whiteness might include one or several issues from the list below: colourant or dye effects; incomplete stain removal (e.g. body soils, sebum etc.); redeposition (greying, yellowing or other discolourations of the object) (removed soils reassociate with other parts of textile, soiled or unsoiled); chemical changes in textile during application; and clarification or brightening of colours. the term “laundering” relates to both household laundering and industrial laundering and means the process of treating textiles with a solution containing a cleaning or detergent composition of the present invention. the laundering process can for example be carried out using e.g. a household or an industrial washing machine or can be carried out by hand. by the term “malodor” is meant an odor which is not desired on clean items. the cleaned item should smell fresh and clean without malodors adhered to the item. one example of malodor is compounds with an unpleasant smell, which may be produced by microorganisms. another example is unpleasant smells can be sweat or body odor adhered to an item which has been in contact with human or animal. another example of malodor can be the odor from spices, which sticks to items for example curry or other exotic spices which smells strongly. the term “mature polypeptide” means a polypeptide in its final form following translation and any post-translational modifications, such as n-terminal processing, c-terminal truncation, glycosylation, phosphorylation, etc. the term “textile” means any textile material including yarns, yarn intermediates, fibers, non-woven materials, natural materials, synthetic materials, and any other textile material, fabrics made of these materials and products made from fabrics (e.g., garments and other articles). the textile or fabric may be in the form of knits, wovens, denims, non-wovens, felts, yarns, and towelling. the textile may be cellulose based such as natural cellulosics, including cotton, flax/linen, jute, ramie, sisal or coir or manmade cellulosics (e.g. originating from wood pulp) including viscose/rayon, cellulose acetate fibers (tricell), lyocell or blends thereof. the textile or fabric may also be non-cellulose based such as natural polyamides including wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane, or blends thereof as well as blends of cellulose based and non-cellulose based fibers. examples of blends are blends of cotton and/or rayon/viscose with one or more companion material such as wool, synthetic fiber (e.g. polyamide fiber, acrylic fiber, polyester fiber, polyvinyl chloride fiber, polyurethane fiber, polyurea fiber, aramid fiber), and/or cellulose-containing fiber (e.g. rayon/viscose, ramie, flax/linen, jute, cellulose acetate fiber, lyocell). fabric may be conventional washable laundry, for example stained household laundry. when the term fabric or garment is used, it is intended to include the broader term textiles as well. the term “variant” means a polypeptide having the activity of the parent or precursor polypeptide and comprising an alteration, i.e., a substitution, insertion, and/or deletion, at one or more (e.g., several) positions compared to the precursor or parent polypeptide. a substitution means replacement of the amino acid occupying a position with a different amino acid; a deletion means removal of the amino acid occupying a position; and an insertion means adding an amino acid adjacent to and immediately following the amino acid occupying a position. a polypeptide having dnase or alpha-mannan degrading activity of the present invention may be obtained from microorganisms of any genus. for purposes of the present invention, the term “obtained from” as used herein in connection with a given source shall mean that the polypeptide encoded by a polynucleotide is produced by the source or by a strain in which the polynucleotide from the source has been inserted. in one aspect, the polypeptide obtained from a given source is secreted extracellularly. sequence identity: the relatedness between two amino acid sequences or between two nucleotide sequences is described by the parameter “sequence identity”. for purposes of the present invention, the sequence identity between two amino acid sequences is determined using the needleman-wunsch algorithm (needleman and wunsch, 1970, j. mol. biol. 48: 443-453) as implemented in the needle program of the emboss package (emboss: the european molecular biology open software suite, rice et al., 2000, trends genet. 16: 276-277), preferably version 6.6.0 or later. the parameters used are a gap open penalty of 10, a gap extension penalty of 0.5, and the eblosum62 (emboss version of blosum62) substitution matrix. the output of needle labeled “longest identity” (obtained using the -nobrief option) is used as the percent identity and is calculated as follows: (identical residues×100)/(length of alignment−total number of gaps in alignment) the invention may further relate to any of the following embodiments; paragraph 1. a cleaning composition comprising at least 0.001 ppm dnase, at least 0.001 ppm alpha-mannan degrading enzyme and a cleaning component, wherein the cleaning component is selected from a. 1 to 40 wt % of at least one a surfactant;b. 0.5 to 30 wt % of at least one builder; andc. 0.1 to 20 wt % of at least one bleach component. paragraph 2. the cleaning composition according to paragraph 1, wherein the dnase comprises one or both of the motif(s) [d/m/l][s/t]gysr[d/n] (seq id no: 73) or asxnrskg (seq id no: 74). paragraph 3. the cleaning composition according to paragraphs 1 or 2, wherein the dnase is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 1,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 2,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 3,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 4,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 5,f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 6,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 7,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 8,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 9,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 10,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 11,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 12,m) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 13,n) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 14,o) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 15,p) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 16,q) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 17,r) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 18,s) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 19,t) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 20,u) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 21,v) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 22,w) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 23,x) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 24, andy) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 25. paragraph 4. the cleaning composition according to paragraph 1, wherein the dnase comprises one or both of the motif(s) [v/i]pl[s/a]nawk (seq id no: 75) or npql (seq id no: 76). paragraph 5. the cleaning composition according to paragraph 1 or 4, wherein the dnase is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 26,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 27,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 28,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 29,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 30,f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 31,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 32,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 33,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 34,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 35,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 36,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 37, andm) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 38. paragraph 6. the cleaning composition according to paragraph 1 wherein the dnase comprises one or both of the motif(s) p[q/e]l[w/y] (seq id no: 77) or [k/h/e]naw (seq id no: 78). paragraph 7. the cleaning composition according to paragraphs 1 or 6, wherein the dnase is selected from the group of polypeptides: a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 39,b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 40,c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 41,d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 42,e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 43f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 44,g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 45,h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 46,i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 47,j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 48,k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 49,l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 50, andm) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity to the polypeptide shown in seq id no: 51. paragraph 8. the cleaning composition according to paragraph 1, wherein the dnase is selected from the group consisting of: a) a polypeptide obtainable from bacillus cibi having a sequence identity to the polypeptide shown in seq id no: 13 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity,b) a polypeptide obtainable from bacillus licheniformis having a sequence identity to the polypeptide shown in seq id no: 65 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity,c) a polypeptide obtainable from bacillus subtilis having a sequence identity to the polypeptide shown in seq id no: 66 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity,d) a polypeptide obtainable from aspergillus oryzae having a sequence identity to the polypeptide shown in seq id no: 67 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity,e) a polypeptide obtainable from trichoderma harzianum having a sequence identity to the polypeptide shown in seq id no: 68 of at least 60%, e.g., at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100% and which have dnase activity, and combinations thereof. paragraph 9. the cleaning component of any of paragraphs 1 to 8 wherein the alpha-mannan degrading enzyme is selected from, (a) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 79 or a fragment thereof having alpha-mannan degrading activity;(b) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 80 or a fragment thereof having alpha-mannan degrading activity;(c) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 81 or a fragment thereof having alpha-mannan degrading activity;(d) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 82 or a fragment thereof having alpha-mannan degrading activity;(e) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 83 or a fragment thereof having alpha-mannan degrading activity;(f) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 84 or a fragment thereof having alpha-mannan degrading activity;(g) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 85 or a fragment thereof having alpha-mannan degrading activity;(h) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 86 or a fragment thereof having alpha-mannan degrading activity;(i) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 87 or a fragment thereof having alpha-mannan degrading activity;(j) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 88 or a fragment thereof having alpha-mannan degrading activity;(k) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 89 or a fragment thereof having alpha-mannan degrading activity;(l) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 90 or a fragment thereof having alpha-mannan degrading activity;(m) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 91 or a fragment thereof having alpha-mannan degrading activity;(n) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 92 or a fragment thereof having alpha-mannan degrading activity;(o) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 93 or a fragment thereof having alpha-mannan degrading activity;(p) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 94 or a fragment thereof having alpha-mannan degrading activity;(q) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 95 or a fragment thereof having alpha-mannan degrading activity;(r) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 96 or a fragment thereof having alpha-mannan degrading activity; and(s) a polypeptide having at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% sequence identity to the polypeptide of seq id no: 97 or a fragment thereof having alpha-mannan degrading activity. paragraph 10. the use of a composition according to any of the previous paragraphs for deep cleaning of an item, wherein the item is a textile or a surface. paragraph 11. a method of formulating a cleaning composition comprising adding a dnase, an alpha-mannan degrading enzyme and at least one cleaning component. paragraph 12. a kit intended for deep cleaning, wherein the kit comprises a solution of an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme. paragraph 13. a method of cleaning e.g. deep cleaning an item, comprising the steps of: a) contacting the item with a solution comprising an enzyme mixture comprising a dnase and an alpha-mannan degrading enzyme; and a cleaning component, wherein the cleaning component is selected from 1 to 40 wt % of at least one a surfactant; 0.5 to 30 wt % of at least one builder; and 0.1 to 20 wt % of at least one bleach component; andb) and optionally rinsing the item, wherein the item is preferably a textile. examples assays assay i dnase activity dnase activity is determined on dnase test agar with methyl green (bd, franklin lakes, n.j., usa), which is prepared according to the manual from supplier. briefly, 21 g of agar is dissolved in 500 ml water and then autoclaved for 15 min at 121° c. autoclaved agar is temperated to 48° c. in water bath, and 20 ml of agar is poured into petri dishes with and allowed to solidify by incubation o/n at room temperature. on solidified agar plates, 5 μl of enzyme solutions are added and dnase activity is observed as colorless zones around the spotted enzyme solutions assay ii dnase activity dnase activity is determined by using the dnasealert™ kit (11-02-01-04, idt intergrated dna technologies) according to the supplier's manual. briefly, 95 μl dnase sample is mixed with 5 μl substrate in a microtiter plate, and fluorescence is immediately measured using a clariostar microtiter reader from bmg labtech (536 nm excitation, 556 nm emission). assay iii reducing end assay (alpha-mannanase activity) for estimating the mannose yield after substrate hydrolysis, a reducing end assay developed by lever (anal. biochem. 47: 273-279, 1972) is used. the assay is based on 4-hydroxybenzoic acid hydrazide, which under alkaline conditions reacts with the reducing ends of saccharides. the product is a strong yellow anion, which absorbs at 405 nm. method. the hydrolysis reaction mixture is composed of 20 μl enzyme and 180 μl substrate dissolved in buffer. the substrate is alfa-1,6-mannan prepared as described elsewhere (cuskin, nature, 2015, 517, 165-169) at a concentration of 2 mg/ml. the buffer is 25 mm acetate, ph5.5, 50 mm kcl, 0.01% triton x-100, 1 mm cacl2. the reaction conditions are 30 minutes, 37° c., and 950 rpm. 4-hydroxybenzhydrazide (pahbah) (sigma, h9882) is diluted in pahbah buffer to a concentration of 15 mg/ml. pahbah buffer contains: 50 g/l k-na-tartrate (merck, 1.08087) and 20 g/l sodium hydroxide (sigma, s8045). this pahbah mix is made just before usage. 70 μl pahbah mix and miliq water are mixed in a 96 well pcr plate (thermo scientific). samples from hydrolysis experiment are added. samples and miliq always reached the total volume of 150 μl, but the dilution of the sample differed. the plate is sealed with adhesive pcr sealing foil sheets (thermo scientific). plates are incubated at 95° c. for 10 min, cooled down and kept at 10° c. for 1 min in ptc-200 thermal cycler (mj research). 100 μl sample is transferred to a 96 well microtiter plate, flat bottomed (nunc™) and color development measured at 405 nm on a spectramax 190 absorbance microplate reader (molecular devices). results are compared to mannose standards, which had undergone the same treatment and dilution as the samples to which they were compared. model detergents model detergent a wash liquor (100%) is prepared by dissolving 3.33 g/l of model detergent a containing 12% las, 11% aeo biosoft n25-7 (ni), 17.63% aeos (sles), 6% mpg, 3% ethanol, 3.33% tea (triethanolamine), 2.75% cocoa soap, 2.75% soya soap, 1.7% glycerol, 1.75% sodium hydroxide, 2% sodium citrate, 1% sodium formate, 0.48% dtmpa and 0.46% pca (all percentages are w/w (weight volume) in water with hardness 15 dh. triple-20 nonionic model detergent (60% surfactant) is prepared by dissolving 3.33 g/i non-ionic detergent containing naoh 0.87%, mpg (monopropylenglycol) 6%, glycerol 2%, soap-soy 2.75%, soap-coco 2.75%, pca (sokalon cp-5) 0.2%, aeo biosoft n25-7(ni) 16%, sodium formiate 1%, sodium citrate 2%, dtmpa 0.2%, ethanol (96%) 3%, adjustment of ph with naoh or citric acid add water to 100% (all percentages are w/w (weight volume) in water with hardness 15 dh. model detergent mc: a medical cleaning model detergent (model detergent mc) is prepared containing 5% mpg (propylene glycol), 5% pluronic pe 4300 (po/eo block polymer; 70%/30%, approx. 1750 g/mol), 2% plurafac lf 305 (fatty alcohol alkoxylate; c6-10+eo/po), 1% mgda (methyl glycine diacetic acid, 1% tea (triethanolamine) (all percentages are w/w). the ph is adjusted to 8.7 with phosphoric acid. example 1 preparation of biofilm swatches biofilm swatches were made by growing brevundimonas sp. on polyester swatches for two days. the biofilm swatches were rinsed twice in water and dried for 1 h under flow and subsequently punched into small circles and stored at 4° c. for further use. washing experiment biofilm swatches punctures were placed in a deep well 96 format plate. the 96 well plate was placed in a hamilton robot and subjected to a wash simulation program using the following conditions: shaking speed: 30 sec at 1000 rpm. duration of wash cycle: 30 minutes with shaking; temperature 30° c.; volume of wash liquor (total): 0.5 ml per well. (490 wash liquor+10 ul sample). for wash performance assay, model detergent a (3.3 g/l) dissolved in water hardness 15° dh was used. soil was subsequently added to reach a concentration of 0.7 g soil/l (wfk 09v pigment soil). a 96 well plate was filled with each enzyme sample, and the program was started on the robot. the dnase (seq id no 13) was used in low dose (0.00001 ppm) to show synergy. the alpha-mannanase (alpha-mannan degrading enzyme) (seq id no 88) was tested in a dose of 0.2 ppm and 0.4 ppm. the blank consisted of biofilm swatches without any enzyme addition. after completion of the wash simulation cycle, the swatch punctures were removed from the wash liquor and dried on a filter paper. the dried swatch punctures were fixed on a sheet of white paper for scanning. the scanned picture was further used with the software colour-analyzer. each sample will have an intensity measurement, from the colour analyzer software analysis, that will be used to calculate the delta intensity (remission), by subtracting the intensity of the blank, without enzyme. values over 40 are visual for the human eye. table 1wash performance of alpha-mannanase (seq id no 88)with and without dnase (seq id no 13).intensitydelta(alpha-intensityintensitymannanase +delta intensity (alpha-(individual)(individual)dnase)mannanase + dnase)0.2 ppmalpha-2413127161mannanase0.4 ppmalpha-27666mannanase0.00001 ppmdnase23121no enzyme,2100blank conclusion: instead of doubling the dose of alpha-mannanase from 0.2 ppm to 0.4 ppm, it was possible to get the same wash performance of 0.4 ppm alpha-mannanase by combining alpha-mannanase (0.2 ppm) with a small amount of dnase (0.00001 ppm).
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044-647-870-816-307
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US
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[
"US"
] |
H04L69/40
| 2017-11-17T00:00:00 |
2017
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[
"H04"
] |
system for generating distributed cloud data storage on disparate devices
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a system is configured to allocate storage space on existing devices within the entity's networked system to create cloud storage space. in particular, unallocated space on computing devices, typically user devices, within an entity's network is utilized as a cloud data repository. cloud data is indexed, divided into chunks, encrypted, and stored on numerous disparate endpoint devices connected to the network. copies of cloud chunk data may be duplicated across multiple endpoint devices to allow for data redundancy, thereby ensuring cloud data uptime according to the availability needs of the entity. cloud data may further be allocated to different devices based on regional data restrictions. in this way, the system provides an efficient and secure way to generate an internal cloud data storage repository within an entity's networked system.
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1 . a system for generating a distributed cloud data repository across a plurality of endpoint devices, comprising: an data management system comprising: a processor; a communication interface; and a memory having executable code stored therein, wherein the executable code, when executed by the processor, causes the processor to: receive a request to store data on the cloud data repository; assign a data identifier to the data within a data reference index; select a first endpoint device and a second endpoint device for storing the data, wherein the first endpoint device is assigned a first device id within a device index, and the second endpoint device is assigned a second device id within the device index; associate the data identifier with the first device id and the second device id; divide the data into a plurality of data portions, the plurality of data portions comprising a first data portion and a second data portion; encrypt the plurality of data portions via a data packing system; transfer, over a network, the first data portion and the second data portion to the first endpoint device; and transfer, over the network, the first data portion and the second data portion to the second endpoint device. 2 . the system according to claim 1 , wherein the executable code further causes the processor to: receive a request to retrieve the data from the cloud data repository; search the data reference index to identify the data identifier associated with the data; determine that the first device id and the second device id are associated with the data identifier; determine, via the first device id and the second device id, that the data is stored on the first endpoint device and the second endpoint device; retrieve, over the network, the first data portion and the second data portion from the first endpoint device; decrypt the first data portion and the second data portion; regenerate the data, wherein the data comprises the first data portion and the second data portion; and transfer, over the network, the data to a computing system. 3 . the system according to claim 1 , wherein the executable code further causing the processor to: retrieve device attribute data associated with the first endpoint device and the second endpoint device from the device index; based on the device attribute data, determine a processing power and a bandwidth capability of the first endpoint device and the second endpoint device; and determine that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data; wherein the first endpoint device and second endpoint device are selected based on determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data. 4 . the system according to claim 1 , wherein the executable code further causes the processor to: attempt to establish a secure communication channel with the first endpoint device; detect that the first endpoint device is offline; based on detecting that the first endpoint device is offline, determine that data uptime has dropped below a required uptime threshold; generate a copy of the first data portion and the second data portion; and transfer, over the network, the first data portion and the second data portion to a third endpoint device. 5 . the system according to claim 1 , wherein the executable code further causes the processor to: attempt to establish a secure communication channel with the first endpoint device; detect that the first endpoint device is experiencing high latency; based on detecting that the first endpoint device is experiencing high latency, determine that data uptime has dropped below a required uptime threshold; generate a copy of the first data portion and the second data portion; and transfer, over the network, the first data portion and the second data portion to a third endpoint device. 6 . the system according to claim 1 , wherein the data is subject to a data restriction, wherein the executable code further causes the processor to: determine that the first endpoint device has violated the data restriction; and delete, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. 7 . the system according to claim 1 , wherein the data is subject to a data restriction, wherein the executable code further causes the processor to deploy a data management application on the first endpoint device, wherein the data management application, when executed by a processor of the first endpoint device, causes the processor of the first endpoint device to: determine that the first endpoint device has violated the data restriction; and delete, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. 8 . the system according to claim 7 , wherein the data restriction is a territorial restriction which restricts a location of the first endpoint device to a predetermined territory, wherein determining that the first endpoint device has violated the data restriction comprises: continuously monitoring the location of the first endpoint device; and detecting that the first endpoint device is located outside of the predetermined territory. 9 . the system according to claim 1 further comprising a machine learning component, which causes the processor to: retrieve historical data related to the data; and based on the historical data, adjust a level of redundancy associated with the data. 10 . the system according to claim 9 , wherein the historical data comprises usage information, wherein adjusting the level of redundancy associated with the data comprises: determining, from the usage information, that the data is frequently accessed; and based on determining that the data is frequently accessed, transfer, over the network, the first data portion and the second data portion to a third endpoint device. 11 . the system according to claim 1 , wherein the first endpoint device is in operative communication with the network via a wireless connection, wherein the second endpoint device is in operative communication with the network via a wired connection, and wherein each of the first endpoint device and second point device is a user computing device. 12 . a computer program product for generating a distributed cloud data repository across a plurality of endpoint devices, the computer program product comprising at least one non-transitory computer readable medium having computer-readable program code portions embodied therein, the computer-readable program code portions comprising: an executable portion for receiving a request to store a data on the cloud data repository; an executable portion for assigning a data identifier to the data within a data reference index; an executable portion for selecting a first endpoint device and a second endpoint device for storing the data, wherein the first endpoint device is assigned a first device id within a device index, and the second endpoint device is assigned a second device id within the device index; an executable portion for associating the data identifier with the first device id and the second device id; an executable portion for dividing the data into a plurality of data portions, the plurality of data portions comprising a first data portion and a second data portion; an executable portion for encrypting the plurality of data portions via a data packing system; an executable portion for transferring, over a network, the first data portion and the second data portion to the first endpoint device; and an executable portion for transferring, over the network, the first data portion and the second data portion to the second endpoint device. 13 . the computer program product according to claim 12 , the computer-readable program code portions further comprising: an executable portion for receiving a request to retrieve the data from the cloud data repository; an executable portion for searching the data reference index to identify the data identifier associated with the data; an executable portion for determining that the first device id and the second device id are associated with the data identifier; an executable portion for determining, via the first device id and the second device id, that the data is stored on the first endpoint device and the second endpoint device; an executable portion for retrieving, over the network, the first data portion and the second data portion from the first endpoint device; an executable portion for decrypting the first data portion and the second data portion; an executable portion for regenerating the data, wherein the data comprises the first data portion and the second data portion; and an executable portion for transferring, over the network, the data to a computing system. 14 . the computer program product according to claim 12 , the computer-readable program code portions further comprising: an executable portion for retrieving device attribute data associated with the first endpoint device and the second endpoint device from the device index; an executable portion for, based on the device attribute data, determining a processing power and a bandwidth capability of the first endpoint device and the second endpoint device; and an executable portion for determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data, wherein the first endpoint device and second endpoint device are selected based on determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data. 15 . the computer program product according to claim 12 , wherein the data is subject to a data restriction, wherein the computer-readable program code portions further comprise: an executable portion for determining that the first endpoint device has violated the data restriction; and an executable portion for deleting, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. 16 . the computer program product according to claim 15 , wherein the data restriction is a territorial restriction which restricts a location of the first endpoint device to a predetermined territory, wherein determining that the first endpoint device has violated the data restriction comprises: continuously monitoring the location of the first endpoint device; and detecting that the first endpoint device is located outside of the predetermined territory. 17 . a computer-implemented method for generating a distributed cloud data repository across a plurality of endpoint devices, said method comprising: receiving a request to store a data on the cloud data repository; assigning a data identifier to the data within a data reference index; selecting a first endpoint device and a second endpoint device for storing the data, wherein the first endpoint device is assigned a first device id within a device index, and the second endpoint device is assigned a second device id within the device index; associating the data identifier with the first device id and the second device id; dividing the data into a plurality of data portions, the plurality of data portions comprising a first data portion and a second data portion; encrypting the plurality of data portions via a data packing system; transferring, over a network, the first data portion and the second data portion to the first endpoint device; and transferring, over the network, the first data portion and the second data portion to the second endpoint device. 18 . the computer-implemented method according to claim 17 , the method further comprising: receiving a request to retrieve the data from the cloud data repository; searching the data reference index to identify the data identifier associated with the data; determining that the first device id and the second device id are associated with the data identifier; determining, via the first device id and the second device id, that the data is stored on the first endpoint device and the second endpoint device; retrieving, over the network, the first data portion and the second data portion from the first endpoint device; decrypting the first data portion and the second data portion; regenerating the data, wherein the data comprises the first data portion and the second data portion; and transferring, over the network, the data to a computing system. 19 . the computer-implemented method according to claim 17 , the method further comprising: retrieving device attribute data associated with the first endpoint device and the second endpoint device from the device index; based on the device attribute data, determining a processing power and a bandwidth capability of the first endpoint device and the second endpoint device; and determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data, wherein the first endpoint device and second endpoint device are selected based on determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data. 20 . the computer-implemented method according to claim 17 , wherein the data is subject to a data restriction, wherein the method further comprises: determining that the first endpoint device has violated the data restriction; and deleting, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. 21 . the computer-implemented method according to claim 20 , wherein the data restriction is a territorial restriction which restricts a location of the first endpoint device to a predetermined territory, wherein determining that the first endpoint device has violated the data restriction comprises: continuously monitoring the location of the first endpoint device; and detecting that the first endpoint device is located outside of the predetermined territory.
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field of the invention the present invention embraces a system, computer program product, and computer-implemented method for generating secured cloud data storage space in a distributed manner across a plurality of disparate devices within a networked system. in particular, the invention provides a way to optimally distribute cloud data across devices having different processing and/or networking capabilities and uptimes such that the cloud data is readily accessible and available. background as the ability of computing systems to gather, process, and retain data increases over time, there is an ongoing need for data storage space. accordingly, there is a need for an efficient way to provide additional storage space available to an existing networked system. brief summary the following presents a simplified summary of one or more embodiments of the invention in order to provide a basic understanding of such embodiments. this summary is not an extensive overview of all contemplated embodiments, and is intended to neither identify key or critical elements of all embodiments, nor delineate the scope of any or all embodiments. its sole purpose is to present some concepts of one or more embodiments in a simplified form as a prelude to the more detailed description that is presented later. the invention is a novel system that allocates storage space on existing devices within the entity's networked system to create cloud storage space. in particular, unallocated space on computing devices, typically user devices, within an entity's network is utilized as a cloud data repository. cloud data is indexed, divided into chunks, encrypted, and stored on numerous disparate endpoint devices connected to the network. copies of cloud chunk data may be duplicated across multiple endpoint devices to allow for data redundancy, thereby ensuring cloud data uptime according to the availability needs of the entity. cloud data may further be allocated to different devices based on regional data restrictions. in this way, the system provides an efficient and secure way to generate an internal cloud data storage repository within an entity's networked system. accordingly, embodiments of the present invention provide a system, a computer program product, and a computer-implemented method for generating a distributed cloud data repository across a plurality of endpoint devices. the invention comprises receiving a request to store data on the cloud data repository; assigning a data identifier to the data within a data reference index; selecting a first endpoint device and a second endpoint device for storing the data, wherein the first endpoint device is assigned a first device id within a device index, and the second endpoint device is assigned a second device id within the device index; associating the data identifier with the first device id and the second device id; dividing the data into a plurality of data portions, the plurality of data portions comprising a first data portion and a second data portion; encrypting the plurality of data portions via a data packing system; transferring, over a network, the first data portion and the second data portion to the first endpoint device; and transferring, over the network, the first data portion and the second data portion to the second endpoint device. in some embodiments, the invention further comprises receiving a request to retrieve the data from the cloud data repository; searching the data reference index to identify the data identifier associated with the data; determining that the first device id and the second device id are associated with the data identifier; determining, via the first device id and the second device id, that the data is stored on the first endpoint device and the second endpoint device; retrieving, over the network, the first data portion and the second data portion from the first endpoint device; decrypting the first data portion and the second data portion; regenerating the data, wherein the data comprises the first data portion and the second data portion; and transferring, over the network, the data to a computing system. in some embodiments, the invention further comprises retrieving device attribute data associated with the first endpoint device and the second endpoint device from the device index; based on the device attribute data, determining a processing power and a bandwidth capability of the first endpoint device and the second endpoint device; and determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data, wherein the first endpoint device and second endpoint device are selected based on determining that the processing power and the bandwidth capability of the first endpoint device and the second endpoint device are sufficient to host the data. in some embodiments, the invention further comprises attempting to establish a secure communication channel with the first endpoint device; detecting that the first endpoint device is offline; based on detecting that the first endpoint device is offline, determining that data uptime has dropped below a required uptime threshold; generating a copy of the first data portion and the second data portion; and transferring, over the network, the first data portion and the second data portion to a third endpoint device. in some embodiments, the invention further comprises attempting to establish a secure communication channel with the first endpoint device; detecting that the first endpoint device is experiencing high latency; based on detecting that the first endpoint device is experiencing high latency, determining that data uptime has dropped below a required uptime threshold; generating a copy of the first data portion and the second data portion; and transferring, over the network, the first data portion and the second data portion to a third endpoint device. in some embodiments, the data is subject to a data restriction. in such embodiments, the invention further comprises determining that the first endpoint device has violated the data restriction; and deleting, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. in some embodiments, the invention comprises deploying a data management application on the first endpoint device, wherein the data management application, when executed by a processor of the first endpoint device, causes the processor of the first endpoint device to determine that the first endpoint device has violated the data restriction; and delete, via an automatic wipe function, the first data portion and the second data portion from the first endpoint device. in some embodiments, the data restriction is a territorial restriction which restricts the location of the first endpoint device to a predetermined territory, wherein determining that the first endpoint device has violated the data restriction comprises continuously monitoring the location of the first endpoint device; and detecting that the first endpoint device is located outside of the predetermined territory. in some embodiments, the invention comprises a machine learning component. in such embodiments, the invention further comprises retrieving historical data related to the data; and based on the historical data, adjusting a level of redundancy associated with the data. in some embodiments, the historical data comprises usage information. in some embodiments, adjusting the level of redundancy associated with the data comprises determining, from the usage information, that the data is frequently accessed; and based on determining that the data is frequently accessed, transferring, over the network, the first data portion and the second data portion to a third endpoint device. in some embodiments, the first endpoint device is in operative communication with the network via a wireless connection, wherein the second endpoint device is in operative communication with the network via a wired connection, and wherein each of the first endpoint device and second point device is a user computing device. the features, functions, and advantages that have been discussed may be achieved independently in various embodiments of the present invention or may be combined with yet other embodiments, further details of which can be seen with reference to the following description and drawings. brief description of the drawings having thus described embodiments of the invention in general terms, reference will now be made to the accompanying drawings, wherein: fig. 1 is a block diagram illustrating an operating environment for the information security threat assessment system, in accordance with one embodiment of the present invention; fig. 2 is a block diagram illustrating the data management system, the data packing system, the first endpoint device, the second endpoint device, and the entity computing system in more detail, in accordance with one embodiment of the present invention; and fig. 3 is a process flow illustrating the transfer of a selected data to the cloud data repository, in accordance with one embodiment of the present invention. detailed description of embodiments of the invention embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all, embodiments of the invention are shown. indeed, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. like numbers refer to elements throughout. where possible, any terms expressed in the singular form herein are meant to also include the plural form and vice versa, unless explicitly stated otherwise. also, as used herein, the term “a” and/or “an” shall mean “one or more,” even though the phrase “one or more” is also used herein. “entity” as used herein may refer to an individual or an organization that owns and/or operates a system of networked computing devices and/or systems on which the cloud storage system described herein is implemented. the entity may be a business organization, a non-profit organization, a government organization, and the like. “user” as used herein may refer to an individual who may log onto the system to view and/or manage the cloud storage system. in other embodiments, the user may be an individual who has ownership or possession of an endpoint device on the network which is used to host a portion of the distributed cloud data repository. typically, the user is authorized by the entity to access the system. accordingly, in some embodiments, the user may be an employee of the entity such as an administrator. “computing system” or “computing device” as used herein may refer to a networked computing device within the entity system. the computing system may include a processor, a non-transitory storage medium, a communications device, and a display. the computing system may support user logins and inputs from any combination of similar or disparate devices. accordingly, the computing system may be a portable electronic device such as a smartphone, tablet, single board computer, smart device, or laptop, or the computing system may be a stationary unit such as a personal desktop computer or networked terminal within an entity's premises. in some embodiments, the computing system may be a local or remote server which is configured to send and/or receive inputs from other computing systems on the network. “endpoint device” as used herein may refer to a computing system within the entity's network which hosts a part of the distributed cloud data repository. each endpoint device typically comprises a storage medium for which at least a portion of the storage space is unused. the unused storage space within each endpoint device is ultimately allocated to store the distributed cloud data. typically, the endpoint device is a user device which is connected to the entity's network. accordingly, endpoint devices are typically desktop computers, laptops, smart phones, tablet computers, and the like. in other embodiments, the endpoint device may be a server with unused storage space. while the endpoint devices are typically devices possessed and/or operated by users within the entity (e.g. employees of the entity), the endpoint device may in some embodiments be user devices or servers located outside of the entity which are able to connect to the entity's network (e.g. through a wan/internet). “cloud,” “cloud storage,” “cloud data storage,” or “cloud data repository” as used herein may refer to a distributed data repository that is shared and accessible to multiple users and systems within a network. the cloud storage may exist as a single logical space which is distributed amongst the various endpoint devices which comprise the cloud storage as a whole. “data,” “data file,” or “cloud data” as used herein may refer to the set of data or particular data file that is to be stored on the cloud data repository. in some embodiments, a user may upload the data to the cloud directly. in other embodiments, certain types of data will automatically be loaded onto the cloud data repository. it should be understood that while portions of the specification may refer to a “data file,” such portions may also be understood to refer to “data” or “sets of data.” “data portion” as used herein may refer to a subset of a set of data or data file. the system may divide data into data portions for storage on various endpoint devices. the endpoint devices may then be multiplexed to produce a data stream of the data files to various user devices within the entity's network. typically, the data portion is a nibble. embodiments of the present invention provide a system, computer program product, and method for generating secured cloud data storage space in a distributed manner across a plurality of disparate devices within a networked system. in particular, the system allocates unused data storage space on a number of endpoint devices on the network to create a cloud data repository. in this way, this cloud data repository allows an entity to address its increasing data storage needs in an efficient way without the need to add additional hardware devices (e.g. computing devices, storage devices, routing devices, and the like). the system may comprise a centralized data management system which indexes data and/or metadata which correlates the files to be stored on the distributed cloud data storage with the particular endpoints on which the files are to be stored. for instance, the file reference id may be correlated to one or more endpoint device id's. the data management system may further track the attributes of the endpoint devices, such as the type of hardware (e.g. the networking cards, the type of storage device used, the processing capabilities), the owner of the device, the degree of latency between the endpoint device and various computing systems within the entity's network, the percentage of time that the device is available on the network, and the like. such data and/or metadata may be compiled in an index generated by the centralized data management system. in this way, the data management system is able to calculate the endpoint device's ability to serve the stored data in an expedient and reliable manner. the data management system may further be configured to flag the indexed files according to the importance or requirements of the files to be stored on the cloud data storage. using this information, the data management system may decide on exactly which endpoint devices certain data should be stored and/or the level of redundancy required for particular data. for example, for more frequently utilized data, it is preferable to store such data on a device with low latency. accordingly, the data management system may determine that such data flagged as having a “low latency” requirement should be stored on a computing device connected to the network via a wired connection with storage space allocated on a solid state drive. as such, the system may establish a latency threshold for a particular set of data or a data file. the system may then periodically monitor the status of the endpoint devices on which the data is stored to ensure that the latency across the devices does not fall below the latency threshold. in some embodiments, the latency across the devices may be calculated as an average. if the average latency across the devices falls above the latency threshold, the system may determine that the data should be transferred to a different and/or additional endpoint device which has the processing power and/or networking bandwidth to allow for low latency retrieval of the data. in addition, the data management system may also address the low latency requirement by increasing the level of redundancy of the data. in such embodiments, the system may replicate the data and store the data on multiple devices. in this way, when the data is recalled from multiple devices, the available bandwidth for retrieving the data is increased, thereby leading to lower latencies. in some embodiments, the indexed files may be flagged to prioritize file integrity. in such embodiments, the system will automatically generate more copies of said data to ensure the accuracy of the flagged data. in some embodiments, if the data does not have a low latency requirement (e.g. the data is archived, infrequently accessed data), the data management system may determine that such data may be stored on a mobile device connected to the network via a wireless connection. furthermore, depending on the uptime of each of the computing devices on the network and the probability of the device being unavailable during a particular time period, the data management system may determine that a number of copies of the data must be stored across a number of different devices to ensure that the data will be available on a consistent basis. for example, the system may further establish a required uptime threshold based on the attributes of the data file. the required uptime threshold may be based on an average percentage of time that the data is available for retrieval (e.g. average 90% uptime), and/or on uptime during a specific time period (e.g. 100% uptime between 9 am and 5 pm). the system may periodically query the endpoint devices to ensure that the data is available for retrieval and constantly monitor the uptime of the endpoint devices in relation to the required uptime threshold. in some embodiments, the uptime of the endpoint devices may fall below the required uptime threshold if one or more endpoint devices are determined by the system to be unavailable. for example, the system may determine that an endpoint device is unavailable based on the endpoint device being unreachable over the network (e.g. the endpoint device is disconnected from the network, shut down, inoperable, etc.). in other embodiments, the system may determine that an endpoint device is unavailable based on the endpoint device experiencing a high degree of latency (e.g. the endpoint device is online/reachable, but has insufficient computing resources to reliably transfer the data file). the data management system may further comprise a machine learning component which stores historical data on the data stored in the cloud data repository, as well as the devices on which the data was stored at various points in time. the data management system may further collect historical data on data uptime, user load, transfer speeds, and the like. using this historical data, the data management system may dynamically adjust the level of redundancy of the data to maximize efficiency. for instance, if the data uptime falls below a certain threshold at a given level of redundancy, the data management system may increase the number of copies created for a given set of data. likewise, if user load (i.e. the frequency with which the data is accessed and/or retrieved from the cloud data repository) associated with a certain set of data falls below a threshold, the data management system may automatically delete a copy of the data on one or more endpoint devices as needed to save computing resources. in some embodiments, the data stored on the cloud data repository may be subject to a minimum level of redundancy to ensure availability of the data even in the event of a data loss incident (e.g. the hard drive becomes corrupt, the user loses the endpoint device, etc.). in some embodiments, the data management system may impose restrictions on the types of data that can be stored on specific endpoint devices. for instance, the data management system may place a geographic restriction on certain types of data, which will in turn limit the types of endpoint devices on which such data may be stored. for example, there may be a regulatory or legal requirement that requires certain data to be kept within a certain territory or country. accordingly, the data management system may exclude certain endpoint devices, such as mobile devices, if said devices are known to be carried outside of the territory or country. in other embodiments, the data management system may place restrictions such that certain data may be stored only on devices that are within the physical control of the entity at all times, such as a stationary server or workstation within the entity's premises. such a restriction would exclude devices such as laptops, smartphones, tablet computers, and the like from being used to store data restricted in such a manner. the system may further comprise a data packing system, which encrypts, stores, retrieves, and decrypts the data on the various endpoint devices. in particular, the data packing system may divide the data to be stored on the cloud into individual chunks, or data portions. the data portions may then be encrypted and transmitted to the endpoint devices over the network for storage. by encrypting the data before it is stored on the endpoint device, the data packing system ensures that the encrypted data is inaccessible to all parties except for those specifically authorized by the entity system to access the data. typically, the encrypted data will further be inaccessible to the user having physical possession of the endpoint device, as the user of the endpoint device may not necessarily be authorized by the entity to access the encrypted data. in some embodiments, multiple copies of each data portion may be generated by the data packing system and subsequently sent to multiple different endpoint devices to achieve the desired level of redundancy to ensure consistent uptime of the data stored on each endpoint device. in some embodiments, the data packing system may be configured to automatically delete (e.g. remote wipe) the data portions stored on a particular endpoint device upon detecting that the endpoint device has been compromised. for instance, the system may detect that the endpoint device has traveled outside of the authorized geographic area, or that the endpoint device has been stolen or cracked. in some embodiments, the remote wipe function may be accomplished via a data management application stored on the endpoint device which communicates with the system and/or automatically wipes the data portions stored on the device upon detecting that the device has been compromised. in other embodiments, the data portions themselves may contain executable code to execute the remote wipe function. in yet other embodiments, the data management application may, upon detecting that the endpoint device has been offline or otherwise unavailable for a predetermined period of time, automatically wipe the data portions stored on the device, thereby ensuring the security of the data stored on devices taken outside of the reach of the entity's network. creating a distributed cloud data storage system in this way addresses a number of technology-centric challenges compared to current technology, specifically with respect to utilizing endpoint devices for storage. in particular, endpoint devices typically vary dramatically in their processing capabilities, network latencies, mobility, uptimes and/or availability, and the like. the invention disclosed herein allows an entity to dynamically adjust the manner in which data is stored on endpoint devices to allow the system to account for differences in endpoint device uptime and network latency. this greatly improves both the reliability and performance of the distributed cloud data storage system. furthermore, the machine learning component of the system allows the entity to find the optimal configuration for maintaining the cloud data storage system, which in turn helps prevent the waste of computing resources associated with generating and/or maintaining extraneous copies of cloud data. the computing resources saved by the system may include processing power, memory space, storage space, cache space, electric power, networking bandwidth, and the like. fig. 1 is a block diagram illustrating an operating environment for the information security threat assessment system, in accordance with one embodiment of the present invention. the operating environment may include a data management system 110 in operative communication with a data packing system 120 , an entity computing system 150 , and a plurality of endpoint devices 130 , 140 over a network 180 . the network 180 may also be a global area network (gan), such as the internet, a wide area network (wan), a local area network (lan), or any other type of network or combination of networks. the network 180 may provide for wireline, wireless, or a combination wireline and wireless communication between devices on the network 180 . it should be understood by those having ordinary skill in the art that although the data management system 110 , the data packing system 120 , the entity computing system 150 , the first endpoint device 130 , and the second endpoint device 140 are depicted as single units, each of the depicted computing systems may represent multiple computing systems. in some embodiments, a given computing system as depicted in fig. 1 may represent multiple systems configured to operate in a distributed fashion. for instance, the data management system 110 may represent a plurality of computing systems which exists within the entity's networks. in other embodiments, the functions of multiple computing systems may be accomplished by a single system. for instance, the functions of the data management system 110 and the data packing system 120 may, in some embodiments, be executed on a single computing system according to the entity's need to efficiently distribute computing workloads. typically, the data management system 110 is a computing system within the entity's premises, such as a server, networked terminal, workstation, and the like. the data management system 110 may be configured to receive a signal from an entity computing system 150 that a user wishes to store data (e.g. one or more data files) on a cloud data repository. to this end, the data management system 110 stores the executable code needed to determine the particular endpoint devices on which to store the data. the data management system 110 may further comprise a cloud data index which contains information about the endpoint devices as well as the cloud data stored on the endpoint devices. typically, each data file or other set of data stored on the cloud data repository will be assigned an identifier (e.g. a unique file reference id) within the index, and each endpoint device will be assigned a device identifier (id) within the index. each data identifier may be associated with one or more device id's, depending on the suitable level of redundancy for the file. in some embodiments, this may depend on the nature of the data, such as the level of confidentiality, the degree of importance to the entity's operations, restrictions on the usage of the data, and the like. typically, these file attributes will be stored along with the data identifier to be used by the data management system 110 to calculate the level of redundancy for each file and/or the specific endpoint devices to be used to store the data. the index may further store additional information along with each device id, where the additional information may be a set of attributes of the endpoint device associated with the device id. the attributes may include the identity of the owner of the endpoint device, the level of latency of communications between the endpoint device and a central entity server, the amount of networking bandwidth and/or computing power available to the endpoint device, the type of device (e.g. workstation, laptop, smartphone, tablet, etc.), the geographic location, device uptime (e.g. the percentage of time the endpoint device is accessible on the entity's network), and the like. based on the attributes of the data to be stored on the cloud and the attributes of the various endpoint devices on the network, the system may determine that a set of endpoint devices, in the aggregate, have enough processing power and/or bandwidth capability to host the data. the system may subsequently match the data, along with the associated data identifiers, to the set of endpoint devices, along with their associated device id's. for example, certain data uploaded to the system may be subject to an uptime requirement, such as when the entity requires a file or set of files to be accessible at all times. the system may then determine that a number of endpoint devices are available to store the data. the system may take into account the average uptime (e.g. a percentage) of the available endpoint devices as well as the periods of time in which the device is online, then replicate the data as many times as desired and send copies of the data to as many endpoint devices as desired to ensure that the data is consistently available 24 hours a day. once the system has determined which endpoint devices will store the data, the data management system 110 may be configured to send the data file to the data packing system 120 to encrypt and transmit the data in data portions to the endpoint devices. in some embodiments, the system may set a required uptime threshold which takes into account the uptime percentages and online periods of the aggregated endpoint devices. in the event that the average uptime of the endpoint devices falls below a certain threshold (e.g. one or more endpoint devices are offline, inoperable, suffering connectivity issues, and the like), the system may create an additional copy of the data to be sent to an alternative and/or additional endpoint device, thus ensuring data availability even during varying conditions. in some embodiments, the data to be uploaded to the system may be subject to a latency requirement, such as when the entity requires the data to be capable of being retrieved in a timely manner. the system may, in some embodiments, set a required latency threshold, which may be measured as the time it takes to transfer a data file of a predetermined size. in such embodiments, the system may assess the computing capabilities of the various endpoint devices in the system, such as by conducting a data transfer test. in this way, the system is able to determine the capabilities of each endpoint device to transfer data efficiently. by taking into account the processing capabilities of the endpoint devices, the system is able to create the number of replications of the data desired to ensure expedient retrieval of the data. in some embodiments, the system may determine that the data may be stored on computing systems which have high processing power and bandwidth. in other embodiments, the system may determine that the data may be stored on a greater number of weaker computing systems such that in the aggregate, the weaker computing systems may still provide the bandwidth to satisfy the required latency threshold. the data management system 110 may further comprise a machine learning component which tracks historical data on the file reference id's and device id's used to store data in the past. the historical data will further include the attributes of the file to be stored, the attributes of the endpoint devices, and the level of redundancy for each file stored on the cloud data repository. the machine learning component may track usage data for the files stored on the cloud and correlate the usage with file uptime and latency in retrieving the file. based on this historical data, the machine learning component may dynamically adjust the level of redundancy and/or the types of endpoint devices used to store similar data files in the future. for example, if a particular type of file (e.g. an executable file to deploy software) consistently sees a high utilization rate compared to the availability of the data file, the machine learning component may increase the level of redundancy and/or store the file on endpoint devices with faster processing speeds and/or network connections to increase file storage/retrieval performance. on the other hand, if a particular type of file sees low utilization compared to existing redundancy and latency, the system may reduce the level of redundancy and/or store the data files on devices with lower uptimes, in order to save computing resources. in some embodiments, the cloud data index may be stored in blockchain form. in such embodiments, the data identifiers, device id's, file attributes, and device attributes are stored in a distributed fashion amongst a plurality of data management systems 110 . in some embodiments, the plurality of data management systems 110 each comprise a complete copy of the blockchain, thus protecting the index from data degradation while simultaneously increasing its security by preventing the introduction of false index data. each block on the blockchain may comprise information related to one file reference id; that is, the block may contain data on the devices on which a data file is stored, the attributes of the file to be stored, and the attributes of the devices on which the file is stored. each block may further comprise a time stamp and contain a reference to the previous block in the chain. in some embodiments, the reference may be in the header of the block. each block may be added to the blockchain via a consensus mechanism amongst the plurality of data management systems 110 . in this way, the data records in the index are comprised of only authorized blocks. a generalized description of the blockchain may be found in u.s. patent application ser. no. 15/291,799, the contents of which are hereby incorporated by reference in its entirety. like the data management system 110 , the data packing system 120 is typically a computing system within the entity's premises. the data packing system 120 may be configured to read the index within the data management system 110 and accept data files (identified by file reference id) from the entity computing system 150 and store the data files in an encrypted form on the endpoint devices (identified by device id). typically, the data packing system 120 first divides the data files provided by the entity computing system 150 into data portions. this is done not only for the purposes of efficiency (i.e. smaller files are easier to transmit and receive), but this also ensures that the users of the endpoint devices are unable to access the content stored within the endpoint device. typically, the data packing system 120 creates duplicates of the data portions to be stored on different endpoint devices according to the level of redundancy associated with each data identifier. once the data portions have been encrypted and/or duplicated, the data packing system 120 may establish a secure communications channel with each endpoint device and transfer the data portions to the endpoint devices for storage. in some embodiments, the data packing system 120 may further be configured to decrypt the data portions stored on the endpoint devices, such as when the data packing system 120 receives a request from the entity computing system 150 or other computing system to retrieve the data files associated with one or more data identifiers. upon receiving such a request, the data packing system 120 may retrieve the encrypted data portions from each endpoint device corresponding to the data identifiers requested, decrypt the data portions, recombine the data portions to form the completed data files, then send the completed data files to the entity computing system 150 over a secure communications channel. the entity computing system 150 is typically a device that may be operated by a user, where the device may be a mobile device such as a smartphone, tablet, or laptop, a personal computing device such as a desktop computer, smart device, single board computer, or a stationary device such as a computer system terminal, workstation, personal computer, and the like. in some embodiments, the user is an employee of the entity who may wish to store and recall data on the cloud data repository in the enterprise context. in other embodiments, the user may be a client of the entity who wishes to store and recall personal data on the cloud data repository. in an exemplary embodiment, the user may wish to store a user data file (e.g. a document) on the cloud data repository. the user may securely log onto the system by providing authentication credentials associated with the user. the authentication credentials may include a username and password, secure token, cryptographic key, and the like. once authenticated, the user may upload the user data file to the data management system 110 . the data management system 110 may index the user data file and assign a file reference id to the data file. the user may further be able to specify certain attributes of the user data file, such as territorial restrictions, level of confidentiality, purpose of use (e.g. long-term backup vs. high performance applications in which rapid retrieval is desirable), and the like. based on the attributes of the user data file, the data management system 110 may assign the file reference id to one or more endpoint devices, which are identified by device id. in an exemplary embodiment, the data management system may assign the user data file to the first endpoint device 130 and the second endpoint device 140 . once the endpoint devices have been identified, the data management system 110 may send the user data file to the data packing system 120 for encryption, chunking, and storage on the specified endpoint devices. continuing the example, the data packing system 120 may divide the user data file into data portions and store the data portions on the first endpoint device 130 and/or the second endpoint device 140 . in some embodiments, each data portion may be replicated and stored on both the first endpoint device 130 and the second endpoint device 140 . in some embodiments, data file attributes and/or device attributes may be stored as metadata with each data portion. like the entity computing system 150 , the first endpoint device 130 and the second endpoint device 140 are typically computing systems that may be operated by a user. in some embodiments, the user may be an employee of the entity, where the endpoint devices are enterprise devices. in other embodiments, the user may be a client of the entity, where the endpoint devices are personal devices. in yet other embodiments, the user may be a third party individual existing outside of the entity's systems who wishes to contract with the entity to allow the entity to store cloud data on the individual's device. typically, all data uploaded to the cloud is encrypted from end to end. thus, the security of the cloud data can be ensured even if the endpoint device is not formally a part of the entity's systems (e.g. the user is not an employee of the entity). in other embodiments, the first endpoint device 130 and/or the second endpoint device 140 may be a server having unused storage space, which may not typically be configured to interface with a user. in some embodiments, the server may exist within the entity's network and/or premises. in other embodiments, the server may be a third party server with unused storage space which remotely connects to the entity's network, e.g. over the internet. both the first endpoint device 130 and the second endpoint device 140 each comprise a storage device for which at least a portion of the storage is unused. the unused portion of the storage for each endpoint device may be allocated by the system to be used to store the cloud data. the system may also dynamically adjust the amount of space allocated on the endpoint device. in an exemplary embodiment, when the storage device has a relatively high amount of free storage space (e.g. 80%), the system may allocate a comparatively larger amount of space to be used to store cloud data (e.g. 20% of the free space). however, as the free storage space on the endpoint device decreases below a certain threshold (e.g. 20%), the system may reduce the allocation of cloud data storage space (e.g. 5% of the free space) in order to ensure that the lack of free space does not hinder the performance of the endpoint device. typically, the allocated cloud data storage space is not accessible to the user of the endpoint device. in some embodiments, the cloud data storage space may be allocated using a cloud application stored on each endpoint device. in other embodiments, the data portions may contain self-executing code which automatically allocates the space needed to store the data portion. in some embodiments, the endpoint devices may be configured to communicate with each other and/or transfer encrypted data portions to and from one another. for instance, if the system decides that the level of redundancy for a certain data file should be increased, the first endpoint device 130 may generate a copy of the encrypted data portions stored therein and send the data portions to the second endpoint device 140 . in this way, excessive computing load on the data packing system 120 may be avoided. the system may take the endpoint device's attributes into account when deciding which data files should be stored on a specific endpoint device. in an exemplary embodiment, the first endpoint device 130 may be a mobile device such as a smartphone which connects to the network primarily through wireless technologies, such as cellular networks or wifi. accordingly, the first endpoint device 130 may experience periods of time in which the first endpoint device 130 is unable to connect to the entity's network (i.e. reducing uptime). furthermore, the mobile nature of the first endpoint device 130 may indicate that the first endpoint device 130 has a comparatively lower processing capability or networking bandwidth. accordingly, the system may determine that the cloud data stored on the first endpoint device 130 must be replicated and stored on other endpoint devices for backup purposes. furthermore, the system may determine that only long-term backup data should be stored on the first endpoint device 130 , rather than frequently used data that may need to be recalled at a high level of speed. on the other hand, the second endpoint device 130 may be a dedicated stationary server within the entity's premises connected via a wired high speed connection (e.g. ethernet). in such an embodiment, the system may determine that the second endpoint device 130 is suitable to store cloud data that is frequently accessed by other users within the entity's systems. in some embodiments, the endpoint devices may comprise an automatic wipe function which deletes the cloud data on the endpoint device within the allocated storage space. in some embodiments, the automatic wipe function is executed by the system or by an application stored on the endpoint device. in other embodiments, the automatic wipe function is embedded into logic code portions of the data portions stored on the endpoint devices. the automatic wipe function may be triggered, for instance, upon the system detecting that the endpoint device has been compromised (e.g. stolen, cracked, or breached). such functionality may be critical in situations in which the cloud data comprises sensitive data, such as confidential information. the automatic wipe function may further be used upon detecting that the cloud data stored on a particular endpoint device is subject to a territorial restriction and the endpoint device is located outside of the territorial area covered by the restriction. the system may detect the endpoint device's location via various methods, such as gps, ip address, cellular tower triangulation, and the like. upon detecting that the territorial restriction has been violated by the endpoint device, the automatic wipe function may be triggered. in some embodiments, the automatic wipe function may be selective in which data portions are automatically deleted. for example, in some embodiments, an endpoint device may be used to store data that is subject to territorial restrictions as well as data that is not subject to any such restrictions. in such scenarios, the automatic wipe function may be configured to selectively delete only the data that is subject to the territorial restriction upon detecting that the condition that triggers the automatic wipe function. in yet other embodiments, the automatic wipe function may be executed by the endpoint device after a predefined period of no communication with the system. for instance, an endpoint device may have been determined to have been offline for a predefined period of 30 days. in such a case, the application within the endpoint device may be configured to automatically wipe the cloud data within the endpoint device. by executing the automatic wipe in this way, the security of the cloud data on the endpoint device may be preserved even in periods in which the system is unable to reach or control the endpoint device. fig. 2 is a block diagram illustrating the data management system 110 , the data packing system 120 , the first endpoint device 130 , the second endpoint device 140 , and the entity computing system 150 in more detail, in accordance with one embodiment of the present invention. the data management system 110 typically contains a processor 221 communicably coupled to such devices as a communication interface 211 and a memory 231 . the processor 221 , and other processors described herein, typically includes circuitry for implementing communication and/or logic functions of the data management system 110 . for example, the processor 221 may include a digital signal processor device, a microprocessor device, and various analog to digital converters, digital to analog converters, and/or other support circuits. the data management system 110 may use the communication interface 211 to communicate with other devices over the network 180 . the communication interface 211 as used herein may include an ethernet interface, an antenna coupled to a transceiver configured to operate on a cellular data, gps, or wifi signal, and/or a near field communication (“nfc”) interface. the data management system 110 may include a memory 231 operatively coupled to the processor 221 . as used herein, memory includes any computer readable medium (as defined herein below) configured to store data, code, or other information. the memory may include volatile memory, such as volatile random access memory (ram) including a cache area for the temporary storage of data. the memory may also include non-volatile memory, which can be embedded and/or may be removable. the non-volatile memory can additionally or alternatively include an electrically erasable programmable read-only memory (eeprom), flash memory or the like. the memory 231 within the data management system 110 may comprise the cloud data index 241 , which may comprise the data identifiers and device id's, as well as the file attributes and device attributes. typically, the cloud data index 241 contains data on files that are currently being stored on the cloud data repository. in some embodiments, a data identifier index is maintained separately from the device id index. in other embodiments, both indices are combined into a single index. the data management system 110 may determine the endpoint devices on which to store user cloud data based on the data within the cloud data index 241 , such as the type/characteristics of the user cloud data and the type/characteristics of the endpoint devices on which the user cloud data is to be stored. the memory 231 may further comprise a historical database 251 , which contains data on files that were once stored on the cloud data repository, as well as other information such as file usage data, level of redundancy for each file, historical device uptime and performance (e.g. computing performance and/or network bandwidth), and the like. from the data within the historical database 251 , the data management system 110 may use machine learning to improve the system's ability to determine the optimal level of redundancy for each data file and/or to select the optimal endpoint devices to store each data file. the data packing system 120 may comprise a communication interface 212 , a processor 222 , and a memory 232 comprising a data packing engine 242 stored thereon. the data packing engine 242 may be responsible for importing the data file (e.g. the user cloud data) specified according to the data identifier referenced in the cloud data index 241 to be stored on one or more endpoint devices as specified by the device id's. in some embodiments, the data packing engine 242 may be configured to divide the user cloud data into data portions for efficient storage on various endpoint devices. the data packing engine 242 may further be configured to encrypt each data portion such that the data portion may not be accessed by the endpoint devices. the data packing engine 242 may further transfer the encrypted data portions to the endpoint devices for storage. in some embodiments, the data packing engine 242 may further be configured to decrypt the encrypted data portions stored on various endpoint devices and combine them to form the original data file, which can then be subsequently accessed by other users within the entity's networks. the first endpoint device 130 may comprise a communication interface 213 , a processor 223 , and a memory 233 . the memory 233 may comprise a first allocated storage 243 , which represents the storage space allocated by the system to serve as the cloud data repository. the first allocated storage 243 may be utilized by the system to store encrypted data portions received from the data packing system 120 . the first endpoint device 130 is typically owned and/operated by a first endpoint user. while the first endpoint user may retain physical possession of the first endpoint device 130 itself, the first endpoint user typically does not have access to the data within the first allocated storage 243 . similar to the first endpoint device 130 , the second endpoint device 140 is typically owned and/or operated by a second endpoint user and may comprise a communication interface 214 , a processor 224 , and a memory 234 . the memory 234 may comprise a second allocated storage 244 , which also represents the storage space allocated by the system to serve as the cloud data repository. accordingly, the second allocated storage 244 may also comprise encrypted data portions received from the data packing system 120 . in some embodiments, the memory 233 of the first endpoint device 130 and the memory 234 of the second endpoint device may each comprise an automatic wipe function, which is configured to automatically delete the data within the first allocated storage 243 or the second allocated storage 244 upon detecting a wipe condition, such as a security or data breach, or the triggering of a territorial restriction. the entity computing system 150 is typically owned and/or operated by a user and includes a processor 225 operatively coupled to a communication interface 215 and a memory 235 . the processor 225 may display a user interface 255 to a user, which may comprise the hardware and software implements to accept input from and provide output to the user. accordingly, the user interface 255 may comprise hardware such as a display, audio output devices, projectors, and the like, or input devices such as keyboards, mice, motion sensors, cameras, biometric sensors, and the like. the user interface 255 may further comprise software such as a graphical or command-line interface through which the user may provide inputs and/or receive outputs from the entity computing system 150 . it should be understood that the display on which the user interface 255 is presented may include an integrated display (e.g. a tablet or smartphone screen) within the entity computing system 150 , or an external display device (e.g. a computer monitor or television). typically, the memory 235 contains user cloud data 245 , which represents the data files that the user wishes to store on the cloud data repository. the user may select the user cloud data 245 to be uploaded to the data management system 110 and/or the data packing system 120 for storage on the cloud data repository. the user may further access the decrypted cloud data on the cloud data repository via the entity computing system 150 . in some embodiments, the user interface 255 may allow the user to specify certain attributes of the user cloud data 245 . for instance, the user may mark the user cloud data 245 as “confidential” or impose territorial restrictions (e.g. the devices on which the data is hosted must remain in the united states). the user may further restrict the number or types of users who may access the user cloud data 245 . the user may further specify availability requirements (e.g. the data must be available during certain time periods), which the system may use to determine the level of redundancy of the user cloud data 245 when storing the data on the various endpoint devices. in this way, the system may ensure both the availability as well as the integrity of the data stored within the cloud data repository. fig. 3 is a process flow illustrating the transfer of a selected data file to the cloud data repository, in accordance with one embodiment of the present invention. the process begins at block 300 , where the system receives a request to store data on a cloud data repository. in some embodiments, the user logs onto the system through the entity computing system to upload the data file to the entity's systems. in some embodiments, the user may upload the data file to the system through an application installed on the entity computing system. in other embodiments, the data file may be uploaded via a website, ftp server, authenticated fileshare, and the like. in other embodiments, a different computing system within the entity's system may request that the data is stored on the cloud. in yet other embodiments, certain types of data (e.g. daily log files) may be stored on the cloud automatically. in some embodiments, the data file may be related to the entity's operations and is intended to be accessed by other users within the entity's network. the user may further be able to set certain file attributes or preferences with respect to the storage and/or access of the file. for instance, the user may be able to mark the data file as restricted in various ways, such as access (e.g. only a certain class of users, such as administrators, may access the data file on the cloud) or territory (e.g. the device may be hosted only on a device that remains within a particular territory). in other embodiments, the rules may be predefined by the system. the file attributes may in some embodiments be stored within the data reference index hosted within the cloud data index on the data management system. in other embodiments, the file attributes may be appended to the data file as metadata. the process continues to block 301 , where the system assigns a data identifier to the data within a data reference index. typically, the data reference index is part of the cloud data index hosted on the data management system. in some embodiments, the data management system may temporarily host the data file in order to extract the metadata and/or transfer the data file to the data packing system. in other embodiments, the data file may be hosted elsewhere while the data management system conducts its functions. the data identifier is typically unique to each data file uploaded to the system. in some embodiments, each data file receives a unique data identifier even if the data file is not currently hosted on the cloud data repository. in this way, even historically uploaded data files may be referenced using a unique data identifier, which may aid the machine learning process. the process continues to block 302 , where the system selects a first endpoint device and a second endpoint device for storing the data, wherein the first endpoint device is assigned a first device id within a device index and the second endpoint device is assigned a second device id within the device index. typically, the device index is a part of the cloud data index within the data management system. each endpoint device is assigned a unique device id to identify which data files may be stored therein. the data management system may decide which endpoint devices should be used to store the data file at least partially on the file attributes and/or preferences provided by the user as well as the attributes of the endpoint devices. for instance, the system may exclude mobile devices based on the data file being flagged as confidential, such that only stationary endpoint devices located on the entity's premises may be selected to store the data file. the data management system may further account for the level of redundancy and/or device uptime needed to ensure data availability and integrity, which may in turn depend on the type of file being stored. for instance, data files serving as infrequently accessed long-term backups may require comparatively lower device uptime and/or redundancy compared to data files that are accessed frequently during the entity's operations. the data management system may also utilize machine learning to determine the optimal configuration of redundancy and/or endpoint device selection for each data file uploaded to the cloud data repository. in an exemplary embodiment, the system may examine the device attributes for both the first endpoint device and the second endpoint device. the device attributes examined may include processing power, networking bandwidth capability, storage device speed, and the like. the system may then determine that the first endpoint device and the second endpoint device, at least in the aggregate, have sufficient attributes to host the data. the sufficiency of the device attributes to host the data may depend at least in part on the file attributes. for instance, if the data is frequently used data that may need to be accessed regularly and expediently, the system may impose greater device attribute requirements on the endpoint devices on which the data may be stored. accordingly, the system may further track usage information of the data, such as how often the data is accessed or predicted to be accessed. in some embodiments, the system may examine device attributes, data attributes, and usage information to make the initial selection of endpoint devices to host the data. in an exemplary embodiment, the data to be uploaded may be subject to a territorial requirement and a 100% uptime requirement between the hours of 9 am and 5 pm and is expected to be distributed to 100 users. in such embodiments, the system may take into account the data attributes (e.g. the various requirements and predicted usage information), and match the data to devices with device attributes that match the data attributes (e.g. devices that are online between 9 am and 5 pm and are currently located within the territory). in some embodiments, the system may further examine device attributes, data attributes, and usage information to make changes to the endpoint devices that currently host the data. for instance, the system may determine that the data is being accessed at a higher rate than expected. accordingly, the system may dynamically generate copies of the data and transfer the data to one or more additional endpoint devices to increase the uptime and availability of the data. on the other hand, the system may also determine that the data is being accessed at a lower rate than expected. in such embodiments, the system may dynamically wipe the data on one or more endpoint devices in order to restore cloud storage space. the process continues to block 303 , where the system associates the data identifier with the first device id and the second device id. the system may create an association between the data identifier and a plurality of device id's and subsequently store the association as data. in some embodiments, the data may exist within the cloud data index. in other embodiments, this association may exist as metadata within the data portions stored on the endpoint devices. in some embodiments, the data reference index may contain pointers to device id's within the device index. the process continues to block 304 , where the system divides the data into a plurality of data portions, the plurality of data portions comprising a first data portion and a second data portion. typically, the number of data portions generated by the system depends on the size of the data file to be uploaded to the cloud. in some embodiments, an endpoint device may be used to store at least a copy of all of the plurality of data portions that make up the data file. in other embodiments, each of the data portions may be sequentially stored across multiple endpoint devices. for instance, the first data portion may be stored on the first endpoint device, the second data portion may be stored on the second endpoint device, a third data portions may be stored on a third endpoint device, a fourth data portions may be stored on the first endpoint device, and so on. in this way, the data may then be multiplexed by the multiple endpoint devices when retrieving the data at a later date, which in turn increases the speed of the data stream. by allowing the system to distribute the data across a number of devices, the system may select the appropriate devices on which to store the data according to its performance requirements. furthermore, the same data portions may be stored on multiple devices. for instance, the first data portion may be stored on both the first endpoint device and the second endpoint device, and so on depending on the redundancy needs of the data file. typically, each data portions is replicated at least once and stored on at least two endpoint devices. in other words, the system may impose a minimum level of redundancy for all data uploaded to the cloud data repository. in this way, the system is able to optimally store data files on the cloud across a number of endpoint devices with disparate capabilities and uptimes. the process continues to block 305 , where the system encrypts the plurality of data portions. this ensures not only that the data portions may not be viewed by external third parties who may intercept the communication to the endpoint devices, but also ensures that the endpoint devices themselves may not access the data within the allocated spaces within the endpoint devices. the process continues to block 306 , where the system transfers, over a network, the first data portion and the second data portion to the first endpoint device. typically, the first data portion and the second data portion are stored within the allocated space within the memory of the first endpoint device. it should be noted that the first data portion is encrypted at this point such that the user of the first endpoint device may not access the first data portion or the second data portion. the process concludes at block 307 , where the system transfers, over the network, the first data portion and the second data portion to the second endpoint device. in an exemplary embodiment, the first endpoint device may be a mobile device that has a limited uptime compared to the second endpoint device, which may be a stationary computing device with a near constant uptime. based on the disparity in uptime, the system may determine that the data file should be replicated on a plurality of devices in order to increase data redundancy, which in turn ensures data availability in case one or more of the endpoint devices are unavailable (e.g. when the endpoint device is offline, during system failures, etc.). in some embodiments, the system may be configured to retrieve data from the cloud data repository. in some embodiments, the system may receive a request to retrieve the data. in other embodiments, certain data is automatically retrieved from the cloud. the system may, based on reading the data reference index, identify the data identifier associated with the data to be retrieved. based on the data identifier, the system may determine device id's associated with the endpoint devices on which the data is stored, which in turn allows the system to correctly identify the endpoint devices which store the data. the system may then retrieve the plurality of data portions from at least one endpoint device for decryption. the system may then regenerate the decrypted data. in some embodiments, the system may subsequently transfer the data to a user. in other embodiments, the system may transfer the data to another computing system within the entity's network. in some embodiments, the system may be configured to create additional copies of the data and upload the data to alternative and/or additional endpoint devices based on changing conditions. for instance, the system may determine that a particular endpoint device hosting a copy of the data is unavailable. in some embodiments, the device may be unavailable due to being offline. in other embodiments, the device may be unavailable due to the endpoint device experiencing high network latency. in such embodiments, the system may detect that data uptime has dropped below a required data uptime threshold due to the unavailability of the device. the system may then generate a copy of the first data portion and the second data portion and transfer them to a third endpoint device. in some embodiments, the data uploaded to the cloud may be subject to a data restriction. for instance, the data restriction may be a requirement that the endpoint device on which the data is stored should remain in a predetermined territory. the system may execute an automatic wipe function based on detecting that an endpoint device has violated the data restriction. in some embodiments, detecting that the endpoint device has violated the data restriction may include continuously monitoring the location of the endpoint device (e.g. by gps), and detecting that the endpoint device is located outside of the predetermined territory. in some embodiments, the system may send an automatic wipe command to the endpoint device over the network. in other embodiments, the system may deploy a data management application on the endpoint device. in some embodiments, the data management application may delete the data from the endpoint device via the automatic wipe function independently of receiving a command from the entity's systems. in some embodiments, the data management application may itself determine that the endpoint device has violated the data restriction (e.g. by determining by gps that the endpoint device is located outside of the predetermined territory). in other embodiments, the data management application may be configured to automatically wipe the data from the endpoint device upon detecting that the endpoint device has not connected to the entity's network for a predetermined period of time. in some embodiments, the system may comprise a machine learning component which allows the system to dynamically adjust the level of redundancy associated with the data using historical data. for instance, the system may determine that the data has not been accessed for a predetermined period of time. based on this data, the system may reduce the level of redundancy (e.g. by wiping the data from one or more endpoint devices) in order to more efficiently allocate cloud space. each communication interface described herein generally includes hardware, and, in some instances, software, that enables the computer system, to transport, send, receive, and/or otherwise communicate information to and/or from the communication interface of one or more other systems on the network. for example, the communication interface of the user input system may include a wireless transceiver, modem, server, electrical connection, and/or other electronic device that operatively connects the user input system to another system. the wireless transceiver may include a radio circuit to enable wireless transmission and reception of information. as will be appreciated by one of ordinary skill in the art, the present invention may be embodied as an apparatus (including, for example, a system, a machine, a device, a computer program product, and/or the like), as a method (including, for example, a business process, a computer-implemented process, and/or the like), or as any combination of the foregoing. accordingly, embodiments of the present invention may take the form of an entirely software embodiment (including firmware, resident software, micro-code, and the like), an entirely hardware embodiment, or an embodiment combining software and hardware aspects that may generally be referred to herein as a “system.” furthermore, embodiments of the present invention may take the form of a computer program product that includes a computer-readable storage medium having computer-executable program code portions stored therein. as the phrase is used herein, a processor may be “configured to” perform a certain function in a variety of ways, including, for example, by having one or more general-purpose circuits perform the function by executing particular computer-executable program code embodied in computer-readable medium, and/or by having one or more application-specific circuits perform the function. it will be understood that any suitable computer-readable medium may be utilized. the computer-readable medium may include, but is not limited to, a non-transitory computer-readable medium, such as a tangible electronic, magnetic, optical, infrared, electromagnetic, and/or semiconductor system, apparatus, and/or device. for example, in some embodiments, the non-transitory computer-readable medium includes a tangible medium such as a portable computer diskette, a hard disk, a random access memory (ram), a read-only memory (rom), an erasable programmable read-only memory (eprom or flash memory), a compact disc read-only memory (cd-rom), and/or some other tangible optical and/or magnetic storage device. in other embodiments of the present invention, however, the computer-readable medium may be transitory, such as a propagation signal including computer-executable program code portions embodied therein. it will also be understood that one or more computer-executable program code portions for carrying out the specialized operations of the present invention may be required on the specialized computer include object-oriented, scripted, and/or unscripted programming languages, such as, for example, java, perl, smalltalk, c++, sas, sql, python, objective c, and/or the like. in some embodiments, the one or more computer-executable program code portions for carrying out operations of embodiments of the present invention are written in conventional procedural programming languages, such as the “c” programming languages and/or similar programming languages. the computer program code may alternatively or additionally be written in one or more multi-paradigm programming languages, such as, for example, f#. embodiments of the present invention are described above with reference to flowcharts and/or block diagrams. it will be understood that steps of the processes described herein may be performed in orders different than those illustrated in the flowcharts. in other words, the processes represented by the blocks of a flowchart may, in some embodiments, be in performed in an order other that the order illustrated, may be combined or divided, or may be performed simultaneously. it will also be understood that the blocks of the block diagrams illustrated, in some embodiments, merely conceptual delineations between systems and one or more of the systems illustrated by a block in the block diagrams may be combined or share hardware and/or software with another one or more of the systems illustrated by a block in the block diagrams. likewise, a device, system, apparatus, and/or the like may be made up of one or more devices, systems, apparatuses, and/or the like. for example, where a processor is illustrated or described herein, the processor may be made up of a plurality of microprocessors or other processing devices which may or may not be coupled to one another. likewise, where a memory is illustrated or described herein, the memory may be made up of a plurality of memory devices which may or may not be coupled to one another. it will also be understood that the one or more computer-executable program code portions may be stored in a transitory or non-transitory computer-readable medium (e.g., a memory, and the like) that can direct a computer and/or other programmable data processing apparatus to function in a particular manner, such that the computer-executable program code portions stored in the computer-readable medium produce an article of manufacture, including instruction mechanisms which implement the steps and/or functions specified in the flowchart(s) and/or block diagram block(s). the one or more computer-executable program code portions may also be loaded onto a computer and/or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer and/or other programmable apparatus. in some embodiments, this produces a computer-implemented process such that the one or more computer-executable program code portions which execute on the computer and/or other programmable apparatus provide operational steps to implement the steps specified in the flowchart(s) and/or the functions specified in the block diagram block(s). alternatively, computer-implemented steps may be combined with operator and/or human-implemented steps in order to carry out an embodiment of the present invention. while certain exemplary embodiments have been described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative of, and not restrictive on, the broad invention, and that this invention not be limited to the specific constructions and arrangements shown and described, since various other changes, combinations, omissions, modifications and substitutions, in addition to those set forth in the above paragraphs, are possible. those skilled in the art will appreciate that various adaptations and modifications of the just described embodiments can be configured without departing from the scope and spirit of the invention. therefore, it is to be understood that, within the scope of the appended claims, the invention may be practiced other than as specifically described herein.
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044-924-619-097-229
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US
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[
"US"
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H04R1/02
| 2012-10-18T00:00:00 |
2012
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[
"H04"
] |
microphone features related to a portable computing device
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a portable computing device includes one or more microphones that function seamlessly with other components within the portable computing device. in one embodiment, a microphone opening is disposed on a side of the personal computing device and configured to be substantially perpendicular to a user. in another embodiment, two microphones can be disposed on an upper region above a keyboard section and can include a third microphone facing toward a rear portion of the portable computing device. in yet another embodiment, a fixture for providing a bonding pressure to microphones is described.
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1 . a microphone assembly for a portable computing device, the assembly, comprising: a first microphone opening disposed on an upper surface of a base portion of the portable computing device; a second microphone opening disposed on a rear facing surface of the base portion of the portable computing device; a first microphone coupled to the first microphone opening configured to receive audio signals; and a second microphone coupled to the second microphone opening configured to receive audio signals. 2 . the assembly of claim 1 , wherein the first and the second microphones are coupled to a flexible cable. 3 . the assembly of claim 1 , wherein the second microphone opening is disposed near rear vents included in the base portion of the portable computing device. 4 . the assembly of claim 3 , wherein at least one of the rear vents adjacent to the second microphone opening is shaped to provide a uniform edge in a region near the second microphone opening. 5 . the assembly of claim 1 , further comprising a third microphone opening disposed on the upper surface of the base portion of the portable computing device. 6 . the assembly of claim 5 , wherein the first microphone opening is separated by a distance d from the third microphone opening wherein the distance d is configured to enhance a frequency response of the first and the third microphones. 7 . a microphone assembly for a portable computing device, the assembly comprising: a first microphone opening disposed on a sideband of a base portion of the portable computing device; a first microphone configured to receive audio signals; a first acoustic cavity comprising a first segment and a second segment configured to couple the first microphone opening to the first microphone, wherein the acoustic cavity is configured to have a particular frequency response. 8 . the assembly of claim 7 , wherein a portion of the first segment of the first acoustic cavity is disposed on the sideband forming the first microphone opening. 9 . the assembly of claim 7 , wherein a portion of the second segment of the first acoustic cavity is coupled to the first microphone. 10 . the assembly of claim 7 , further comprising: a second microphone opening disposed on the sideband a distance d from the first microphone; a second microphone configured to receive audio signals; a second acoustic cavity comprising a third and a fourth segments configured to couple the second microphone opening to the second microphone. 11 . the assembly of claim 10 , wherein the base portion includes an inner surface configured to accept a surface of the first and the second microphones. 12 . the assembly of claim 11 , wherein the base portion further comprises a notch configured to accept a flexible cable. 13 . the assembly of claim 12 , wherein the first and the second microphones are coupled to a flexible cable. 14 . the assembly of claim 10 , further comprising a bi-stable spring configured to hold at least one microphone in place against a surface of the base portion. 15 . the assembly of claim 10 , wherein the first and second segments are substantially similar to the third and fourth segments respectively. 16 . the assembly of claim 10 , wherein the distance d is selected to enhance a frequency response of the first and the second microphones. 17 . a fixture for applying a bonding pressure to a microphone assembly for use in a portable computing device, the fixture comprising: a plunger support configured to align with features included in a top case of a portable computing device; and a plunger configured to be supported by the plunger support and including a first surface configured to contact a first microphone and a second surface configured to receive pressure and transmit the pressure to the first microphone. 18 . the fixture of claim 17 , wherein the plunger is divided into a first portion and a second portion, wherein the first portion includes the first surface and the second surface and a second portion includes a third surface configured to contact a second microphone and a fourth surface configured to receive bonding pressure and transmit the bonding pressure to the second microphone. 19 . the fixture of claim 18 , wherein the first portion and the second portions of the plunger can be actuated separately. 20 . the fixture of claim 17 , wherein a first bonding pressure can be applied to the first microphone and a second bonding pressure different from the first bonding pressure can be applied to a second microphone.
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cross reference to related applications this u.s. patent application claims priority under 35 usc 119(e) to u.s. provisional patent application no. 61/715,799 filed oct. 18, 2012 entitled “microphone features related to a portable computing device” by espiritu et al. which is incorporated by reference in its entirety for all purposes. technical field the present invention relates generally to portable computing devices. more particularly, the present embodiments relate to microphone arrays for portable computing devices. background portable computing devices have grown in popularity and capability. early uses for portable computing devices were often limited to simple computing tasks such as number manipulation and word processing. present applications can include advanced graphical rendering, musical composition, movie and music presentation and more. in order to support the ever expanding list of applications desired by users, portable computing devices are including more sophisticated components into the space defined by the enclosure of the device. while users expect more performance and features from their portable computing devices, users also want a compact unit; that is, users want the enclosure to be as compact as feasible. including a microphone in a portable computing device can be difficult, especially as the device becomes more compact and increased audio quality and capability is desired. as the portable computing device becomes smaller, internal component density increases which can result in a microphone implementation that can yield poor audio performance. therefore, it would be beneficial to provide a portable computing device that can support microphone capabilities within design constraints of the enclosure space. summary the present application describes various embodiments regarding systems and methods for incorporating microphone openings and microphones into a portable computing device. in one embodiment, a microphone assembly for a portable computing device can include a first microphone opening located on an upper portion of a base portion of the portable computing device, a second microphone opening disposed on a rear facing surface of the base portion, a first microphone coupled to the first microphone opening and a second microphone coupled to the second microphone opening wherein the first and the second microphones are configured to receive audio signals. in another embodiment, a microphone assembly for a portable computing device can include a first microphone opening disposed on a sideband of a base portion of the portable computing device, a first microphone configured to receive audio signals and a first acoustic cavity, the acoustic cavity can include a first segment and a second segment and is configured to couple the first microphone to the first microphone opening, where the first acoustic cavity is configured to have a frequency response. a fixture for applying a bonding pressure to a microphone assembly can include a plunger support configured to align with features included in a top case of a portable computing device and a plunger configured to be supported by the plunger support and including a first surface configured to contact a first microphone and a second surface configured to receive pressure and transmit the pressure to the first microphone. other apparatuses, methods, features and advantages of the invention will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. it is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the invention, and be protected by the accompanying claims. brief description of the drawings the included drawings are for illustrative purposes and serve only to provide examples of possible structures and arrangements for the disclosed inventive apparatuses and methods for providing portable computing devices. these drawings in no way limit any changes in form and detail that may be made to the invention by one skilled in the art without departing from the spirit and scope of the invention. the embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings, wherein like reference numerals designate like structural elements, and in which: fig. 1 shows a front facing perspective view of an embodiment of the portable computing device in the form of portable computing device in an open (lid) state. fig. 2 shows portable computing device in a closed (lid) configuration that shows rear cover and logo. fig. 3 shows another embodiment of the portable computing device in the form of portable computing device also in the open state. fig. 4 shows microphone region of top case. figs. 5a-5b are cross section views of microphone openings from fig. 4 . fig. 6 shows microphone region of top case. figs. 7a and 7b are cross section views of microphone openings shown in fig. 6 . fig. 8 is a cross section view of another embodiment of a microphone region on top case. fig. 9 is a view of another embodiment of a microphone region. fig. 10 shows another view of the microphone region shown in fig. 9 including a microphone assembly. fig. 11 shows an interior view of the top case near the microphone region of fig. 9 . fig. 12 shows an interior view of top case near the microphone region of fig. 9 with a microphone assembly. fig. 13 shows an internal view of the top case in the region of a first microphone disposed on an upper region of the top case. fig. 14 shows a reverse view of a mounting substrate. fig. 15 shows an internal view of a clutch assembly including a second microphone. fig. 16 is a cross sectional view a-a of another embodiment of a microphone region configured to include sideband microphone openings as shown in fig. 4 . fig. 17 is an interior view of the top case in the region of the cross section shown in fig. 16 . fig. 18 is an interior view of the top case in the region of the cross section shown in fig. 16 including a microphone assembly. fig. 19 shows one embodiment of bi-stable spring configured to affix a microphone assembly in place with respect to top case. fig. 20 shows a fixture for applying pressure to a microphone assembly to assist in mounting the microphone assembly in top case. detailed description representative applications of apparatuses and methods according to the presently described embodiments are provided in this section. these examples are being provided solely to add context and aid in the understanding of the described embodiments. it will thus be apparent to one skilled in the art that the presently described embodiments can be practiced without some or all of these specific details. in other instances, well known process steps have not been described in detail in order to avoid unnecessarily obscuring the presently described embodiments. other applications are possible, such that the following examples should not be taken as limiting. the following relates to a portable computing device such as a laptop computer, net book computer, tablet computer, etc. the portable computing device can include a multi-part housing having a top case and a bottom case joining at a reveal to form a base portion. the portable computing device can have an upper portion (or lid) that can house a display screen and other related components whereas the base portion can house various processors, drives, ports, battery, keyboard, touchpad and the like. the base portion can be formed of a multipart housing that can include top and bottom outer housing components each of which can be formed in a particular manner at an interface region such that the gap and offset between these outer housing components are not only reduced, but are also more consistent from device to device during the mass production of devices. these general subjects are set forth in greater detail below. the top case can also include one or more microphones to capture audio signals for recording or processing. two or more microphones can be used together to determine an audio source direction that can be used to improve audio capture performance. in one embodiment, the spacing between two microphones can correspond to increasing sensitivity to audio signals centered about a selected frequency. in one embodiment, the selected frequency can be around 8 khz, which can be in a human voice range. in one embodiment, microphone holes for receiving audio signals can be located in a sideband of the top case. microphone holes can be coupled to microphones through resonant cavities. the resonant cavities can shape a frequency response of the related microphones. in one embodiment, the resonant cavities can peak or boost the frequency response around 8 khz. in another embodiment, microphone holes can be positioned on a keyboard web, approximately centered horizontally on the portable computing device. microphones can be coupled to microphone holes through cavities. in one embodiment, a cavity can be formed within a fastener that can simultaneously be configured to attach a keyboard to the keyboard web. in yet another embodiment, microphone openings can be disposed on the keyboard web and can be hidden by keycaps. these and other embodiments are discussed below with reference to figs. 1-20 . however, those skilled in the art will readily appreciate that the detailed description given herein with respect to these figures is for explanatory purposes as the invention extends beyond these limited embodiments. figs. 1-20 show various views of the portable computing device in accordance with various embodiments. fig. 1 shows a front facing perspective view of an embodiment of the portable computing device in the form of portable computing device 100 in an open (lid) state. portable computing device 100 can include base portion 102 formed of bottom case 104 fastened to top case 106 . base portion 102 can be pivotally connected to lid portion 108 by way of clutch assembly 110 hidden from view by a cosmetic wall. base portion 102 can have an overall uniform shape sized to accommodate clutch assembly 110 and inset portion 112 suitable for assisting a user in lifting lid portion 108 by, for example, a finger. top case 106 can be configured to accommodate various user input devices such as keyboard 114 and touchpad 116 . keyboard 114 can include a plurality of low profile keycap assemblies each having an associated key pad 118 . in one embodiment, an audio transducer (not shown) can use selected portions of keyboard 114 to output audio signals such as music. in the described embodiment, a microphone can be located at a side portion of top case 106 that can be spaced apart to improve frequency response of an associated audio circuit. each of the plurality of key pads 118 can have a symbol imprinted thereon for identifying the key input associated with the particular key pad. keyboard 114 can be arranged to receive a discrete input at each keypad using a finger motion referred to as a keystroke. in the described embodiment, the symbols on each key pad can be laser etched thereby creating an extremely clean and durable imprint that will not fade under the constant application of keystrokes over the life of portable computing device 100 . in order to reduce component count, a keycap assembly can be re-provisioned as a power button. for example, key pad 118 - 1 can be used as power button 118 - 1 . in this way, the overall number of components in portable computing device 100 can be commensurably reduced. touch pad 116 can be configured to receive finger gesturing. a finger gesture can include touch events from more than one finger applied in unison. the gesture can also include a single finger touch event such as a swipe or a tap. the gesture can be sensed by a sensing circuit in touch pad 116 and converted to electrical signals that are passed to a processing unit for evaluation. in this way, portable computing device 100 can be at least partially controlled by touch. lid portion 108 can be moved with the aid of clutch assembly 110 from the closed position to remain in the open position and back again. lid portion 108 can include display 120 and rear cover 122 (shown more clearly in fig. 2 ) that can add a cosmetic finish to lid portion 108 and also provide structural support to at least display 120 . in the described embodiment, lid portion 108 can include mask (also referred to as display trim) 124 that surrounds display 120 . display trim 124 can be formed of an opaque material such as ink deposited on top of or within a protective layer of display 120 . display trim 124 can enhance the overall appearance of display 120 by hiding operational and structural components as well as focusing attention onto the active area of display 120 . display 120 can display visual content such as a graphical user interface, still images such as photos as well as video media items such as movies. display 120 can display images using any appropriate technology such as a liquid crystal display (lcd), oled, etc. portable computing device 100 can also include image capture device 126 located on a transparent portion of display trim 124 . image capture device 126 can be configured to capture both still and video images. lid portion 108 can be formed to have uni-body construction that can provide additional strength and resiliency to lid portion 108 which is particularly important due to the stresses caused by repeated opening and closing. in addition to the increase in strength and resiliency, the uni-body construction of lid portion 108 can reduce overall part count by eliminating separate support features. data ports 128 - 132 can be used to transfer data and/or power between an external circuit(s) and portable computing device 100 . data ports 128 - 132 can include, for example, input slot 128 that can be used to accept a memory card (such as a flash memory card), data ports 130 and 132 can take be used to accommodate data connections such as usb, firewire, thunderbolt, and so on. in some embodiments, speaker grid 134 can be used to port audio from an associated audio component enclosed within base portion 102 . in one embodiment, microphones for capturing audio can be located in microphone region 136 . although not shown in fig. 1 , in other embodiments, microphones for capturing audio can be located in region 138 . fig. 2 shows portable computing device 100 in a closed (lid) configuration that shows rear cover 122 and logo 202 . in one embodiment, logo 202 can be illuminated by light from display 120 . it should be noted that in the closed configuration, lid portion 108 and base portion 102 form what appears to be a uniform structure having a continuously varying and coherent shape that enhances both the look and feel of portable computing device 100 . fig. 3 shows another embodiment in the form of portable computing device 300 that is smaller than portable computing device 100 . since portable computing device 300 is smaller in size than portable computing device 100 , certain features shown in fig. 1 are modified, or in some cases lacking, in portable computing device 300 . for example, base portion 302 can be reduced in size such that separate speakers (such as speaker grid 134 ) are replaced with an audio port embodied as part of keyboard 114 . however, bottom case 304 and top case 306 can retain many of the features described with regards to portable computing device 100 (such as display 120 though reduced to an appropriate size). similar to fig. 1 , in one embodiment, microphones for capturing audio can be located in microphone region 136 . although not shown in fig. 3 , in other embodiments, microphones for capturing audio can be located in region 138 . fig. 4 shows microphone region 136 of top case 106 having first microphone opening 401 and second microphone opening 403 suitable for receiving audio signals. in this embodiment, microphone openings 401 , 403 are disposed on sideband 410 of top case 106 and spaced apart distance “d1” in order to facilitate error correction in speech recognition algorithms. distance d1 can vary depending upon a desired frequency response. for example, distance d can be on the order of about 15 mm. in other embodiments, microphone openings 401 , 403 can be spaced apart a distance between 10 and 30 mm. in one embodiment, microphone openings 401 and 403 can be substantially perpendicular to users of portable computing device 100 . such a positioning of microphone openings can advantageously remove the openings from a line of sight of the user. microphone openings 401 , 403 can be substantially centered vertically (as shown) on side of top case 106 . in one embodiment, microphone openings 401 , 403 can take the form of an ellipse. in another embodiment, openings 401 and 403 can be substantially circular. although not readily apparent from fig. 5 , microphone openings 401 , 403 can be part of an internal microphone system. in one case, the microphone openings 401 , 403 can lead to audio ports (cavities) that lead to an audio circuit having a transducer for converting audio signals (in the form of a voice, for example) into digital data for subsequent processing. the audio ports can be formed as part of top case 106 . in other embodiments, more than two microphone openings can be disposed on sideband 410 . in those embodiments, spacing between microphone openings need not be equal, but can be different. for example the distance between a first and a second microphone opening can be 15 mm, while the distance between the second and a third microphone openings can be 20 mm. different microphone opening spacing can enable different available frequency responses compared to an embodiment with only two microphones. top case 106 can also include an opening for a headphone jack 424 . figs. 5a-5b are cross section views of microphone openings 401 , 403 from fig. 4 . fig. 5a in particular, is a bottom view of cross section a-a. although fig. 5a is a cross section of microphone opening 403 , cross section of microphone opening 401 can be substantially similar. microphone opening 403 is shown on sideband 410 . in one embodiment, the diameter of cavity 501 is 0.5 millimeters. in other embodiments, the diameter of cavity 501 can range from 0.5 to 1.00 mm. other embodiments can include other diameters. microphone 503 can be aligned with cavity 501 such that the opening of microphone 503 can be substantially centered with cavity 501 . in one embodiment, cavity 501 can act as a resonant cavity coupling microphone opening 403 to microphone 503 . the resonant cavity can affect, at least in part, a frequency response of microphone 503 . microphone 503 can be attached to a substrate 505 and couple signals from microphone 503 to other devices or circuits. substrate 505 can be a printed circuit board, flexible circuit, rigid flex or any other technically feasible substrate. in one embodiment, microphone 503 can be sealed to cavity 501 to improve acoustic performance and reduce sensitivity to stray noise. fig. 5b shows a top view of cross section a-a from fig. 5 . microphone opening 403 is shown on sideband 410 . microphone 503 can be positioned with respect to top case 106 , by carrier 520 , mounting flange 525 or a combination of both. in one embodiment, cavity 501 can be configured at an angle with respect to sideband 403 . in one embodiment, cavity 501 can be fifteen degrees in elevation with respect to a top or bottom surface of top case 106 . in one embodiment, microphones associated with both first and second microphone openings 401 and 403 can be configured substantially similar to the configuration shown figs. 5a-5b . by configuring the microphone openings 401 , 403 , related cavities and related microphones substantially similar, acoustic performance aspects of individual microphones can be substantially similar, enhancing the performance of a microphone array based on microphones coupled to first and second microphone openings 401 , 403 . in one embodiment, microphone openings 401 and 403 can be co-planar on sideband 410 . fig. 6 shows microphone region 138 of top case 106 in accordance with one embodiment of the specification. microphone region 138 can be disposed on keyboard web 602 . the exemplary embodiment shown in fig. 6 shows two microphone openings positioned on keyboard web 602 . in one embodiment, the distance d separating first microphone opening 604 and second microphone opening 606 can be between 15 and 20 mm. first microphone opening 604 can be disposed toward one edge of keyboard 602 , adjacent to the area for keyboard 114 . second microphone opening 606 can be positioned between key openings on keyboard web 602 . in one embodiment, microphone openings 604 and 606 can be centered horizontally on keyboard web 602 such that microphone openings 604 and 606 can be substantially equally distant from right and left edges of the portable computing device 100 . this microphone position can advantageously center the microphone openings 604 and 606 substantially in-line with the user. microphone separation distance d2 between first microphone opening 604 and second microphone opening 606 can be selected to enable microphones coupled to first 604 and second 606 microphone openings to increase a frequency response in a frequency band. in one embodiment, a separation of 15 mm can enhance a frequency response around 8 khz, which can be a frequency related to human voices. figs. 7a and 7b are cross section views of microphone openings shown in fig. 7 . fig. 7a shows cross section b-b, as viewed from the top of keyboard web 602 . keyboard web 602 can include first microphone opening 604 and second microphone opening 606 . first microphone 704 can be aligned with first microphone opening 604 . in one embodiment, first cavity 702 can be disposed between and couple first microphone 704 to first microphone opening 604 and first cavity 702 can also function as a resonant cavity to shape an audio frequency response of the first microphone 704 . in one embodiment, first cavity can be formed keyboard web 602 . second microphone 706 can be aligned with second microphone opening 606 . second cavity 712 can couple second microphone 706 to second microphone opening 606 . in one embodiment, second cavity 712 can be formed by fastener 713 where a central portion of the fastener 713 is removed. in one embodiment, fastener 713 can be a machined screw. the fastener 713 can be used to attach a keyboard assembly to the top case 106 as well as act as second cavity 712 . in one embodiment, the dimensions of the central portions of fastener 713 can define, at least in part, related resonant cavity characteristics. fig. 7b is a bottom view of cross section b-b from fig. 7 . first cavity 702 and second cavity 712 are shown. first microphone 704 and second microphone 706 can be affixed to a common substrate 720 to ease manufacturing and help route microphone signals. the substrate 720 can be a flex circuit, rigid flex circuit, or any other technically feasible substrate. in one embodiment, first microphone 704 and second microphone 706 can be sealed to first cavity 702 and second cavity 712 respectively to increase acoustic performance and reduce sensitivity to stray noise sources. fig. 8 is a cross section view of another embodiment of a microphone region 800 on top case 106 . in this embodiment, microphone openings 801 and 803 can be placed underneath keycaps 118 of a keyboard 114 of portable computing device 100 . first microphone 811 and second microphone 813 can be disposed underneath keyboard web 602 . in one embodiment, first and second microphone openings 801 and 803 can be spaced 15 millimeters apart. in other embodiments, microphone spacing can be between 10 and 30 millimeters apart. first cavity 821 can couple first microphone 811 to first microphone opening 801 and second cavity 823 can couple second microphone 813 to second microphone opening 803 . in one embodiment, cavities 821 and 823 in keyboard web 602 can also serve, at least in part, as resonant cavities to help shape the frequency response of microphones 811 and 813 . as shown, microphone openings 801 and 803 can be advantageously hidden underneath keycaps 118 . fig. 9 is a view of another embodiment of a microphone region 900 . in this embodiment, two microphone openings can be disposed on an upper region of top case 106 . as shown, a first microphone opening 902 and a second microphone opening 904 can be disposed on a rear portion of top case 106 above the keyboard web. in one embodiment, the first and the second microphone openings 902 and 904 can be separated by a distance d. as described above, the distance d can be selected to facilitate detection and error correction in speech recognition algorithms. in one embodiment, distance d can vary depending upon a desired frequency response. microphone region 900 can include a third microphone opening 906 disposed on a rear facing portion of top case 106 . in one embodiment, the third microphone opening 906 can be disposed near rear vents co-located on the rear facing portion of top case 106 . fig. 10 shows another view of the microphone region 1000 shown in fig. 9 including a microphone assembly 1002 . microphone assembly 1002 can support three microphones configured to receive audio signals. in one embodiment, microphone assembly 1002 can include a flexible cable configured to act as a mounting substrate for the three microphones. as shown, the first microphone opening 902 and the second microphone opening 904 can be disposed on an upper region of top case 106 . the third microphone opening 906 can be formed in two steps. a first step can form an acoustic cavity 1004 between an outer surface of top case 106 and an inner surface of top case 106 in the region of a third microphone. a second step can shape a surface feature of acoustic cavity 1004 to be substantially round. the second step can mask an ellipsoid shape that can result when acoustic cavity 1004 is formed at an angle with respect to the rear facing wall of top case 106 . fig. 11 shows an interior view of top case 106 near the microphone region of fig. 9 . the third microphone opening 906 is shown in relation to rear vents 1108 and 1110 . in one embodiment, a mounting surface 1102 can be formed in top case 106 for top facing microphones. in one embodiment, an edge of rear vents 1108 and 1110 can be shaped to accommodate top facing microphones. in some embodiments, edge 1104 of vents 1108 and 1110 can be uniformly shaped with respect to each other, but in contrast to other vent edges 1112 . fig. 12 shows an interior view of top case 106 near the microphone region of fig. 9 with microphone assembly 1002 . microphone assembly 1002 can include a first microphone 1202 that can be coupled to the first microphone opening 902 , a second microphone 1204 that can be coupled to the second microphone opening 904 and a third microphone 1206 that can be coupled to the third microphone opening 906 . a flexible cable 1208 can act as a mounting substrate for the microphones. the first and second microphones 1202 and 1204 can be disposed adjacent to mounting surface 1102 . in another embodiment of a microphone region, a first microphone opening can be disposed on a upper region of top case 106 (similar to microphone opening 902 shown in fig. 9 ) and a second microphone can be disposed within clutch assembly 110 . fig. 13 shows an internal view 1300 of top case 106 in the region of a first microphone 1302 disposed on an upper region of top case 106 . first microphone can be affixed to a mounting substrate 1304 . a flexible cable 1306 can be coupled to first microphone 1302 and can carry electrical signals from first microphone 1302 to audio processing circuitry. the first microphone 1302 and mounting substrate 1304 can be configured to mount within a well 1308 formed in top case 106 . fig. 14 shows a reverse view 1400 of the mounting substrate 1304 . the first microphone 1302 can include a microphone port 1402 that can be accurately aligned with an acoustic cavity in the top case 106 configured to receive acoustic sounds. one or more tabs 1406 can be formed in the mounting substrate 1304 to help accurately locate the microphone port 1402 to a selected acoustic cavity. in some embodiments, a gasket 1404 can be used to help seal microphone 1302 to top case 106 . in yet other embodiments, gasket 1404 can include an adhesive layer configured to affix microphone 1302 and substrate 1304 to top case 106 . fig. 15 shows an internal view of a clutch assembly 110 including a second microphone 1502 . the first microphone 1302 and the second microphone 1520 can be used together to perform acoustic detection and error correction in speech recognition algorithms. in one embodiment, distance between the first and the second microphones can vary depending upon a desired frequency response. fig. 16 is a cross sectional view a-a 1600 of another embodiment of a microphone region configured to include sideband 410 microphone openings as shown in fig. 4 . although the cross section 1600 shows a single microphone region, first and second microphone regions can be substantially similar. the first microphone opening 401 can be coupled to a first acoustic cavity 1606 formed with a first segment 1602 and a second segment 1604 . in one embodiment, the first acoustic cavity 1606 can be configured to enhance a frequency response of a first microphone. in one embodiment, the diameter of the first segment can be about 0.7 mm. the first microphone can be mounted to a first microphone mounting surface 1608 . one method for forming the first acoustic cavity 1606 can include the steps of forming the first segment 1602 by machining the first segment 1602 from the outside of the top case 106 and then forming the second segment 1604 by machining the second segment from inside the top case 106 . in one embodiment, pulsating air can be used to flush debris from the first acoustic cavity 1606 and to continue to prevent foreign material from settling within the first acoustic cavity 1606 . fig. 17 is an interior view 1700 of the top case 106 in the region of the cross section shown in fig. 16 . the second segment 1604 of the first acoustic cavity 1606 is shown within the first microphone mounting surface 1608 . the first acoustic cavity 1606 can be coupled to the first microphone opening 401 of fig. 4 . a second segment 1704 of a second acoustic cavity is shown within a second microphone mounting surface 1708 . the second acoustic cavity can be coupled to the second microphone opening 403 of fig. 4 . one or more notches 1706 can be formed on an interior surface of top case 106 to accommodate flexible cables that can be used to couple signals from first and second microphones to electrical circuitry. fig. 18 is an interior view 1800 of the top case 106 in the region of the cross section shown in fig. 16 including a microphone assembly 1802 . the microphone assembly 1802 can include a first microphone 1804 and a second microphone 1806 . in one embodiment, the first and second microphones 1804 , 1806 can be mounted to a flexible circuit 1808 . in one embodiment, first microphone 1804 can be coupled to first microphone opening 401 and second microphone 1806 can be coupled to second microphone opening 403 . in another embodiment, the flexible circuit 1808 can include an adhesive, such as a pressure sensitive adhesive to affix the microphone assembly 1802 to the top case 106 . in particular, regions of the flexible circuit 1808 that can contact the first and second microphone mounting surfaces 1608 , 1708 can include a pressure sensitive adhesive. fig. 19 shows one embodiment 1900 of bi-stable spring 1902 configured to affix a microphone assembly in place with respect to top case 106 . a microphone 1904 can be disposed within a holder 1906 . the holder 1906 can be configured to position the microphone 1904 at a proper mating angle to engage a microphone mounting surface formed within top case 106 . in one embodiment, the microphone mounting surface can be similar to microphone mounting surface 1608 illustrated in fig. 16 . a bi-stable spring 1902 can be configured to engage a notch 1908 formed in top case 106 and force microphone holder 1906 against the microphone mounting surface. the bi-stable spring 1902 can enable relatively easy removal of microphone 1904 since no adhesive is used to attach the microphone 1904 to the top case 106 . fig. 20 shows a fixture for applying pressure to a microphone assembly to assist in mounting the microphone assembly in top case 106 . in one embodiment, the microphone assembly 1802 can be as described in fig. 18 . when microphone assembly 1802 includes a pressure sensitive adhesive, the assembly 1802 can be forced, at least temporarily, against a surface of top case 106 to help ensure contact of the adhesive between the assembly 1802 and the top case 106 . in some embodiments, access to the microphone assembly 1802 can be limited. a fixture can be used to properly apply pressure to the microphone assembly 1802 without damaging microphones 1804 and 1806 . fig. 20a shows one embodiment of the fixture that can include two pieces: a plunger support 2002 and a plunger 2004 . the plunger support 2002 can use existing features formed within top case 106 to establish a proper position with respect to microphone assembly 1802 . plunger 2004 can be supported at an angle by plunger support 2002 . plunger 2004 can include a first surface 2006 configured to receive a bonding pressure. the bonding pressure is transferred to surfaces 2010 that can be placed against microphone assembly 1802 . an angled surface on plunger support 2002 can ensure that bonding pressure is delivered to surfaces 2010 at a correct orientation. by splitting surfaces 2010 into two distinct surfaces, pressure can be individually applied to the first and the second microphones 1804 and 1806 respectively. although the foregoing invention has been described in detail by way of illustration and example for purposes of clarity and understanding, it will be recognized that the above described invention may be embodied in numerous other specific variations and embodiments without departing from the spirit or essential characteristics of the invention. certain changes and modifications may be practiced, and it is understood that the invention is not to be limited by the foregoing details, but rather is to be defined by the scope of the appended claims.
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046-242-636-336-724
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JP
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[
"TW",
"US",
"CN"
] |
H01L21/338,H01L21/28,H01L29/40,H01L29/78,H01L21/02,H01L29/778,H01L29/04,H01L29/20,H01L29/66,H01L21/306,H01L21/308,H01L21/335,H01L29/08
| 2020-07-16T00:00:00 |
2020
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[
"H01"
] |
method for producing nitride-based high electron mobility transistor and nitride-based high electron mobility transistor
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to provide a pec etching technique which is to be used for manufacturing a nitride-based high-electron mobility transistor. a method for manufacturing a nitride-based high-electron mobility transistor comprises the steps of: providing a conductive member on a substrate outside a device region in plan view; forming, on the substrate, a mask having an opening in at least one of a source recess etching region and a drain recess etching region; exposing the substrate to light in a state in which the substrate having the conductive member provided thereon and the mask formed thereon is put in contact with an etchant containing an oxidizing agent capable of receiving an electron, thereby performing a photoelectrochemical etching process to form at least one of a source recess and a drain recess; and forming a device isolation structure.
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1 . a method for manufacturing a nitride-based high electron mobility transistor, comprising: providing a conductive member on a nitride semiconductor crystal substrate, outside an element region of the high electron mobility transistor in a plan view; forming a mask on the nitride semiconductor crystal substrate, the mask having an opening in at least one of a source recess etching region where a source recess is formed, which is a recess in which a source electrode of the high electron mobility transistor is arranged, and a drain recess etching region where a drain recess is formed, which is a recess in which a drain electrode of the high electron mobility transistor is arranged; performing photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light to form at least one of a source recess and a drain recess, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons; and forming an element separation structure of the high electron mobility transistor. 2 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein the providing the conductive member, the forming the mask, the forming at least one of the source recess and the drain recess, and the forming the element separation structure are performed in an order described in claim 1 . 3 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein the nitride semiconductor crystal substrate includes on a base substrate, at least: a channel layer on which a two-dimensional electron gas is formed, a barrier layer formed on the channel layer, and a cap layer formed on the barrier layer and which is composed of a group iii nitride having a bandgap smaller than that of a group iii nitride constituting the barrier layer, and in the photoelectrochemical etching, the cap layer is removed. 4 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 3 , wherein the conductive member is electrically connected to the source recess etching region or the drain recess etching region through at least one of the cap layer and the two-dimensional electron gas. 5 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein in the formation of the element separation structure, the element separation structure is formed so as to have an overlap in a plan view with at least one part of the source recess etching region and the drain recess etching region. 6 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein in the formation of the element separation structure, the element separation structure is formed by any one of the techniques of ion implantation, dry etching, and photoelectrochemical etching. 7 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein in the formation of the element separation structure, the element separation structure is formed so as not to have overlap with an arrangement area of the conductive member in a plan view. 8 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 7 , wherein in the formation of the element separation structure, the element separation structure is formed by ion implantation using the conductive member as at least a part of a mask. 9 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 7 , wherein in the formation of the element separation structure, the element separation structure is formed by dry etching, at least in a state where a mask is formed to cover the source recess or the drain recess and the conductive member so as not to be exposed. 10 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 7 , wherein in the formation of the element separation structure, the element separation structure is formed by photoelectrochemical etching, in a state where a mask is formed to expose at least a part of the conductive member. 11 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 10 , wherein photoelectrochemical etching in the formation of at least one of the source recess and the drain recess is performed using an acidic etching solution, and photoelectrochemical etching in the formation of the element separation structure is performed using an alkaline etching solution. 12 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , wherein in the formation of the element separation structure, the element separation structure is formed so as to have an overlap with an arrangement region of the conductive member in a plan view. 13 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 12 , wherein the formation of the element separation structure is performed after removing the conductive member. 14 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , in the manufacturing of the nitride-based high electron mobility transistor, a plurality of high electron mobility transistors are manufactured, which are arranged in at least one direction of a gate length direction and a gate width direction on the nitride semiconductor crystal substrate, and the conductive member is arranged between at least one of the high electron mobility transistor elements adjacent to each other in the gate length direction and the high electron mobility transistor elements adjacent to each other in the gate width direction. 15 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 14 , wherein the conductive member arranged between the high electron mobility transistor elements adjacent to each other in the gate length direction has a shape extending in the gate width direction. 16 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 14 , wherein the conductive member arranged between the high electron mobility transistor elements adjacent to each other in the gate width direction has a shape extending in the gate length direction. 17 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 1 , further comprising: forming another mask on the nitride semiconductor crystal substrate, the mask having an opening in a gate recess etching region where a gate recess is formed, which is a recess in which a gate electrode of the high electron mobility transistor is arranged; forming the gate recess by performing other photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons. 18 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 17 , wherein the nitride semiconductor crystal substrate includes on a base substrate, at least: a channel layer on which a two-dimensional electron gas is formed, a barrier layer formed on the channel layer, and a cap layer formed on the barrier layer and which is composed of a group iii nitride having a bandgap smaller than that of a group iii nitride constituting the barrier layer, and in the photoelectrochemical etching, the cap layer is removed, and in the above other photoelectrochemical etching, the cap layer and a part of the barrier layer are removed. 19 . the method for manufacturing a nitride-based high electron mobility transistor according to claim 17 , wherein in the photoelectrochemical etching and the above other photoelectrochemical etching, light irradiation is performed using a same light source, and the photoelectrochemical etching is stopped by time control, and the above other photoelectrochemical etching is stopped by self-stop. 20 . a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer, a barrier layer arranged on the channel layer, and a cap layer arranged on the barrier layer; a source electrode, a gate electrode, and a drain electrode; an element separation structure, wherein plasma damage is not introduced into at least a group iii nitride layer located directly under the source electrode and the drain electrode.
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background technical field the present disclosure relates to a method for manufacturing a nitride-based high electron mobility transistor and a nitride-based high electron mobility transistor. description of related art group iii nitrides such as gallium nitride (gan) are used as materials for manufacturing semiconductor devices such as light emitting devices and transistors. photoelectrochemical (pec) etching has been proposed as an etching technique for forming various structures on group iii nitrides such as gan (see, for example, non-patent document 1). the pec etching is a wet etching with less damage than a general dry etching, and is preferable because a device is simple, compared to special dry etching with less damage such as neutral particle beam etching (see, for example, non-patent document 2) and atomic layer etching (see, for example, non-patent document 3). prior art document non-patent document [non-patent document 1] k. miwa, appl. phys. express 13, 026508 (2020).[non-patent document 2] s. samukawa, jjap, 45 (2006) 2395.[non-patent document 3] t. ohba, jpn. j. appl. phys. 56, 06hb06 (2017). summary of the invention an object of the present disclosure is to provide a pec etching technique used for manufacturing a nitride-based high electron mobility transistor. according to an aspect of the present disclosure, there is provided a method for manufacturing a nitride-based high electron mobility transistor, including: providing a conductive member on a nitride semiconductor crystal substrate, outside an element region of the high electron mobility transistor in a plan view; forming a mask having an opening in at least one of a source recess etching region where a source recess is formed, which is a recess in which a source electrode of the high electron mobility transistor is arranged, and a drain recess etching region where a drain recess is formed, which is a recess in which a drain electrode of the high electron mobility transistor is arranged; performing photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light to form at least one of a source recess and a drain recess, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons; and forming an element separation structure of the high electron mobility transistor. according to other aspect of the present disclosure, there is provided a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer, a barrier layer arranged on the channel layer, and a cap layer arranged on the barrier layer; a source electrode, a gate electrode, and a drain electrode; an element separation structure; and at least one of a source recess formed on the group iii nitride layer and a drain recess formed on the group iii nitride layer, wherein plasma damage is not introduced into at least a group iii nitride layer located directly under the source electrode and the drain electrode. advantage of the invention there is provided a pec etching techniques used in a manufacture of a nitride-based high electron mobility transistor. brief description of the drawings fig. 1a is a schematic cross-sectional view illustrating hemt according to an embodiment of the present disclosure, and fig. 1b is a schematic cross-sectional view illustrating a pec etching apparatus. figs. 2a to 2c are schematic cross-sectional views illustrating hemt manufacturing steps according to the present embodiment. figs. 3a to 3c are schematic cross-sectional views illustrating hemt manufacturing steps according to the present embodiment. figs. 4a to 4c are schematic cross-sectional views illustrating hemt manufacturing steps according to the present embodiment. figs. 5a to 5c are schematic cross-sectional views illustrating hemt manufacturing steps according to the present embodiment. figs. 6a and 6b are schematic plan views illustrating hemt manufacturing steps according to the present embodiment. figs. 7a and 7b are schematic plan views illustrating hemt manufacturing steps according to the present embodiment. figs. 8a and 8b are schematic cross-sectional views schematically illustrating a mechanism of pec etching for forming a gate recess. fig. 9a is a schematic plan view illustrating a planar arrangement example of an element separation structure according to a first modified example, and fig. 9b is a schematic plan view illustrating a planar arrangement example of an element separation structure 160 according to a second modified example. figs. 10a and 10b are schematic cross-sectional views illustrating hemt manufacturing steps according to a second modified example. fig. 11 is a schematic plan view illustrating a planar arrangement example of a cathode pad according to a third modified example. fig. 12 is a schematic cross-sectional view illustrating hemt according to a fourth modified example. fig. 13 is a schematic cross-sectional view illustrating the steps of another embodiment in which the element separation structure is formed by pec etching. fig. 14 is a schematic plan view illustrating another embodiment in which a part of a cathode pad overlaps with a device region. figs. 15a and 15b are schematic cross-sectional views illustrating hemt manufacturing steps according to another embodiment in which the cathode pad (cathode portion) is composed of a group iii nitride, respectively, and are schematic cross-sectional views illustrating the hemt. fig. 16 is a schematic cross-sectional view illustrating a hemt according to still another embodiment in which the cathode pad (cathode portion) is composed of a group iii nitride. detailed description of the disclosure in a high electron mobility transistor (nitride-based high electron mobility transistor) using a group iii nitride, a technique of forming a cap layer on a barrier layer is used. the barrier layer is made of, for example, aluminum gallium nitride (algan), and the cap layer is made of, for example, gan. hereinafter, the nitride-based high electron mobility transistor is also simply referred to as hemt. in a conventional technique, a source electrode and a drain electrode of hemt are formed on the cap layer, and due to this, a contact resistance of the source electrode and the drain electrode cannot be reduced. it is conceivable to reduce the contact resistance of the source electrode and the drain electrode by removing the cap layer. however, the conventional technique for etching the cap layer is dry etching, and due to an etching damage caused by the dry etching, the contact resistance cannot be reduced even when the cap layer is removed. photoelectrochemical (pec) etching has been proposed as a new technique for etching group iii nitrides such as gan while suppressing etching damage. as a pec etching technique related to hemt, the inventors of the present application have so far proposed a technique for forming a gate recess by pec etching by using a source electrode or a drain electrode as a cathode pad (japanese patent application no. 2019-140027). the cathode pad is a conductive member used for advancing electrodeless pec etching, as will be described in detail later. in the gate recess forming technique, the cap layer interposed under the source electrode or the drain electrode could not be removed by pec etching. the source electrode and the drain electrode are formed on the cap layer, and it was not possible to reduce a contact resistance caused by the cap layer of the source electrode and the drain electrode. by using the pec etching, etching damage can be suppressed and the cap layer can be removed. however, it is not known how to perform the pec etching to remove the cap layer under the source electrode or under the drain electrode. the present inventors propose such a technique in the following embodiments. embodiment a nitride-based high electron mobility transistor (hemt) 150 according to an embodiment of the present disclosure will be described. fig. 1a is a schematic cross-sectional view illustrating hemt 150 , showing one hemt element. the hemt 150 includes a laminate 10 , a source electrode 151 , a gate electrode 152 , a drain electrode 153 , an element separation structure 160 , and an insulating film 170 . the laminate (nitride semiconductor crystal substrate) 10 has a substrate (base substrate) 11 and a group iii nitride layer 12 (hereinafter, also referred to as an epi layer 12 ) formed on the substrate 11 . the substrate 11 is a crystal substrate that serves as a base for epitaxially growing the epi layer 12 , and for example, a semi-insulating substrate is used as the substrate 11 . here, “semi-insulating property” means, for example, a state in which a specific resistance is 10 5 ωcm or more. as the semi-insulating substrate, for example, a semi-insulating silicon carbide (sic) substrate is used, and for example, a semi-insulating gallium nitride (gan) substrate is used. the semi-insulating gan substrate is, for example, a (fe)-doped or manganese (mn)-doped gan substrate. a laminated structure including, for example, a nucleation layer 12 a made of aluminum nitride (aln), a channel layer 12 b made of gan, a barrier layer 12 c made of gallium nitride (algan), and a cap layer 12 d made of gan, is used as the epi layer 12 at the time of using the sic substrate for the substrate 11 . in the laminated structure of the channel layer 12 b and the barrier layer 12 c , a two-dimensional electron gas (2deg) serving as a channel of hemt150 is formed in the vicinity of an upper surface of the channel layer 12 b . algan may be used as a material of the channel layer 12 b , in addition to gan. a material having a lower al composition (smaller bandgap) than the algan used for the barrier layer 12 c is used as the algan used for the channel layer 12 b. the substrate 11 is not limited to the sic substrate, and other substrates (sapphire substrate, silicon (si) substrate, (semi-insulating) gan substrate, etc.) may be used. the laminated structure of the epi layer 12 may be appropriately selected depending on the type of the substrate 11 , the characteristics of the hemt 150 to be obtained, and the like. for example, in the epi layer 12 when a gan substrate is used as the substrate 11 , the nucleation layer 12 a may be omitted. an upper surface of the epi layer 12 is composed of a c-plane of the group iii nitride constituting the epi layer 12 . “composed of a c-plane” means that a crystal plane with a lowest index closest to the upper surface is the c-plane of the group iii nitride crystal constituting the epi layer 12 . the group iii nitride constituting the epi layer 12 has dislocations (through dislocations), and the dislocations are distributed at a predetermined density on the upper surface. the laminate 10 may have a passivation insulating film 13 (hereinafter, also referred to as an insulating film 13 ) arranged on the epi layer 12 . the insulating film 13 is made of, for example, silicon nitride. of the epi layer 12 , a portion under the channel layer 12 b is referred to as an epi lower layer 12 l, and a portion above the channel layer 12 b is referred to as an epi upper layer 12 u. the epi lower layer 12 l includes the channel layer 12 b in which 2deg is formed. the epi upper layer 12 u includes the barrier layer 12 c formed on the channel layer 12 b and the cap layer 12 d formed on the barrier layer 12 c . the barrier layer 12 c is composed of a group iii nitride having a bandgap larger than that of the group iii nitride constituting the channel layer 12 b , to generate 2deg in the channel layer 12 b . the cap layer 12 d is composed of a group iii nitride having a smaller bandgap than the group iii nitride constituting the barrier layer 12 c. in the hemt 150 of the present embodiment, the gate electrode 152 is arranged in a gate recess 110 g, the source electrode 151 is arranged in a source recess 110 s, and the drain electrode 153 is arranged in a drain recess 1101 d. the gate recess 110 g, the source recess 110 s, and the drain recess 1101 d are recesses formed in the epi upper layer 12 u (structure formed by etching the epi upper layer 12 u), respectively. hereinafter, the source recess 110 s and the drain recess 110 d may be collectively referred to as an ohmic recess 110 sd (to represent at least one of the source recess 110 s and drain recess 110 d without any distinction). the gate recess 110 g is a recess formed in the epi upper layer 12 u by etching the cap layer 12 d and a part of the barrier layer 12 c , and the barrier layer 12 c is exposed at a bottom of the gate recess 110 g. a thickness of the barrier layer 12 c under the gate recess 110 g (thickness from the upper surface of the channel layer 12 b to the bottom of the gate recess 110 g) may be set to a predetermined value so that a threshold gate voltage of the hemt150 becomes a predetermined value. the ohmic recess 110 sd is a recess formed in the epi upper layer 12 u by etching the cap layer 12 d (only), and the barrier layer 12 c is exposed at a bottom of the ohmic recess 110 sd. the ohmic recess 110 sd is shallower than the gate recess 110 g. since the source electrode 151 and the drain electrode 153 are respectively arranged in the ohmic recess 110 sd, the contact resistance of the source electrode 151 and the drain electrode 153 can be reduced. it is considered that this is because the source electrode 151 and the drain electrode 153 come into direct contact with the barrier layer 12 c , and lifting of the band caused by the cap layer 12 d is suppressed. the gate electrode 152 is formed of, for example, a ni/au layer in which a gold (au) layer is laminated on a nickel (ni) layer. each of the source electrode 151 and the drain electrode 153 , is formed of, for example, a ti/al/ti/au layer in which an aluminum (al) layer is laminated on a titanium (ti) layer, a ti layer is laminated on the al layer, and an au layer is further laminated on the ti layer. the element separation structure 160 is a structure that divides the cap layer 12 d and 2deg between adjacent hemt elements, and the hemt elements adjacent to each other with the element separation structure 160 interposed between them, are electrically separated from each other. as the element separation structure 160 , for example an element separation groove is shown in the present embodiment, but the element separation structure 160 may be formed by ion implantation instead of forming the groove. the element separation structure 160 , which is an element separation groove, is formed so that its bottom reaches a depth in the middle of the channel layer 12 b. the element separation structure 160 defines an element region 180 that functions as a hemt element. in a plan view, an internal region of a closed edge (hemt element side, that is, an inner edge) surrounding the hemt element of the element separation structure 160 is an element region 180 (see fig. 7a ). the insulating film 170 has an opening on upper surfaces of the source electrode 151 and the drain electrode 153 , covers the element separation structure 160 , and extends to the outside of the element separation structure 160 . the insulating film 170 of the present embodiment is provided as a gate insulating film, and is interposed between the gate recess 110 g and the gate electrode 152 . the insulating film 170 is made of, for example, aluminum oxide. according to the present embodiment, an ohmic recess 110 sd is formed by etching the epi-upper layer 12 u by photoelectrochemical (pec) etching. also, according to the present embodiment, the gate recess 110 g is also formed by etching the epi upper layer 12 u by pec etching. in the manufacturing step of the hemt150, an intermediate structure that is subjected to various processing until the hemt150 is completed, is referred to as a processing object 100 . fig. 1b is a schematic cross-sectional view illustrating a pec etching apparatus 200 . the pec etching apparatus 200 includes a container 210 for accommodating a processing object 100 and an etching solution 201 , and a light source 220 for emitting light 221 . the processing object 100 in the pec etching includes a laminate 10 (at least the epi lower layer 12 l and the epi upper layer 12 u), a cathode pad 30 , and a mask 50 . the laminate 10 (more specifically, the epi upper layer 12 u) has a region 21 to be etched (etching region 21 ) that is etched by the pec etching. the region 21 to be etched is defined by the mask 50 . the processing object 100 in the pec etching is more specifically illustrated in figs. 2c and 3b . the pec etching is performed by irradiating the region 21 to be etched with light 221 through the etching solution 201 , in a state where the processing object 100 is immersed in the etching solution 201 , and the region 21 to be etched and the cathode pad 30 are in contact with the etching solution 201 (the pec etching is performed by irradiating the laminate 10 with light 221 , in a state where the laminate 10 on which the cathode pad 30 is provided and the mask 50 is formed, is in contact with the etching solution 201 ). a mechanism of the pec etching will be described, and the etching solution 201 , the cathode pad 30 , and the like will be described in more detail. gallium nitride (gan) will be described as an example of the group iii nitride that is pec-etched. the pec etching is a wet etching, and is performed in a state where the processing object 100 is immersed in the etching solution 201 . an alkaline or acidic etching solution 201 containing oxygen used to generate an oxide of a group iii element contained in the group iii nitride constituting the region 21 to be etched, and further containing an oxidizing agent that receives electrons, is used as the etching liquid 201 . peroxodisulfuric acid ion (s 2 o 8 2− ) is preferably used as the oxidizing agent, and an aqueous solution obtained by dissolving a salt of (at least) peroxodisulfuric acid ion (s 2 o 8 2− ) in water at a predetermined concentration is used as the etching solution 201 . more specifically, the oxidizing agent functions in such a manner that a sulfate ion radical (so 4 − *) generated from s 2 o 8 2− receives electrons and changes into a sulfate ion (so 4 2− ). the salt of s 2 o 8 2− used in the etching solution 201 , includes, for example, ammonium persulfate (nh 4 ) 2 s 2 o 8 , potassium peroxodisulfate (k 2 s 2 o 8 ), sodium peroxodisulfate (na 2 s 2 o 8 ), etc. from a viewpoint of suppressing a residual alkali metal element caused by the etching solution 201 , it is preferable to use (nh 4 ) 2 s 2 o 8 which does not contain alkali metal. all of these aqueous solutions of s 2 o 8 2− salts are acidic. for example, an alkaline etching solution 201 can be obtained by mixing an alkaline aqueous solution such as a koh aqueous solution with an aqueous solution of these s 2 o 8 2− salts at an appropriate concentration. the reaction in the pec etching of the present embodiment can be summarized as in (chemical formula 1). the reaction for producing so 4 − * from s 2 o 8 2− contained in the etching solution is shown in (chemical formula 2). that is, so 4 − * can be produced by at least one of heating s 2 o 8 2− and irradiating s 2 o 8 2− with light. as shown in (chemical formula 1), holes (h + ) and electrons (e − ) are generated in the group iii nitride by irradiating the group iii nitride with light 221 having a wavelength corresponding to a band gap of the group iii nitride or a wavelength less than this wavelength (in this example, ultraviolet light 221 having a wavelength of 365 nm or less corresponding to the band gap of gan). due to generation of the holes, the group iii nitride (gan in this example) is decomposed into group iii element cations (ga 3+ in this example) and nitrogen gas (n 2 gas), and the cations of the group iii element combine with oxygen contained in water (h 2 o) to generate an oxide of the group iii element (ga 2 o 3 in this example). the oxide of the group iii element is dissolved in the alkaline or acidic etching solution 201 , to thereby etch the group iii nitride. the electrons generated in the group iii nitride are consumed by combining with so 4 − * to generate so 4 2− . as the pec etching proceeds, a hydrogen ion (h+) concentration increases, which reduces ph of the etching solution 201 . the pec etching can be performed regardless of whether the etching solution 201 is alkaline or acidic. however, when using a resist mask, it is preferable to use an etching solution 201 that is acidic (from the start of the pec etching), because resist masks have low resistance to alkalis. further, as described in other embodiments described later, it is preferable to use the etching solution 201 which is acidic (from the start of the pec etching), from a viewpoint of self-stopping pec etching by reducing 2deg (suppressing excessively deep pec etching). the cathode pad 30 is a conductive member made of a conductive material such as metal, and is provided so as to be in contact with at least a part of a surface of a conductive region of the processing object 100 which is electrically connected to the region 21 to be etched through at least one of the cap layer 12 d and 2deg (see fig. 8a ). further, the cathode pad 30 is provided so that at least a part of the cathode pad 30 , for example, an upper surface thereof comes into contact with the etching solution 201 during the pec etching. the cathode pad 30 is made of, for example, titanium (ti). in the region 21 to be etched by the pec etching, the oxide of the group iii element is generated due to the generation of the holes by light irradiation. that is, the region 21 to be etched functions as an anode in which the holes are consumed. due to irradiating the region 21 to be etched with light, the electrons generated in pairs with the holes can flow to the cathode pad 30 through at least one of the cap layer 12 d and 2deg. the surface of the cathode pad 30 that comes into contact with the etching solution 201 , functions as a cathode consumed by emitting the electrons to the etching solution 201 . by making the cathode pad 30 function as a cathode in this way, the pec etching can proceed. in the pec etching according to the present embodiment, the pec etching can proceed by consuming the electrons generated together with the holes by light irradiation of the group iii nitride by s 2 o 8 2− (more specifically, so 4 − * generated from s 2 o 8 2− ) contained in the etching solution 201 as an oxidizing agent. that is, the pec etching can be performed in such a manner that the electrons are directly emitted from the processing object 100 into the etching solution 201 (without passing through external wiring). in contrast, a pec etching technique that does not use such an oxidizing agent, includes pec etching performed in such a manner that electrons generated in the group iii nitride are discharged into an etching solution from a cathode electrode immersed in the etching solution, through wiring extending outside the etching solution. in contrast of electroded pec etching using such a cathode electrode, the pec etching according to the present embodiment is an electrodeless (contactless) pec etching that does not require such a cathode electrode. the pec etching can also be performed to the group iii nitride other than the exemplified gan. the group iii element contained in the group iii nitride may be at least one of aluminum (al), gallium (ga) and indium (in). the concept of the pec etching for the al component or in component in the group iii nitride is the same as the concept described for the ga component with reference to (chemical formula 1). that is, the pec etching can be performed by generating the holes by irradiating the group iii nitride with light to generate an oxide of al or an oxide of in, and dissolving these oxides in an alkaline or acidic etching solution. the wavelength of the light 221 for irradiation may be appropriately changed depending on the composition of the group iii nitride to be etched. when al is contained based on the pec etching of gan, light 221 having a shorter wavelength may be used, and when in is contained, light 221 having a longer wavelength can also be used. that is, the light 221 having a wavelength at which the group iii nitride is pec-etched can be appropriately selected and used, depending on the composition of the group iii nitride to be etched. next, a manufacturing method of the hemt150 according to the present embodiment will be described. the manufacturing method of the present embodiment includes: providing a cathode pad 30 on a laminate 10 outside an element region 180 of a hemt 150 in a plan view (see figs. 2b and 6a ); forming a mask 50 on the laminate 10 , the mask having an opening in a region 21 sd to be etched in which an ohmic recess 110 sd is formed (see fig. 3b ); forming an ohmic recess 110 sd by pec etching (see fig. 3c ); and forming an element separation structure 160 (see fig. 4b ). a plurality of hemt elements are periodically arranged side by side in at least one direction of a gate length direction and a gate width direction, on a wafer of the laminate 10 on which the hemt150 is formed. correspondingly, a plurality of cathode pads 30 may be periodically arranged side by side in at least one direction of the gate length direction and the gate width direction. figs. 2a to 5c are schematic cross-sectional views illustrating a manufacturing process of the hemt150 according to the present embodiment. in order to avoid complexity of the drawing, figs. 2a to 5c illustrates a portion of the laminated 10 above the channel layer 12 b . figs. 2a to 5c illustrate a cross-sectional view of one hemt element. figs. 6a to 7b are schematic plan views illustrating a manufacturing process of the hemt150 according to the present embodiment. figs. 6a to 7b illustrate a plan view of two hemt elements arranged in a gate length direction. fig. 2a is used for reference. a wafer of the laminate 10 is prepared. the laminate 10 has regions to be etched 21 g, 21 sd, 21 is and 21 cp. the region to be etched 21 g is a region to be etched to form a gate recess 110 g, which is a recess in which the gate electrode 152 is arranged. the region to be etched 21 sd is a region to be etched to form an ohmic recess 110 sd, which is a recess in which the source electrode 151 or the drain electrode 153 is arranged. the region to be etched 21 is is a region to be etched to form the element separation structure 160 which is an element separation groove. the region 21 cp to be etched is a region to be etched to form a recess 110 cp in which the cathode pad 30 is arranged. hereinafter, each of the regions to be etched 21 g to 21 cp is also simply referred to as regions 21 g to 21 cp respectively. fig. 2b is used for reference. by photolithography and etching, recesses in which the cap layer 12 d is exposed are formed in the regions 21 g, 21 sd, 21 is, and 21 cp of the insulating film 13 . for etching of the insulating film 13 , for example, wet etching with a buffered hydrofluoric acid aqueous solution, a hydrofluoric acid aqueous solution, or the like is used, and further, for example, low-damage dry etching by atomic layer etching, neutral particle beam etching, or the like is used. further, by photolithography and etching, a recess 110 cp in which the barrier layer 12 c is exposed on the bottom, is formed in the region 21 cp of the cap layer 12 d . for the etching of the cap layer 12 d forming the recess 110 cp, for example, low-damage dry etching by atomic layer etching, neutral particle beam etching, or the like is used. after forming the recess 110 cp, for example, a ti film is deposited on an entire upper surface of the processing object 100 , and the cathode pad 30 is formed by removing an unnecessary ti film on the outside of the recess 110 cp by lift-off. since the cap layer 12 d is usually doped into n-type (having n-type conductivity), the cathode pad 30 may be formed on the cap layer 12 d . by forming the cap layer 12 d in the recess 110 cp from which the cap layer 12 d has been removed, that is, directly above the barrier layer 12 c , the contact resistance of the cathode pad 30 can be reduced. on the other hand, by forming the cathode pad 30 on the cap layer 12 d , the steps of photolithography and etching for removing the cap layer 12 d of the recess 110 cp can be omitted. the cathode pad 30 formed on the cap layer 12 d or the barrier layer 12 c and the region 21 to be pec-etched using the cathode pad 30 , are electrically connected through at least one of the cap layer 12 d and 2deg. the conductivity of 2deg is higher than that of the cap layer 12 d. fig. 2c is used for reference. for example, a silicon oxide film is deposited on the entire upper surface of the processing object 100 . by photolithography and etching, the portion of the silicon oxide film located on the region 21 g and the upper surface of the cathode pad 30 is removed, to form a hard mask 51 arranged above the cap layer 12 d . for the etching of the silicon oxide film, for example, a buffered hydrofluoric acid aqueous solution is used. as used herein, a hard mask means a mask made of an inorganic or metallic material (as opposed to a resist mask made of an organic material). fig. 3a is used for reference. the gate recess 110 g is formed by etching the cap layer 12 d and the barrier layer 12 c of the region 21 g by pec etching using the hard mask 51 (and the insulating film 13 or the like interposed under the hard mask 51 ) as the mask 50 . figs. 8a and 8b are schematic cross-sectional views schematically illustrating a mechanism of the pec etching for forming the gate recess 110 g. fig. 8a illustrates a situation in which the pec etching proceeds, and fig. 8b illustrates a situation in which the pec etching is stopped. as described above, electrons generated by light irradiation toward the region 21 g to be etched flow to the cathode pad 30 through at least one of the cap layer 12 d and 2deg, and discharged from the surface of the cathode pad 30 to the etching solution 201 , to thereby make the pec etching proceed. fig. 8a illustrates a schematic flow of the electrons indicated by an arrow 35 . when the barrier layer 12 c becomes thinner as the pec etching proceeds and the 2deg under the gate recess 110 g decreases, the pec etching becomes difficult to proceed, and eventually, as illustrated in fig. 8b , the pec etching automatically stops (self-stop) with the barrier layer 12 c having a predetermined thickness remaining under the gate recess 110 g. the predetermined thickness can be adjusted by, for example, the intensity of light 221 and can be set so that a threshold gate voltage of the hemt 150 becomes a predetermined value. fig. 3b is used for reference. a resist mask 52 (mask 50 ) having an opening on the region 21 sd and the upper surface of the cathode pad 30 , is formed. by etching the hard mask 51 on the region 21 sd using the resist mask 52 as a mask, the cap layer 12 d of the region 21 sd is exposed. fig. 3c is used for reference. the cap layer 12 d of the region 21 sd is etched by pec etching, with the resist mask 52 (and the hard mask 51 and the insulating film 13 interposed under the resist mask 52 ) used as the mask 50 , to thereby form the ohmic recess 110 sd. thereafter, the resist mask 52 is removed. fig. 4a is used for reference. a resist mask 53 having an opening on the region 21 is is formed. the gate recess 110 g and the ohmic recess 110 sd are filled with the resist mask 53 , to cover an entire upper surface of the cathode pad 30 . fig. 4b is used for reference. the element separation structure 160 , which is an element separation groove, is formed by etching the cap layer 12 d , the barrier layer 12 c , and the channel layer 12 b of the region 21 is, with the resist mask 53 (and the hard mask 51 and the insulating film 13 interposed under the resist mask 53 ) used as the mask 50 . for the etching to form the element separation structure 160 , for example, dry etching such as inductively coupled plasma reactive ion etching is used. the device separation structure 160 may be formed by ion implantation into the epi layer 12 instead of etching the epi layer 12 . fig. 4c is used for reference. the resist mask 53 and the hard mask 51 are removed. further, for example, the processing object 100 is washed with a mixed aqueous solution (hydrochloric acid excess water) of hydrochloric acid (hcl) and hydrogen peroxide (h 2 o 2 ). for example, the cathode pad 30 can be removed by washing with hydrochloric acid hydrogen peroxide. as described above, dislocations are distributed at a predetermined density on the upper surface of the epi layer 12 . since a lifetime of the holes is short in dislocations, pec etching is unlikely to occur. therefore, convex portions are likely to be formed as undissolved portions of the pec etching, at positions corresponding to dislocations, at the bottom of the gate recess 110 g and ohmic recess 110 sd formed by the pec etching. according to the findings obtained by the inventor of the present application, for example, washing with hydrogen peroxide can be used to etch the convex portion, that is, to improve the flatness of the bottoms of the gate recess 110 g and the ohmic recess 110 sd. thus, in the present embodiment, the washing treatment performed after the formation of the element separation structure 160 also serves as a removal treatment of the cathode pad 30 and a flattening treatment of the bottoms of the gate recess 110 g and the ohmic recess 110 sd. such a washing treatment may be performed using hydrochloric acid (hcl) aqueous solution, mixed aqueous solution (piranha solution) of sulfuric acid (h 2 so 4 ) and hydrogen peroxide (h 2 o 2 ), tetramethylammonium hydroxide (tmah) aqueous solution, hydrogen fluoride aqueous solution (hydrofluoric acid), and potassium hydroxide (koh) aqueous solution, etc., other than the hydrochloric acid hydrogen peroxide. fig. 5a is used for reference. the source electrode 151 and the drain electrode 153 are formed by lift-off using a resist mask having an opening on the ohmic recess 110 sd. the source electrode 151 and the drain electrode 153 are formed of, for example, a ti/al/ti/au layer. fig. 5b is used for reference. for example, an aluminum oxide film is deposited on the entire upper surface of the processing object 100 . the insulating film 170 is formed by removing a portion of the aluminum oxide film arranged on the upper surface of the source electrode 151 and the drain electrode 153 by photolithography and etching. for the etching of the silicon oxide film, for example, a buffered hydrofluoric acid aqueous solution is used. fig. 5c is used for reference. the gate electrode 152 is formed by lift-off using the resist mask having an opening on the gate recess 110 g. the gate electrode 152 is formed of, for example, a ni/au layer. the gate electrode 152 is formed on the gate recess 110 g through the insulating film 170 which is a gate insulating film. as described above, the hemt150 is manufactured. fig. 6a is a schematic plan view corresponding to fig. 2b , and illustrates a planar arrangement example of the cathode pad 30 . as illustrated in figs. 2b and 6a , the cathode pad 30 is provided outside the element region 180 of the hemt 150 (in plan view) on the laminate 10 . fig. 6b is a schematic plan view corresponding to fig. 3c , and illustrates a planar arrangement example of the gate recess 110 g and the ohmic recess 110 sd. according to the present embodiment, the cathode pad 30 is provided outside the element region 180 . by using the cathode pad 30 provided in this way, the ohmic recess 110 sd can be formed by pec etching. further, by providing the cathode pad 30 outside the element region 180 , the degree of freedom in the shape, arrangement, etc. of the cathode pad 30 can be increased. such a cathode pad 30 can also be used for forming the gate recess 110 g by pec etching. in this example, more specifically, the cathode pad 30 is arranged between the hemt elements adjacent to each other in a gate length direction (left-right direction on a paper surface). for example, as illustrated in fig. 6b , a certain cathode pad 32 is arranged between a drain recess 111 d of the first hemt element on the left side of the paper, and a source recess 112 s of the second hemt element (hemt element on the right side of the paper) adjacent to the first hemt element. thereby, for example, the cathode pad 30 can be provided at equal positions from the drain recess 111 d of the first hemt element and the source recess 112 s of the second hemt element, and therefore it becomes easy to improve the uniformity of pec etching conditions for forming both recesses. further in this example, the cathode pad 30 has a shape extending in the gate width direction (paper surface vertical direction), that is, a shape extending in a direction parallel to a length direction of the ohmic recess 110 sd. thereby, for example, it is easy to improve the uniformity of the pec etching conditions in the length direction of the ohmic recess 110 sd. the present embodiment is an embodiment in which the ohmic recess 110 sd is formed after forming the gate recess 110 g. due to the formation of the gate recess 110 g, the cap layer 12 d of the portion of the gate recess 110 g is removed, and the 2deg under the gate recess 110 g is reduced. due to this, the source recess 110 s and the drain recess 1101 d of the same hemt element are less likely to conduct with the same cathode pad 30 . for example, as illustrated in fig. 6b , the cathode pad 31 arranged on the source recess 111 s side of the first hemt element is difficult to conduct with the drain recess 111 d arranged on the side opposite to the cathode pad 31 with respect to the gate recess 111 g. however, the drain recess 111 d of the first hemt element can easily conduct with the cathode pad 32 arranged on the same side as the drain recess 111 d with respect to the gate recess 111 g. further, similarly, the source recess 112 s of the second hemt element can easily conduct with the cathode pad 32 arranged on the same side as the source recess 112 s with respect to the gate recess 112 g. thus, in this example, since the cathode pad 30 arranged between the hemt elements adjacent to each other in the gate length direction is shared in the pec etching for forming the ohmic recess 110 sd of these hemt elements, the formation of the ohmic recess 110 sd can be performed well. thereby, for example, it is possible to improve the uniformity of the pec etching conditions in the hemt elements adjacent to each other in the gate length direction, and to facilitate the formation of the ohmic recess 110 sd after forming the gate recess 110 g. fig. 7a is a schematic plan view corresponding to fig. 4b , and illustrates an example of a planar arrangement of the element separation structure 160 . the element separation structure 160 defines an element region 180 that functions as a hemt element. in a plan view, the element region 180 is an internal region of a closed edge (hemt element side, that is, an inner edge shown by a thick broken line) surrounding the hemt element of the element separation structure 160 . the present embodiment is an embodiment in which the element separation structure 160 is formed with the cathode pad 30 provided. the cathode pad 30 functions as at least a part of the mask 50 when forming the element separation structure 160 (when performing dry etching, ion implantation, etc.). therefore, in this example, the element separation structure 160 is formed so as not to overlap (in a plan view) with the arrangement region of the cathode pad 30 . in the embodiment in which the element separation structure 160 is formed with the cathode pad 30 provided, it is preferable to perform dry etching to form the element separation structure 160 , in a state of forming a mask (resist mask 53 ) that covers the cathode pad 30 so as not to be exposed (see fig. 4b ). thereby, it is possible to suppress etching of the cathode pad 30 by the dry etching, and suppress unnecessary contamination caused by a material (for example, a metal such as ti) constituting the cathode pad 30 . in the element separation structure 160 , the 2deg is divided, and the conduction by the cap layer 12 d is also lost. therefore, after the element separation structure 160 is formed, the ohmic recess 110 sd (or gate recess 110 g) arranged in the device region 180 cannot be formed by the pec etching using the cathode pad 30 provided outside the device region 180 . therefore, according to the present embodiment, the element separation structure 160 is formed after forming the ohmic recess 110 sd (and gate recess 110 g) by pec etching using the cathode pad 30 provided outside the device region 180 . fig. 7b is a schematic plan view corresponding to fig. 5c , and illustrates a planar arrangement example of the source electrode 151 , the gate electrode 152 , and the drain electrode 153 . a gate length lg of the hemt element is defined by a width of the gate electrode 152 . the source electrode 151 , the gate electrode 152 , and the drain electrode 153 are arranged side by side in a gate length direction. a direction orthogonal to the gate length direction is the gate width direction, and a gate width wg is defined by a length of the element region 180 in the gate width direction. the source electrodes 151 , the gate electrodes 152 , and the drain electrodes 153 may be electrically connected to each other between adjacent hemt elements, if necessary. according to the present embodiment, both the etching for forming the gate recess 110 g and the etching for forming the ohmic recess 110 sd are performed by pec etching. hereinafter, the pec etching for forming the gate recess 110 g is also referred to as a pec etching for the gate recess 110 g, and the pec etching for forming the ohmic recess 110 sd is also referred to as a pec etching for forming the ohmic recess 110 sd. the light source 220 may be switched (the wavelength characteristic of the light 221 may be changed) for each of the pec etching for the gate recess 110 g and the pec etching for the ohmic recess 110 sd. however, it is preferable to use the same light source 220 (light 221 having the same wavelength properties) for both pec etchings, from a viewpoint of simplifying the structure of the pec etching apparatus 200 . in the example in which the cap layer 12 d is made of gan and the barrier layer 12 c is made of algan, the cap layer 12 d (gan) can also be pec-etched by the short-wavelength light 221 capable of pec-etching the barrier layer 12 c (algan). the pec etching for the gate recess 110 g can be stopped by self-stop as described above. on the other hand, when performing pec etching for the ohmic recess 110 sd using such short wavelength light 221 , etching will proceed deeply until it stops by itself if no time limit is set. therefore, the pec etching for the ohmic recess 110 sd is stopped by time control. thereby, both pec etchings can be performed using the same light source 220 . in pec etching for the ohmic recess 110 sd, etching may be stopped when a total thickness of the cap layer 12 d is etched by using a long wavelength light 221 possible to pec-etch the cap layer 12 d but not possible to pec-etch the barrier layer 12 c. the time required for the pec etching for the gate recess 110 g is longer than the time required for the pec etching for the ohmic recess 110 sd, which is shallower than the pec etching for the gate recess 110 g. according to the present embodiment, the pec etching for the gate recess 110 g, which takes a long time, is performed using a hard mask 51 . pec etching for gate recess 110 g may be performed using a resist mask (only). however, it is preferable to use the hard mask 51 for the pec etching for the gate recess 110 g in order to further improve a resistance of the mask to the etching solution 201 and further improve patterning accuracy. according to the present embodiment, after the pec etching for the gate recess 110 g, the pec etching for the ohmic recess 110 sd is performed. during the pec etching for the gate recess 110 g, the cap layer 12 d of the region 21 sd corresponding to the ohmic recess 110 sd is in a state of being protected by the hard mask 51 (see fig. 3a ). thereby, unnecessary etching of the cap layer 12 d of the region 21 sd can be further suppressed as compared with a state in which the cap layer 12 d is protected by a resist mask (only). the pec etching for the ohmic recess 110 sd is performed using the hard mask 51 having an opening formed on the region 21 sd and a resist mask 52 , and is performed in a state where the gate recess 110 g is filled with the resist mask 52 , preferably at least the resist mask 52 covers a side surface of the gate recess 110 g made of group iii nitride (see fig. 3c ). since the side surface of the gate recess 110 g is protected by the resist mask 52 , unnecessary side etching of the side surface can be suppressed in the pec etching for the ohmic recess 110 sd. in this example, the gate recess 110 g is protected only by the resist mask during the pec etching for the ohmic recess 110 sd. however, the time required for the pec etching for the ohmic recess 110 sd is short, and therefore a problem is unlikely to occur. it is no problem whichever the pec etching for the gate recess 110 g or the pec etching for the ohmic recess 110 sd is performed first, depending on a situation. further, whichever the resist mask or the hard mask may be used to perform the pec etching for the gate recess 110 g and the pec etching for the ohmic recess 110 sd, depending on a situation. the hemt 150 according to the present embodiment has the following features for example, reflecting the above-described manufacturing method. in the manufacturing method according to the present embodiment, the source recess 110 s and the drain recess 1101 d (and further the gate recess 110 g) can be formed by pec etching. therefore, a plasma damage that would be introduced when the source recess and drain recess are formed by conventional dry etching, is not introduced into the hemt 150 of the present embodiment. that is, in the hemt150 of the present embodiment, no plasma damage has been introduced into the group iii nitride layer located at least directly under the source and drain electrodes (more preferably, also in the group iii nitride layer directly under the gate electrode). in the manufacturing method of the present embodiment, the source recess 110 s and drain recess 110 d (and further the gate recess 110 g) are formed by pec etching using the cathode pad 30 provided outside the element separation structure 160 . in an arrangement region of the cathode pad 30 , the cap layer 12 d is removed to form the recess 110 cp. reflecting this, as illustrated in fig. 5c , the insulating film 170 of the hemt 150 may have a portion 171 provided on the barrier layer 12 c through the cap layer 12 d and a portion 172 provided directly above the barrier layer 12 c , outside the element separation structure 160 with respect to the region where the source electrode 151 , the gate electrode 152 , and the drain electrode 153 are arranged. first modified example a first modified example will be described. fig. 9a is a schematic plan view illustrating a planar arrangement example of the element separation structure 160 according to a first modified example. as illustrated in fig. 9a , the element separation structure 160 may be formed so that at least one end in the gate width direction and the gate length direction of the region 21 sd to be etched in which the ohmic recess 110 sd is formed, and the element separation structure 160 are overlapped (in plan view). that is, the device separation structure 160 may be formed so as to have an overlap (in plan view) with a part of the region 21 sd to be etched in which the ohmic recess 110 sd is formed. thereby, it is possible to more ensure that the ohmic recess 110 sd is arranged without a gap so as to extend to the end of the element region 180 in the gate width direction or the gate length direction. that is, the region 21 sd to be etched may be defined so as to be slightly wider than an effective recess portion that is arranged in the element region 180 and actually functions as the ohmic recess 110 sd. second modified example a second modified example will be described. fig. 9b is a schematic plan view illustrating a planar arrangement example of the element separation structure 160 according to a second modified example. the above-described embodiment is an embodiment in which the element separation structure 160 is formed so as not to overlap with the arrangement region of the cathode pad 30 (in a plan view). as illustrated in fig. 9b , the element separation structure 160 may be formed so as to have an overlap (in a plan view) with the arrangement region of the cathode pad 30 . figs. 10a and 10b are schematic cross-sectional views illustrating a manufacturing step of the hemt150 according to a second modified example. in this modified example, as illustrated in fig. 10a , the cathode pad is removed after the ohmic recess 110 sd (and gate recess 110 g) is formed and before the device separation structure 160 is formed. the cathode pad 30 is removed, for example, by hydrochloric acid hydrogen peroxide. after the cathode pad 30 is removed, the element separation structure 160 is formed in a region overlapping with the arrangement region of the cathode pad 30 as illustrated in fig. 10b . since the cathode pad 30 is removed, the element separation structure 160 can be formed also in the arrangement region of the cathode pad 30 . as in the above embodiment, in a structure in which the arrangement region of the cathode pad 30 and the element separation structure 160 do not overlap, that is, the arrangement region of the cathode pad 30 is provided outside the element separation structure 160 , the arrangement region of the cathode pad 30 cannot be effectively utilized as, for example, the element separation structure 160 . in this modified example, since the element separation structure 160 is formed after removing the cathode pad 30 , the arrangement region of the cathode pad 30 can be effectively utilized. third modified example a third modified example will be described. fig. 11 is a schematic plan view illustrating a planar arrangement example of the cathode pad 30 according to the third modification. the above-described embodiment is an embodiment in which the cathode pad 30 is arranged between the hemt elements adjacent to each other in the gate length direction. as illustrated in fig. 11 , the cathode pad 30 may be arranged between the hemt elements adjacent to each other in the gate width direction. the cathode pad 30 has, for example, a shape extending in the gate length direction, that is, a shape extending in a direction orthogonal to a length direction of the ohmic recess 110 sd. owing to the cathode pad 30 of this modified example, for example the uniformity of the pec etching conditions in the hemt elements adjacent to each other in the gate width direction, can be improved. fourth modified example a fourth modified example will be described. fig. 12 is a schematic cross-sectional view illustrating hemt 150 according to the fourth modified example. the above embodiment (see fig. 1 ) is an embodiment in which the gate recess 110 g is also formed by pec etching, together with the ohmic recess 110 sd. the fourth modified example is an example in which the gate recess 110 g is not formed. as illustrated in fig. 12 , the hemt 150 according to this modified example has the ohmic recess 110 sd but does not have the gate recess. the gate electrode 152 is formed on, for example, the cap layer 12 d . further in this modified example, no gate insulating film is interposed under the gate electrode 152 . for example, even in the hemt150 of such an embodiment, similarly to the above-described embodiment, the ohmic recess 110 sd can be formed by pec etching using the cathode pad 30 provided outside the element region 180 . other embodiments as described above, the embodiments and modified examples of the present disclosure have been specifically described. however, the present disclosure is not limited to the above-described embodiments and modified examples, and various modifications, improvements, combinations, and the like can be made without departing from the gist thereof. the above-described embodiment and various modified examples, as well as other embodiments described below, may be used in combination as appropriate. the above-described embodiments show that dry etching is used as the etching to form the element separation structure 160 which is an element separation groove. however, pec etching, which is a wet etching, may also be used as the etching. it is found by the present inventors that in order to self-stop the pec etching by reducing 2deg, that is, to stop the pec etching at a depth in the middle of the barrier layer 12 c , it is preferable to make the etching solution 201 acidic. in other words, by making the etching solution 201 alkaline, although the mechanism is unknown, (high-speed) pec etching that penetrates the barrier layer 12 c and reaches a depth in the middle of the channel layer 12 b is likely to occur. from the above finding, it is preferable to use the etching solution 201 that is acidic (from the start of the pec etching), for the pec etching for forming the gate recess 110 g and the ohmic recess 110 sd. further, by using the alkaline etching solution 201 , it is possible to form the element separation structure 160 , which is an element separation groove, by pec etching. fig. 13 is a schematic cross-sectional view illustrating a step of forming the element separation structure 160 by pec etching (corresponding to fig. 4b described above). in the example illustrated in fig. 13 , a mask 53 a that exposes at least a part of the cathode pad 30 is formed in order to perform pec etching. in this step, the device separation structure 160 is formed by performing pec etching at a depth at which the channel layer 12 b is exposed on the bottom, using the alkaline etching solution 201 . in contrast, in the steps shown in figs. 3a and 3c , the gate recess 110 g and the ohmic recess 110 sd are formed by performing pec etching at a depth at which the barrier layer 12 c is exposed on the bottom, preferably using the acidic etching solution 201 respectively. in the above-described embodiments, the cathode pad 30 provided outside the element region 180 has been described. however, a part of the cathode pad 30 may have an overlap (in plan view) with the element region 180 . fig. 14 is a schematic plan view illustrating an embodiment in which a part of the cathode pad 30 overlaps with the element region 180 . in the example illustrated in fig. 14 , two hemt elements are arranged side by side in the gate length direction, and these two hemt elements are formed in a common element region 180 . that is, these two hemt elements are surrounded by a common element separation structure 160 . in this example, the cathode pad 33 arranged on the left side of the hemt element on the left side of the paper surface is provided outside the element region 180 , and the cathode pad 34 arranged between the two hemt elements has an overlap with the element region 180 . the above-described embodiment is an embodiment in which a conductive member that is separate from the laminate (nitride semiconductor crystal substrate) 10 is used as the cathode pad (conductive member that functions as a cathode for electrodeless pec etching) 30 . however, as described below, a conductive member (conductive region) composed of a group iii nitride as a part of the laminate 10 may be used as the cathode pad 30 . when comprehensively considering a case where a conductive member different from the laminate 10 is used as the cathode pad 30 , and a case where a conductive member composed of a group iii nitride is used as a part of the laminate 10 , the expression of the cathode portion 30 may be used instead of the expression of the cathode pad 30 . figs. 15a and 15b are schematic cross-sectional views illustrating an embodiment in which the cathode portion 30 is formed by ion-implanting an n-type impurity into the epi layer 12 . fig. 15a corresponds to fig. 2b of the above-described embodiment and illustrates a step of forming the cathode portion 30 . in fig. 15a , a region that becomes the cathode portion 30 is shown by a thick line. in this example, the region in which the cathode portion 30 is arranged in a plan view is referred to as a region 21 cp. the cathode portion 30 is formed by ion-implanting an n-type impurity such as si into the epi layer 12 , by ion-implanting the n-type impurity such as si into the epi layer 12 in a state where a mask having an opening is formed in the region 21 cp. for example, ion implantation is performed so that the cathode portion 30 having an n-type impurity concentration of 1×10 17 cm −3 or more and 1×10 19 cm −3 or less and a depth (thickness) of 100 nm or more and 200 nm or less is formed. for example, in the region 21 cp, the cathode portion 30 is formed by ion-implanting the n-type impurity to a total thickness of the cap layer 12 d , a total thickness of the barrier layer 12 c , and an upper part of the channel layer 12 b. the cathode portion 30 reaches 2deg because it is formed to a depth that reaches the upper part of the channel layer 12 b , and the region 21 to be etched, which is etched by pec etching, and the cathode portion 30 are electrically connected through at least one of the cap layer 12 d and 2deg. in this example, since the cathode portion 30 is directly connected to the 2deg, electrons can be emitted from the cathode portion 30 more effectively. in this example, the region 21 to be etched and the cathode portion 30 are both composed of group iii nitride. further, when the region 21 to be etched is irradiated with the light 221 , the cathode portion 30 is also irradiated with the light 221 . however, the group iii nitride constituting the cathode portion 30 has an n-type impurity concentration higher than that of the region 21 to be etched (preferably, for example, 10 times or more higher). thereby, in the cathode portion 30 having a higher electron concentration than the region 21 to be etched, an anodizing reaction can be suppressed by consuming photoexcited holes in a short time, and therefore the cathode portion 30 is suppressed from being pec-etched and can function as a cathode for pec etching. this also applies to the embodiment in which the cathode portion 30 is formed by regrowth described later. it can be said that the region 21 to be etched by pec etching is a cap layer 12 d or a barrier layer 12 c , which is a portion of the epi layer 12 above a lower surface of the barrier layer 12 c . typically, the n-type impurity is not added to the barrier layer 12 c , and the n-type impurity is added to the cap layer 12 d . the n-type impurity is added so that the cathode portion 30 has an n-type impurity concentration higher than that of the cap layer 12 d , that is, an n-type impurity concentration higher than a highest n-type impurity concentration in the region 21 to be etched (preferably, for example, 10 times or more higher). the step after forming the cathode portion 30 is the same as that of the above-described embodiment. during the pec etching of the region 21 to be etched, by bringing the cathode portion 30 into contact with the etching solution 201 , the cathode portion 30 functions as a cathode for pec etching. the cathode portion 30 (the group iii nitride layer constituting the cathode portion 30 ) may not be removed and may remain after the formation of the device separation region 160 . the cathode portion 30 may be removed by etching at the time of forming the element separation region 160 which is an element separation groove. the cathode portion 30 may be ion-implanted for element separation when the element separation region 160 is formed by ion implantation. fig. 15b corresponds to fig. 1a of the above-described embodiment and schematically illustrates the hemt150 of this example. the epi layer 12 of the hemt 150 of this example may have the cathode portion 30 having a depth reaching the upper part of the channel layer 12 b outside the element region 180 in a plan view, reflecting the above-described manufacturing method. the cathode portion 30 has an n-type impurity concentration higher than a (highest) n-type impurity concentration in the portion above the lower surface of the barrier layer 12 c in the epi layer 12 in the device region 180 in a plan view. fig. 16 is a schematic cross-sectional view illustrating an embodiment in which the cathode portion 30 is formed by regrowth of the group iii nitride layer to which the n-type impurity is added. this example may be regarded as an embodiment in which, for example, the cathode portion 30 made of ti in the above-described embodiment is composed of a group iii nitride having a high n-type impurity concentration instead of ti. a method of forming the cathode portion 30 of this example will be described with reference to fig. 2b . the cathode portion 30 is formed by regrowth of gan to which the n-type impurity such as si is added above the barrier layer 12 c in a state where the mask having an opening is formed in the region 21 cp. as a method of the regrowth, sputtering, pulsed laser deposition (pld), organometallic chemical vapor deposition (mocvd), molecular beam epitaxy (mbe), or the like may be appropriately used. for example, the cathode portion 30 having an n-type impurity concentration of 1×10 17 cm −3 or more and 1×10 19 cm −3 or less and a thickness of about 50 nm, is grown. the cathode portion 30 may be provided on the cap layer 12 d in the same manner as described in the embodiment in which the cathode portion 30 is made of ti. the step after forming the cathode pad 30 is the same as that of the above-described embodiment. also in this example, the cathode portion 30 may not be removed and may remain after the formation of the element separation region 160 . fig. 16 corresponds to fig. 1a of the above-described embodiment and schematically illustrates the hemt150 of this example. the epi layer 12 of the hemt 150 of this example may have the cathode portion 30 grown above the barrier layer 12 c (or above the cap layer 12 d ) outside the element region 180 in a plan view, reflecting the above-described manufacturing method. the cathode portion 30 has an n-type impurity concentration higher than an n-type impurity concentration in the portion above the lower surface of the barrier layer 12 c in the epi layer 12 in the device region 180 in a plan view. <preferable aspects of the present disclosure> hereinafter, preferable aspects of the present disclosure will be supplementarily described. (supplementary description 1) there is provided a method for manufacturing a nitride-based high electron mobility transistor, including: providing a conductive member on a nitride semiconductor crystal substrate, outside an element region of the high electron mobility transistor in a plan view; forming a mask on the nitride semiconductor crystal substrate, the mask having an opening (and having an opening that exposes the conductive member) in at least one of a source recess etching region where a source recess is formed, which is a recess in which a source electrode of the high electron mobility transistor is arranged, and a drain recess etching region where a drain recess is formed, which is a recess in which a drain electrode of the high electron mobility transistor is arranged; performing photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light to form at least one of a source recess and a drain recess, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons; and forming an element separation structure (that defines the element region) of the high electron mobility transistor (after the photoelectrochemical etching). (supplementary description 2) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 1, wherein each of the above steps is performed in an order described in the supplementary description 1. (supplementary description 3) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 1 or 2, wherein the nitride semiconductor crystal substrate includes on the base substrate at least: a channel layer on which two-dimensional electron gas is formed; a barrier layer formed on the channel layer, and a cap layer formed on the barrier layer and which is composed of a group iii nitride having a bandgap smaller than that of a group iii nitride constituting the barrier layer, and in the photoelectrochemical etching, the cap layer (only) is removed. (supplementary description 4) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 3, wherein the conductive member is electrically connected to the source recess etching region or the drain recess etching region, through at least one of the cap layer and the two-dimensional electron gas. (supplementary description 5) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 4, wherein in the formation of the element separation structure, the element separation structure is formed so as to have an overlap in a plan view with at least one part of the source recess etching region and the drain recess etching region. (supplementary description 6) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 5, wherein in the formation of the element separation structure, the element separation structure is formed by any one of the techniques of ion implantation, dry etching, and photoelectrochemical etching. (supplementary description 7) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 6, wherein in the formation of the element separation structure, the element separation structure is formed so as not to have an overlap with an arrangement region of the conductive member in a plan view. (supplementary description 8) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 7, wherein in the formation of the element separation structure, the element separation structure is formed by ion implantation using the conductive member as at least a part of a mask. (supplementary description 9) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 7, wherein in the formation of the element separation structure, the element separation structure is formed by dry etching, at least in a state where a mask is formed to cover the source recess or the drain recess and the conductive member so as not to be exposed. (supplementary description 10) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 7, wherein in the formation of the element separation structure, the element separation structure is formed, in a state where a mask is formed to expose at least a part of the conductive member. (supplementary description 11) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 10, wherein photoelectrochemical etching in the formation of at least one of the source recess and the drain recess is performed using an acidic etching solution, and photoelectrochemical etching in the formation of the element separation structure is performed using an alkaline etching solution. preferably, photoelectrochemical etching in the formation of the gate recess of the supplementary description 17 is performed using an acidic etching solution. (supplementary description 12) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 6, wherein in the formation of the element separation structure, the element separation structure is formed so as to have an overlap with an arrangement region of the conductive member in a plan view. (supplementary description 13) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 12, wherein the formation of the element separation structure is performed after removing the conductive member. (supplementary description 14) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 13, wherein in the manufacturing of a nitride-based high electron mobility transistor, a plurality of high electron mobility transistors are manufactured, which are arranged in at least one direction of a gate length direction and a gate width direction on the nitride semiconductor crystal substrate, and the conductive member is arranged between at least one of the high electron mobility transistor elements adjacent to each other in the gate length direction and the high electron mobility transistor elements adjacent to each other in the gate width direction. the plurality of conductive members may be arranged side by side in at least one direction of the gate length direction and the gate width direction. (supplementary description 15) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 14, wherein the conductive member arranged between the high electron mobility transistor elements adjacent to each other in the gate length direction has a shape extending in the gate width direction. (supplementary description 16) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 14 or 15, wherein the conductive member arranged between the high electron mobility transistor elements adjacent to each other in the gate width direction has a shape extending in the gate length direction. (supplementary description 17) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 1 to 16, further including: forming another mask on the nitride semiconductor crystal substrate, the mask having an opening (and an opening that exposes the conductive member) in a gate recess etching region where a gate recess is formed, which is a recess in which a gate electrode of the high electron mobility transistor is arranged; forming the gate recess by performing other photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons; and forming the element separation structure (after the photoelectrochemical etching and the other photoelectrochemical etching). (supplementary description 18) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 17, wherein the nitride semiconductor crystal substrate includes on a base substrate, at least: a channel layer on which a two-dimensional electron gas is formed, a barrier layer formed on the channel layer, and a cap layer formed on the barrier layer and which is composed of a group iii nitride having a bandgap smaller than that of the group iii nitride constituting the barrier layer, and in the photoelectrochemical etching, the cap layer (only) is removed, and in the other photoelectrochemical etching, the cap layer and a part of the barrier layer are removed. (supplementary description 19) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to the supplementary description 17 or 18, wherein in the photoelectrochemical etching and the other photoelectrochemical etching, light irradiation is performed using a same light source (light having the same wavelength properties), and the photoelectrochemical etching is stopped by time control, and the above other photoelectrochemical etching is stopped by self-stop. (supplementary description 20) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 17 to 19, wherein the above other photoelectrochemical etching is performed prior to the photoelectrochemical etching, and in the above other photoelectrochemical etching, the above other mask is formed using a hard mask made of an inorganic material or a metallic material. (supplementary description 21) there is provided the method for manufacturing a nitride-based high electron mobility transistor according to any one of the supplementary descriptions 17 to 20, wherein in the photoelectrochemical etching, the mask is formed using a resist mask. (supplementary description 22) there is provided a method for manufacturing a nitride-based high electron mobility transistor, including: providing a conductive member on a nitride semiconductor crystal substrate, outside an element region of the high electron mobility transistor in a plan view; forming a mask on the nitride semiconductor crystal substrate, the mask having an opening (and having an opening that exposes the conductive member) in a gate recess etching region where a gate recess is formed, which is a recess in which a gate electrode of the high electron mobility transistor is arranged: performing photoelectrochemical etching by irradiating the nitride semiconductor crystal substrate with light to form the gate recess, in a state where the nitride semiconductor crystal substrate on which the conductive member is provided and the mask is formed is in contact with an etching solution containing an oxidizing agent that receives electrons; and forming an element separation structure (that defines the element region) of the high electron mobility transistor (after the photoelectrochemical etching). (supplementary description 23) there is provided a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer, a barrier layer arranged on the channel layer, and a cap layer arranged on the barrier layer; a source electrode, a gate electrode, and a drain electrode; and an element separation structure, wherein plasma damage is not introduced into at least a group iii nitride layer located directly under the source electrode and the drain electrode. (supplementary description 24) there is provided a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer, a barrier layer arranged on the channel layer, and a cap layer arranged on the barrier layer; a source electrode, a gate electrode, and a drain electrode; and an element separation structure, wherein the insulating film covers the element separation structure and is provided so as to extend to outside of the element separation structure with respect to a region where the source electrode, the gate electrode, and the drain electrode are arranged, and has a portion provided on the barrier layer through the cap layer and a portion provided directly above the barrier layer, outside the element separation structure. (supplementary description 25) there is provided a method for manufacturing a structure, including: preparing a processing object including a region to be etched composed of a group iii nitride, and a cathode portion composed of a group iii nitride having a higher concentration of n-type impurities than the region to be etched and electrically connected to the region to be etched; etching the region to be etched by irradiating the region to be etched (and the cathode portion) with light in a state where the region to be etched and the cathode portion are in contact with an etching solution containing an oxidizing agent that receives electrons. (supplementary description 26) there is provided a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer and a barrier layer arranged on the channel layer (preferably further having a cap layer arranged on the barrier layer); and a source electrode, a gate electrode, and a drain electrode; and an element separation structure, wherein the group iii nitride layer has a cathode portion having a depth reaching an upper part of the channel layer outside an element region of the high electron mobility transistor in a plan view, and the cathode portion has an n-type impurity concentration higher than the n-type impurity concentration in a portion above a lower surface of the barrier layer in the group iii nitride layer in the element region of the high electron mobility transistor in a plan view. (supplementary description 27) a nitride-based high electron mobility transistor, including: a group iii nitride layer having at least a channel layer and a barrier layer arranged on the channel layer (preferably further having a cap layer arranged on the barrier layer); and a source electrode, a gate electrode, and a drain electrode; and an element separation structure, wherein the group iii nitride layer has a cathode portion grown above the barrier layer outside the element region of the high electron mobility transistor in a plan view, and the cathode portion has an n-type impurity concentration higher than an n-type impurity concentration in a portion above the lower surface of the barrier layer in the group iii nitride layer in the element region of the high electron mobility transistor in a plan view.
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049-781-182-116-840
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CN
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A23L33/115,C12N1/14,C12P7/64,A23L33/00,C12N1/00,C12P7/00,C12P7/6463,A23L29/00,C12N1/12,C12P7/6472,C12R1/89,C12R1/645,A23D9/02,C11B1/10
| 2019-11-26T00:00:00 |
2019
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schizochytrium strain and use thereof, microbial oil containing dha at sn-2 position and preparation and use thereof
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a schizochytrium and an application thereof, and an sn-2 dha-rich microbial oil, a preparation method therefor, and an application thereof. the proportion of sn-2 dha in triglycerides in the microbial oil is not less than 23%. the preparation method for the microbial oil comprises inoculating a schizochytrium strain into a fermentation medium to carry out fermentation to give the product. the schizochytrium strain is schizochytrium sp. with the deposit number gdmcc no. 60733. the proportion of sn-2 dha in the triglycerides in the microbial oil is not less than 23%, so that the human body absorption rate of dha in the microbial oil is significantly higher than that of a microbial oil produced from conventional strains, promoting the absorption and utilization of the functional fatty acid dha by the human body.
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a microbial oil, comprising: a triglyceride; wherein sn-2 fatty acids of the triglyceride comprises 23% or more by weight of dha. the microbial oil according to claim 1, characterized in that a weight percentage of total dha in the microbial oil is not less than 38%. a method for producing a microbial oil, comprising: inoculating a schizochytrium strain into a fermentation medium for fermentation to produce the microbial oil; wherein the schizochytrium strain is schizochytrium sp. gdmcc no. 60733; the fermentation is carried out at ph 6-7.5 and 27-31°c for 4-8 days under a ventilation rate of 0.45-1.1 vvm; the fermentation medium comprises 5-70 g/l of a carbon source, 15-45 g/l of a nitrogen source, 5-40 g/l of an inorganic salt, 0.01-0.04 g/l of a trace element and 0.01-0.04 g/l of a vitamin; the nitrogen source comprises glutamate; and a concentration of glutamate in the fermentation medium is 5-15 g/l. the method according to claim 3, characterized in that the method comprises: inoculating the schizochytrium sp. gdmcc no. 60733 into an activation medium for activation to obtain an activated schizochytrium suspension; inoculating the activated schizochytrium suspension into a seed culture medium for expansion culture to obtain a seed liquid; and inoculating the seed liquid into the fermentation medium for the fermentation to produce the microbial oil; wherein the activation is carried out at 27.5-28.5°c and 150-200 r/min for 48-72 hours; the activation medium comprises 30-50 g/l of a carbon source, 25-45 g/l of a nitrogen source, 25-40 g/l of an inorganic salt, 0.015-0.025 g/l of a trace element and 0.01-0.02 g/l of a vitamin; the expansion culture is carried out at 27-28.5°c under a ventilation rate of 0.5-0.8 vvm for 48-72 hours; and the seed culture medium comprises 25-60 g/l of a carbon source, 10-30 g/l of a nitrogen source, 15-35 g/l of an inorganic salt, 0.01-0.02 g/l of a trace element and 0.01-0.02 g/l of a vitamin. the method according to claim 3 or 4, characterized in that the carbon source in the fermentation medium, the carbon source in the activation medium and the carbon source in the seed culture medium are independently selected from the group consisting of glucose, sucrose and a combination thereof; the nitrogen source in the fermentation medium, the nitrogen source in the activation medium and the nitrogen source in the seed culture medium are independently selected from the group consisting of sodium glutamate, yeast powder, yeast extract and a combination thereof; the inorganic salt in the fermentation medium, the inorganic salt in the activation medium and the inorganic salt in the seed culture medium are independently selected from the group consisting of calcium salt, phosphate, potassium salt, sodium salt, magnesium salt, ammonium salt and a combination thereof; the trace element in the fermentation medium, the trace element in the activation medium and the trace element in the seed culture medium are independently selected from the group consisting of nickel, copper, molybdenum, cobalt, zinc, iron, manganese and a combination thereof; and/or the vitamin in the fermentation medium, the vitamin in the activation medium and the vitamin in the seed culture medium are independently selected from the group consisting of vitamin b 1 , vitamin b 12 , vitamin b 6 , calcium pantothenate, biotin and a combination thereof. the method according to claim 3, further comprising: subjecting a product of the fermentation to extraction to produce the microbial oil. a microbial oil produced by the method according to any one of claims 3-6, comprising: a triglyceride; wherein sn-2 fatty acids of the triglyceride comprise 23% or more by weight of dha; and a weight percentage of total dha in the microbial oil is not less than 38%. the microbial oil according to claim 1, 2 or 7 for use in the preparation of a food, characterized in that the food is an infant formula food, a nutraceutical or a health food. a schizochytrium strain, characterized in that the schizochytrium strain has an accession number of gdmcc no. 60733. the schizochytrium strain of claim 9 for use in the production of a microbial oil, characterized in that the microbial oil comprises a triglyceride; wherein sn-2 fatty acids of the triglyceride comprise 23% or more by weight of dha; and a weight percentage of total dha in the microbial oil is not less than 38%.
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technical field the present disclosure relates to microbial technology, and more particularly to a schizochytrium strain and a use thereof, a microbial oil containing dha at an sn-2 position, and a preparation and a use thereof. background docosahexaenoic acid (dha) is a primary structural fatty acid in the brain and eyes, accounting for 97% and 93% of all n-3 fatty acids in the brain and eyes, respectively. it has been reported that the triglycerides with the sn-2 position dha are easier to be absorbed by intestinal mucosa. meanwhile, it has also been demonstrated that when the intake of those lipids with the sn-2 position dha will make dha most enriched in the brain, whereas when people take in lipids with dha at other positions, of the highest level of dha will occur in the liver, which indicates that triglycerides with different structures will experience different fatty acid metabolism routes, in other words, the fatty acids at the sn-2 position can be more effectively absorbed than those at the sn-1 or sn-3 position. as a primary lipase, pancreatic lipase attaches to a water-oil interface to hydrolyze dietary fat molecules. meanwhile, pancreatic lipase is specific to the hydrolysis of ester bonds at the sn-1 and sn-3 positions. as a consequence, after digested by pancreatic lipase, the triglyceride structure is converted into free fatty acids (from sn-1 and sn-3 positions) and a monoglyceride (formed by the glycerol skeleton and the sn-2 fatty acid).the free fatty acids have difficulty in penetrating into bile salt micelle to be absorbed, and thus are prone to combining with calcium and magnesium ions in the intestine to form insoluble soap salts to be wasted, whereas the monoglyceride formed from the fatty acid at the sn-2 position can easily penetrate into the bile salt micelle to be absorbed. therefore, the absorption rate of fatty acids at the sn-2 position in human body is higher than that of the fatty acids at the sn-1 and sn-3 positions. as consumers become more aware of the health and function of dha, microbial oils, as primary resources of dha, have been largely adopted in infant food and nutraceuticals, and their nutritional benefits are increasingly recognized by public. consequently, more and more attention has been paid to the absorption rate of dha in microbial oils. more than 90% of the fatty acids in the microbial oil exist in the form of triglyceride, and the existing dha-containing microbial oils are mainly produced by fermentation using ukenella, schizochytrium, thraustochytrium, cryptodinium, and yeast. however, the incorporation rate of dha at sn-2 position of the glycerol skeleton is far lower than that at the sn-1 and sn-3 positions, and a large amount of sn-1 and sn-3 dha is converted into soap salts to be wasted, attenuating the benefits of the microbial oils. summary the object of the present disclosure is to provide a schizochytrium strain and use thereof, a microbial oil containing dha at an sn-2 position and preparation and use thereof to solve the problem that human body has a poor adsorption to dha in the microbial oil since dha on the triglyceride in the microbial oil is dominated by sn-1 and sn-3 dha. the schizochytrium strain provided herein is schizochytrium sp, and the microbial oil provided herein is produced through the fermentation using schizochytrium sp, in which sn-2 fatty acids of the triglyceride include 23% or more by weight of dha, effectively improving the absorption of dha in human body. technical solutions of this application are described as follows. in a first aspect, the present disclosure provides a microbial oil, which comprises: a triglyceride; wherein sn-2 fatty acids of the triglyceride contain 23% or more by weight of dha. in some embodiments, the microbial oil contains 38% or more by weight of dha. in a second aspect, the present disclosure further provides a method for producing the microbial oil mentioned above, comprising: inoculating a schizochytrium strain into a fermentation medium for fermentation to produce the microbial oil; wherein the schizochytrium strain has an accession number of gdmcc no. 60733. in a third aspect, the present disclosure provides a microbial oil prepared by the above-mentioned method, comprising: a triglyceride; wherein sn-2 fatty acids of the triglyceride contain 23% or more by weight of dha. in a fourth aspect, the present disclosure provides a food comprising the above-mentioned microbial oil, and the food is infant formula food, nutraceutical or health food. in a fifth aspect, the present disclosure provides a schizochytrium strain, where the schizochytrium strain has an accession number of gdmcc no. 60733. in a sixth aspect, the present disclosure provides a use of the schizochytrium strain in the preparation of the above-mentioned microbial oil. the schizochytrium sp.-derived microbial oil provided herein is rich in dha, and a weight percentage of dha at the sn-2 position of the triglyceride in total sn-2 fatty acids is not less than 23%, which effectively facilitates the absorption and utilization of dha in the microbial oil in human body. the features and beneficial effects will be further described in detail below with reference to the embodiments. deposit of microorganisms the schizochytrium strain used herein has been deposited in guangdong microbial culture collection center (gdmcc, guangdong institute of microbiology, 5 th floor, no. 59 building, no. 100 xianliezhong road, guangzhou, china, 510070) on august 8, 2019 with an accession number of gdmcc no. 60733. detailed description of embodiments it should be noted that endpoints and values within ranges disclosed herein are only exemplary, and are intended to include any values close to these values or ranges. any possible combination of values within the numerical range to form one or more new ranges should be considered to be expressly disclosed in this disclosure. in a first aspect, the present disclosure provides a microbial oil, which includes a triglyceride, where sn-2 fatty acids of the triglyceride include 23% or more by weight of dha. the dha is abbreviation of docosahexenoic acid. in some embodiments, a weight percentage of the triglyceride in the microbial oil is not less than 90%. in some embodiments, a weight percentage of total dha in the microbial oil is not less than 38%. it should be understood that the total dha is a total amount of dha in the microbial oil, and can be measured according the method of gb 26400-2011. the contents of other fatty acids are measured according to the method of gb 5009.168-2016. triglyceride dha means that dha is linked to the glycerol backbone through ester bonds. in some embodiments, a weight percentage of dha at the sn-2 position of the triglyceride in the microbial oil is not less than 23%. in some embodiments, a weight percentage of dha at the sn-2 position of the triglyceride in the microbial oil is not less than 23%, and a weight percentage of total dha in the microbial oil is not less than 38%. in a second aspect, the present disclosure further provides a method for producing the microbial oil mentioned above. a schizochytrium strain is inoculated into a fermentation medium for fermentation, where an accession number of the schizochytrium strain is gdmcc no.60733. the strain for preparing the microbial oil can be obtained by a conventional method in the art. the schizochytrium strain provided herein is obtained by mutagenesis. the mutagenesis is performed according to a conventional method, such as physical mutagenesis (ultraviolet mutagenesis, atmospheric room temperature plasma (artp) mutagenesis) and chemical mutagenesis. in some embodiments, the mutagenesis is performed by artp mutagenesis. the artp mutagenesis is carried out in a conventional mutagenesis system such as multifunctional mutagenesis system (mpms) produced by adhoc interteck co., ltd. (beijing, china). the mutagenesis is performed according to conventional operations in the art. in an embodiment, the mutagenesis is performed at a plasma mutagenesis power of 80-120 w, a gas flow rate of 8-12 slm (standard liter per minute) and a treatment distance of 1-3 mm. the mutagenesis time is 5-60 s, preferably 15-30 s. the mutagenesis is performed on a bacterial suspension with od 600 of 0.6-0.8 or a bacterial concentration of 10 6 -10 8 cfu/ml. in some embodiments, the mutagenesis is performed such that a lethality of the schizochytrium strain is 90-95%. the starting strain is subjected to mutagenesis and multiple screenings to obtain a strain with high oil yield and high sn-2 position dha content. it should be understood by those skilled in the art that the percentage of the triglyceride with dha at the sn-2 position is used as an indicator for the screening of a desired high yield strain. the content of sn-2 fatty acids is determined according to the method recited in gb/t 24984-2010/iso 6800:1997 "animal and vegetable fats and oils-determination of the composition of fatty acids in the 2-position of the triglyceride molecules". in order to obtain a strain with high stability, the screened strain can also be evaluated for genetic stability. it has been accepted in the verification of genetic stability in the modern breeding that if the strain obtained from the mutation breeding can still meet the expected requirements of biological characteristics after five passages, it is considered to have high stability. through the mutagenesis, screening and genetic stability evaluation mentioned above, a strain with high yield of the sn-2 dha is obtained. the schizochytrium strain of the present disclosure has been deposited in guangdong microbial culture collection center (gdmcc, guangdong institute of microbiology, 5 th floor, no. 59 building, no. 100 xianliezhong road, guangzhou, 510070, china) on august 8, 2019 with an accession number of gdmcc no. 60733. after the fermentation, the schizochytrium strain provided herein can produce an sn-2 dha-rich microbial oil, and the fermentation method has no special requirements as long as it enables the proliferation of the schizochytrium strain. there are no special requirements for the fermentation by the schizochytrium strain. in some embodiments, the fermentation is performed at ph 6-7.5 and 27-31°c for 4-8 days under a ventilation rate of 0.5-1.1 vvm. when the schizochytrium strain is inoculated in the form of a seed liquid, the inoculation amount can be selected in a wide range, such as 5-10% (v/v). the fermentation medium used herein can be a medium commonly used in the art for the fermentation by the schizochytrium strain. in an embodiment, the fermentation medium includes a carbon source, a nitrogen source, an inorganic salt, a trace element and a vitamin. the carbon source is glucose, sucrose, or other substances that can provide a carbon source or a combination thereof, and the nitrogen source is sodium glutamate, yeast powder, yeast extract or other substances that can provide a nitrogen source or a combination thereof. in some embodiments, the carbon source is selected from the group consisting of glucose, sucrose and a combination thereof. in some embodiments, the nitrogen source is selected from the group consisting of sodium glutamate, yeast powder, yeast extract and a combination thereof. in some embodiments, the inorganic salt is selected from the group consisting of calcium salt, phosphate, potassium salt, sodium salt, magnesium salt, ammonium salt and a combination thereof. in some embodiments, the trace element is selected from the group consisting of nickel, copper, molybdenum, cobalt, zinc, iron, manganese and a combination thereof. in some embodiments, the vitamin is selected from the group consisting of vitamin b 1 , vitamin b 12 , vitamin b 6 , calcium pantothenate, biotin and a combination thereof. the carbon source, nitrogen source and inorganic salt can be directly added to a medium. however, when a volume of the medium is small, it is difficult to directly add the trace element and the vitamin to the medium, and at this time, the trace element and the vitamin are often prepared into a mother liquor to be added. contents of each component in the trace-element mother liquor can be selected within a wide range. in some embodiments, the trace-element mother liquor contains 1-3 g/l of nickel sulfate, 1-3 g/l of copper sulfate, 0.02-0.08 g/l of sodium molybdate, 2-4 g/l of manganese chloride, 0.02-0.08 g/l of cobalt chloride, 2-4 g/l of zinc sulfate and 8-10 g/l of ferrous sulfate. contents of each component in a vitamin mother liquor can be selected within a wide range. in some embodiments, the vitamin mother liquor contains 9-11 g/l of vitamin b 1 , 0.1-0.3 g/l of vitamin b 12 , 2-4 g/l of calcium pantothenate and 0.005-0.01 g/l of biotin. in some embodiments, the nitrogen source in the fermentation medium includes glutamate. a concentration of the glutamate can be selected in a wide range. in some embodiments, the concentration of the glutamate in the fermentation medium is 5-15 g/l. a concentration of the carbon source can be selected in a wide range. in some embodiments, the concentration of the carbon source in the fermentation medium is 5-70 g/l. in an embodiment, the fermentation medium contains 5-70 g/l of the carbon source, 15-45 g/l of the nitrogen source, 5-40 g/l of the inorganic salt, 0.01-0.04 g/l of the trace element and 0.01-0.04 g/l of the vitamin, preferably 40-60 g/l of the carbon source, 20-35 g/l of the nitrogen source, 10-25 g/l of the inorganic salt, 0.015-0.035 g/l of the trace element and 0.01-0.03 g/l of the vitamin. in an embodiment, the fermentation medium further includes 0.1-0.5 g/l of an anti-foaming agent. during the fermentation process, the addition of the carbon source and the nitrogen source is continuously performed to adjust the carbon-to-nitrogen ratio. when approaching the fermentation end, the carbon source is not supplied into the medium any more so that the residual sugar is reduced to 0. in this way, an auxotrophic condition is formed by adjusting the carbon-to-nitrogen ratio to improve the oil production of the schizochytrium strains. in order to increase a yield of the fermentation product, in some embodiments, the method includes: activating the schizochytrium strain by shake flask culture to obtain a seed liquid; and inoculating the seed liquid into a seed culture medium followed by transferring to a fermentation medium for the fermentation. in some embodiments, the method includes: inoculating the schizochytrium strain into an activation medium for activation to obtain an activated schizochytrium suspension; inoculating the activated schizochytrium suspension into a seed culture medium for proliferation to obtain a seed liquid; and inoculating the seed liquid into the fermentation medium for the fermentation to produce the microbial oil. the schizochytrium strain provided herein is preserved in an ampoule or a glycerin tube. in some embodiments, in the activating process, the schizochytrium strains stored in a frozen glycerin tube are thawed and inoculated into an activation medium for activation. the activation can be performed once or multiple times to prepare the activated schizochytrium suspension. the activation conditions can be selected in a wide range. in some embodiments, the activation is carried out at 27.5-28.5°c and 150-200 r/min for 48-72 hours. preferably, the activation medium includes a carbon source, a nitrogen source, an inorganic salt, a trace element and a vitamin. in an embodiment, the activation medium contains 30-50 g/l of the carbon source, 25-45 g/l of the nitrogen source, 25-40 g/l of the inorganic salt, 0.015-0.025 g/l of the trace element and 0.01-0.02 g/l of the vitamin. in an embodiment, the activation is performed through steps of: thawing the schizochytrium strain stored in a frozen glycerin tube followed by inoculation into a sterilized activation medium using a sterile pipette; and culturing the schizochytrium strain at 27.5-28.5°c and 150-200 r/min for 48-72 hours. in an embodiment, the activation medium contains 30-50 g/l of a carbon source, 25-45 g/l of a nitrogen source, 25-40 g/l of an inorganic salt, 0.015-0.025 g/l of a trace element and 0.01-0.02 g/l of a vitamin. preferably, the strain in one tube is inoculated into 4-6 500 ml flasks each containing 200-300 ml of the activation medium. in the expansion culture, the activated schizochytrium suspension is inoculated into a seed culture medium for expansion to obtain a seed liquid. preferably, the expansion culture is carried out at 27-28.5°c under a ventilation rate of 0.5-0.8 vvm for 48-72 hours. preferably, the seed culture medium includes 25-60 g/l of a carbon source, 10-30 g/l of a nitrogen source, 15-35 g/l of an inorganic salt, 0.01-0.02 g/l of a trace element and 0.01-0.02 g/l of a vitamin. preferably, the seed culture medium further includes 0.1-0.5 g/l of an anti-foaming agent. in an embodiment, the expansion culture is performed through steps of: inoculating the activated schizochytrium suspension into a primary seed culture medium for primary expansion followed by inoculation into a secondary seed culture medium for secondary propagation to obtain the seed liquid. preferably, the primary expansion is carried out at 27-28.5°c under a ventilation rate of 0.5-0.8 vvm for 48-60 hours. preferably, the secondary propagation is carried out at 27-28.5°c under a ventilation rate of 0.5-0.8 vvm for 12-24 hours. preferably, the primary seed culture medium contains 25-35 g/l of the carbon source, 10-30 g/l of the nitrogen source, 15-35 g/l of the inorganic salt, 0.01-0.02 g/l of the trace element and 0.01-0.02 g/l of the vitamin. preferably, the secondary seed culture medium contains 40-60 g/l of the carbon source, 10-15 g/l of the nitrogen source, 15-20 g/l of the inorganic salt, 0.01-0.02 g/l of the trace element and 0.01-0.02 g/l of the vitamin. types of components of the activation medium and the seed culture medium are the same as those of the fermentation medium, the present disclosure may further process the above-mentioned fermentation product to obtain a microbial oil. there are no special requirements for the processing method as long as the method can extract the microbial oil from the fermentation product. in order to improve the production of the microbial oil, the fermentation product is subjected to wall breaking and extraction. in a third aspect, the present disclosure provides a microbial oil prepared by the above method, including a triglyceride, where sn-2 fatty acids of the triglyceride includes 23% or more by weight of dha. preferably, a weight percentage of total dha in the microbial oil is not less than 38%. in a fourth aspect, the present disclosure provides a food including the above-mentioned microbial oil. the food is infant formula food, nutraceutical or health food. in a fifth aspect, the present disclosure provides a schizochytrium strain with an accession number of gdmcc no. 60733. the method for obtaining the schizochytrium strain is described in the second aspect, and will not be repeated here. in a sixth aspect, the present disclosure provides a use of the schizochytrium strain in the production of the above-mentioned microbial oil. preferably, the microbial oil includes a triglyceride, where sn-2 fatty acids of the triglyceride include 23% or more by weight of dha. preferably, a weight percentage of total dha in the microbial oil is not less than 38%. the present disclosure will be further described in detail below with reference to the embodiments. in the embodiments, a content of dha and a fatty acid composition in a microbial oil are detected according to gb26400-2011 and gb 5009.168-2016, respectively. the absorption rate of dha in human body is detected by an efficacy trial, where male and female subjects are required to take in the microbial oil produced by the method of the present disclosure and a control dha oil, and then blood samples are collected to determine a content of the dha and a content of the sn-2 dha in the blood to calculate the absorption rate of dha. the conventional schizochytrium strain is provided by china center of industrial culture collection, and has an accession number of cicc 11091s. the glucose, sucrose, yeast powder, sodium glutamate, yeast extract, sodium chloride, magnesium sulfate, calcium chloride, potassium dihydrogen phosphate, nickel sulfate, copper sulfate, sodium molybdate, cobalt chloride, zinc sulfate, ferrous sulfate, manganese chloride, vitamin b 1 , vitamin b 12 , vitamin b 6 , calcium pantothenate, biotin, sodium bicarbonate, sodium sulfate, ammonium sulfate and potassium chloride are all commercially available. in the embodiments, the trace-element mother liquor contains 2 g/l of nickel sulfate, 1.9 g/l of copper sulfate, 0.04 g/l of sodium molybdate, 2.8 g/l of manganese chloride, 0.04 g/l of cobalt chloride, 3.2 g/l of zinc sulfate and 9 g /l of ferrous sulfate; and the vitamin mother liquor contains 10.3 g/l of vitamin b 1 , 0.16 g/l of vitamin b 12 , 3.2 g/l of calcium pantothenate and 0.008 g/l of biotin. preparation example preparation of schizochytrium strain (gdmcc no.60733) a parent strain preserved in the ampoule was inoculated into an activation medium and activated at 28°c for 2 days, where the activation medium contained 40 g/l of glucose, 31 g/l of sodium glutamate, 19 g/l of sodium chloride, 5.8 g/l of yeast extract, 8 g/l of magnesium sulfate, 5.7 g/l of potassium dihydrogen phosphate, 1 g/l of trace element and 1 g/l of vitamin (the activation medium plate further contained 18 g/l of agar). the activated schizochytrium suspension was spread on an activation medium plate, and then subjected to artp mutagenesis in a multifunctional mutagenesis system (mpms) produced by adhoc interteck co., ltd. (beijing, china), where the artp mutagenesis was carried out at a plasma mutagenesis power of 100 w, a gas flow rate of 10 slm and a treatment distance of 2 mm for 25 s; the schizochytrium suspension used for the mutagenesis had an od 600 of 0.6-0.8 or a concentration of 10 6 -10 8 cfu/ml; and a lethality rate was 92.54%. well-grown single colonies were selected for passage, and then inoculated into a shake flask containing the activation medium and cultured at 27°c for 4 days. a preliminary screening was performed to detect a content of dha and a content of the sn-2 position dha in the culture to select high-yield strains. the high-yield strains obtained by the preliminary screening were subjected to secondary screening by culture in a shake flask at 27°c for 4 days to further select high-yield strains. the genetic stability of the high-yield strains obtained by the secondary screening was investigated. after 5 passages, the strain with stable genetic traits was used as the production strain and stored for long-term use. after screening, the schizochytrium strain gdmcc no. 60733 of the present disclosure was obtained, which had been deposited in guangdong microbial culture collection center (gdmcc, guangdong institute of microbiology, 5th floor, no. 59 building, no. 100 xianliezhong road, guangzhou, 510070, china) on august 8, 2019. example 1 30 l fermentation and production using the schizochytrium strain gdmcc no. 60733 an activation medium used herein contained 40 g/l of glucose, 31 g/l of sodium glutamate, 5.8 g/l of yeast extract, 19 g/l of sodium chloride, 8 g/l of magnesium sulfate, 5.7 g/l of potassium dihydrogen phosphate, 1 g/l of trace element and 1 g/l of vitamin. a seed culture medium used herein contained 30 g/l of glucose, 6.3 g/l of sodium glutamate, 8.3 g/l of yeast extract, 8.3 g/l yeast powder, 1.45 g/l of sodium chloride, 5.18 g/l of magnesium sulfate, 1.66 g/l of potassium dihydrogen phosphate, 0.25 g/l of calcium chloride, 0.25 g/l of sodium bicarbonate, 9.34 g/l of sodium sulfate, 1.04 g/l of ammonium sulfate, 0.83 g/l of potassium chloride, 1 g/l of trace element, 1 g/l of vitamin and 0.3 g/l of a defoamer. a fermentation medium used herein contained 50 g/l of glucose, 15 g/l of sodium glutamate, 10.9 g/l of yeast extract, 2.6 g/l of sodium chloride, 5.8 g/l of magnesium sulfate, 2.4 g/l of potassium dihydrogen phosphate, 0.25 g/l of calcium chloride, 0.22 g/l of sodium bicarbonate, 3.62 g/l of sodium sulfate, 1.13 g/l of ammonium sulfate, 0.94 g/l of potassium chloride, 1.1 g/l of a trace-element mother liquor, 1.1 g/l of a vitamin mother liquor and 0.19 g/l of a defoamer. the fermentation was performed as follows. (1) an ordinary schizochytrium strain and the schizochytrium strain gdmcc no. 60733 were activated, respectively. specifically, the schizochytrium strain stored in each frozen glycerin tube was thawed and inoculated into four shake flasks containing 200 ml of the activation medium, and cultured on a shaker at 28°c and 180 r/min for 48 hours to obtain an activated schizochytrium suspension. (2) the activated schizochytrium suspension obtained from step (1) was inoculated into a shake flask containing 200 ml of the activation medium at 3% (v/v), and cultured on a shaker at 28°c and 180 r/min for 72 hours for proliferation. (3) 200 ml of the culture obtained from step (2) was inoculated into a seed tank containing 3 l of the seed culture medium, and cultured at 28°c, 0.03 mpa and 180 r/min under a ventilation rate of 0.6 vvm for 50 hours. (4) all of the culture in the seed tank was inoculated into a fermentation tank containing 14 l of the fermentation medium, and cultured at ph 6.8 and 29°c at a rotation speed of 140 r/min for 5-6 days, where the ventilation rate and the tank pressure were controlled at 0.95 vvm and 0.03 mpa, respectively. during the fermentation, a sterile glucose solution (250 g/l) and a sterile sodium glutamate solution (250 g/l) were added in fed-batch to maintain the glutamate concentration at 5-8 g/l and the carbon source concentration at 10-23 g/l. after 96 hours of the fermentation, the supply of carbon source and glutamate was stopped to obtain a fermentation broth. (5) 5 l of the fermentation broth obtained from step (4) was subjected to enzymatic wall disruption, and then centrifuged by a high speed centrifuge to separate a water phase, a solid phase, and an oil phase to obtain a microbial oil. (6) the microbial oil obtained from step (5) was analyzed to obtain a content of dha, fatty acid composition and a weight percentage of dha at the sn-2 position of the triglyceride, and the results were showed in table 1. table-tabl0001 table 1 parameters of the microbial oils in example 1 ordinary schizochytrium strain schizochytrium strain gdmcc no. 60733 dha (c22:6), g/100g 40.256 43.139 palmitic acid (c16:0), g/100g 21.894 20.974 stearic acid (c18:0), g/100g 1.542 1.301 oleic acid (c18:1), g/100g 0.312 0.273 docosapentaenoic acid (c22:5), g/100g 11.012 10.330 weight percentage of dha at sn-2 position of triglyceride, % 21.97 43.24 weight percentage of dha at sn-1 and sn-3 positions of triglyceride, % 56.98 47.55 absorption rate of dha, % 44.17 61.8 example 2 100 l fermentation and production using schizochytrium strain gdmcc no. 60733 an activation medium used herein contained 30 g/l of glucose, 20 g/l of sodium glutamate, 5 g/l of yeast extract, 15 g/l of sodium chloride, 6 g/l of magnesium sulfate, 4 g/l of potassium dihydrogen phosphate, 0.8 g/l of trace element and 0.75 g/l of vitamin. a seed culture medium used herein contained 25 g/l of glucose, 5.5 g/l of sodium glutamate, 7 g/l of yeast extract, 7 g/l of yeast powder, 1.1 g/l of sodium chloride, 4 g/l of magnesium sulfate, 1.2 g/l of potassium dihydrogen phosphate, 0.15 g/l of calcium chloride, 0.15 g/l of sodium bicarbonate, 7 g/l of sodium sulfate, 0.8 g/l of ammonium sulfate, 0.6 g/l of potassium chloride, 0.8 g/l of trace element, 0.75 g/l of vitamin and 0.2 g/l of a defoamer. a fermentation medium used herein contained 30 g/l of glucose, 10 g/l of sucrose, 12 g/l of sodium glutamate, 9 g/l of yeast extract, 2 g/l of sodium chloride, 4.5 g/l of magnesium sulfate, 2 g/l of potassium dihydrogen phosphate, 0.2 g/l of calcium chloride, 0.2 g/l of sodium bicarbonate, 2.8 g/l of sodium sulfate, 1 g/l of ammonium sulfate, 0.8 g/l of potassium chloride, 0.9 g/l of trace element, 0.9 g/l of vitamin and 0.15 g/l of a defoamer. the specific steps were shown as follows. (1) the ordinary schizochytrium strain and the schizochytrium strain gdmcc no. 60733 were activated, respectively. the schizochytrium strain stored in each frozen glycerin tube was thawed and inoculated into five shake flasks each containing 200 ml of the activation medium, and cultured on a shaker at 28.5°c and 150 r/min for 72 hours to obtain an activated schizochytrium suspension. (2) two shake flasks of the activated schizochytrium suspension obtained from step (1) were inoculated into five shake flasks each containing 200 ml of the activation medium, and cultured on a shaker at 28°c and 150 r/min for 48 hours. (3) 400 ml of the culture obtained from step (2) was inoculated into a seed tank containing 6 l of the seed culture medium, and cultured at 28°c and 150 r/min for 48 hours, where a ventilation rate and a tank pressure were controlled at 0.5 vvm and 0.03 mpa, respectively. (4) all of the culture in the seed tank was inoculated into a fermentation tank containing 45 l of the fermentation medium, and cultured at 28-29°c and 90-120 r/min for 5-6 days, where a ventilation rate and a tank pressure were controlled at 0.5-0.8 vvm and 0.03 mpa, respectively. during the fermentation, a sterile glucose solution (250 g/l) and a sterile sodium glutamate solution (250 g/l) were added in fed-batch to maintain a concentration of glutamate at 8-12 g/l and a concentration of carbon source at 40-65 g/l. after 96 hours of the fermentation, the supply of carbon source and glutamate was stopped to obtain a fermentation broth. (5) 10 l of the fermentation broth obtained from step (4) was subjected to enzymatic wall disruption, and then centrifuged by a high speed centrifuge to obtain a microbial oil. (6) the microbial oil obtained from step (5) was analyzed to obtain a content of dha, a fatty acid composition and a weight percentage of dha at the sn-2 position of triglyceride, and the results were showed in table 2. table-tabl0002 table 2 parameters of the microbial oils in example 2 ordinary schizochytrium strain schizochytrium strain gdmcc no. 60733 dha (c22:6), g/100g 42.689 46.786 palmitic acid (c16:0), g/100g 23.13 21.05 stearic acid (c18:0), g/100g 1.56 1.31 oleic acid (c18:1), g/100g 0.314 0.271 docosapentaenoic acid (c22:5), g/100g 11.012 10.301 weight percentage of dha at sn-2 position of triglyceride, % 22.76 43.68 weight percentage of dha at sn-1 and sn-3 positions of triglyceride, % 57.37 46.68 absorption rate of dha, % 43.98 62.8 example 3 45 m 3 industrial fermentation and production using schizochytrium strain gdmcc no. 60733 a seed culture medium used herein contained 50 g/l of glucose, 35 g/l of sodium glutamate, 10 g/l of yeast extract, 22 g/l of sodium chloride, 10 g/l of magnesium sulfate, 8 g/l of potassium dihydrogen phosphate, 1.4 g/l of trace element and 1.5 g/l of vitamin. a primary seed culture medium used herein contained 35 g/l of glucose, 8 g/l of sodium glutamate, 10 g/l of yeast extract, 10 g/l of yeast powder, 1.9 g/l of sodium chloride, 6 g/l of magnesium sulfate, 2.1 g/l of potassium dihydrogen phosphate, 0.4 g/l of calcium chloride, 0.4 g/l of sodium bicarbonate, 12 g/l of sodium sulfate, 1.3 g/l of ammonium sulfate, 1.1 g/l of potassium chloride, 1.2 g/l of trace element, 1.2 g/l vitamin and 0.4 g/l of a defoamer. a secondary seed culture medium was: 50 g/l of glucose, 5.65 g/l of sodium glutamate, 5.65 g/l of yeast extract, 1.3 g/l of sodium chloride, 4.65 g/l of magnesium sulfate, 1.49 g/l of potassium dihydrogen phosphate, 0.22 g/l of calcium chloride, 0.22 g/l of sodium bicarbonate, 8.39 g/l of sodium sulfate, 0.93 g/l of ammonium sulfate, 0.74 g/l of potassium chloride, 0.93 g/l of trace element, 0.93 g/l of vitamin and 0.3 g/l of a defoamer. a fermentation medium used herein contained 40 g/l of glucose, 20 g/l of sucrose, 20 g/l of sodium glutamate, 12 g/l of yeast extract, 3.2 g/l of sodium chloride, 7 g/l of magnesium sulfate, 3 g/l of potassium dihydrogen phosphate, 0.4 g/l of calcium chloride, 0.3 g/l of sodium bicarbonate, 4.5 g/l of sodium sulfate, 1.5 g/l of ammonium sulfate, 1.2 g/l of potassium chloride, 1.6 g/l of trace element and 1.6 g/l of vitamin. the specific steps of the fermentation were shown as follows. (1) the ordinary schizochytrium strain and the schizochytrium strain gdmcc no. 60733 were activated, respectively. the schizochytrium strain stored in each frozen glycerin tube were thawed and inoculated into six shake flasks containing 200 ml of the activation medium, and cultured on a shaker at 28°c and 180 r/min for 60 hours to obtain an activated schizochytrium suspension. (2) two shake flasks of the activated schizochytrium suspension obtained from step (1) were inoculated into five flasks each containing 200 ml of the activation medium, and cultured on a shaker at 28±0.5°c and 180 r/min for 60 hours for proliferation. (3) 500 l of the primary seed culture medium was sterilized and cooled to 40°c or lower, and then transferred to a primary seed tank. 1 l of the culture obtained from step (2) was inoculated into the primary seed tank, and cultured at ph 6.8, 28±0.5°c and 150 r/min for 55 hours. (4) 6 m 3 of the secondary seed culture medium was sterilized and cooled to 40°c or lower, and then transferred to a secondary seed tank. all of the culture in the primary seed tank was aseptically inoculated into the secondary seed tank, and cultured at ph 6.8, 28±0.5°c and 150 r/min for 18 hours. (5) 22 m 3 of the fermentation medium was sterilized and cooled to 40°c or lower, and then transferred to a fermentation tank. all of the culture in the secondary seed tank was inoculated into the fermentation tank, and cultured at ph 7.5, 28±0.5°c and 100 r/min for 5 days, where a ventilation rate was controlled at 1.0 vvm. during the fermentation, a sterile glucose solution (250 g/l) and a sterile sodium glutamate solution (250 g/l) were added in fed-batch to maintain a concentration of glutamate at 12-15 g/l and a concentration of carbon source at 55-70 g/l. after 96 hours of the fermentation, the supply of carbon source and glutamate was stopped to obtain a fermentation broth. (6) the fermentation broth was subjected to enzymatic wall disruption, preheated to 85-90°c, and then centrifuged by a triple-phase centrifuge to obtain a microbial oil. (7) the microbial oil obtained from step (6) was analyzed to obtain a content of dha, a fatty acid composition of and a weight percentage of dha at the sn-2 position of triglyceride, and the results were showed in table 3. table-tabl0003 table 3 parameters of the microbial oils in example 3 ordinary schizochytrium strain schizochytrium strain gdmcc no. 60733 dha (c22:6), g/100g 45.768 50.664 palmitic acid (c16:0), g/100g 22.913 20.859 stearic acid (c18:0), g/100g 1.321 1.293 oleic acid (c18:1), g/100g 0.314 0.277 docosapentaenoic acid (c22:5), g/100g 12.435 10.366 weight percentage of dha at sn-2 position of triglyceride, % 22.148 43.96 weight percentage of dha at sn-1 and sn-3 positions of triglyceride, % 54.56 46.33 absorption rate of dha, % 44.78 63.1 the above-mentioned embodiments are only preferred embodiments, and not intend to limit the scope of the present disclosure. it should be noted that variations and modifications made by those skilled in the art without departing from the spirit of the disclosure should fall within the scope of the present disclosure.
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050-239-686-539-973
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GB
|
[
"CA",
"EP",
"GB",
"WO"
] |
H04L49/111
| 1995-11-29T00:00:00 |
1995
|
[
"H04"
] |
controlled available bit rate service in an atm switch
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an atm switch (10) has a plurality of link controllers (12) each having a fifo (30) for each vc established, a fifo (32) for each priority level, and a traffic shaping fifo (34) for pointers to abr cells. cells are pushed into the vc fifo (30) and a pointer to the vc fifo (30) is pushed into an arbitration fifo (32) for the priority level of the vc fifo (30). pointers to abr cells with onward tramsmission times are pushed into the traffic shaping fifo (34). the arbitration fifos (32) are examined according to a schedule and cells are popped from vc fifos (30) according to priority for exit from the controller (12). a leaky bucket processor (22) calculates an average output cell rate ocr and abr cells are popped from vc fifos out of turn if the mcr for the abr vc exceed the ocr.
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claims : 1. an atm network switch, comprising: a) at least one switch fabric; and b) a plurality of controllers, each controller having, an input link and an output link to said switch fabric, at least one external link to an atm network, means for receiving atm cells from the atm network, means for determining the vc of cells received from the atm network, a plurality of cell buffer means for separately buffering groups of cells of each vc, means for determining whether each cell received from the atm network is an abr cell, means for creating a pointer to each abr cell, said pointer including an onward transmission time, traffic shaping buffer means for buffering said pointers to said abr cells, look-up table means for storing an mcr for each abr vc, means for determining available output bandwidth for abr traffic, calculating means for calculating an allocated output cell rate for each abr vc, means for reading pointers from said traffic shaping buffer means, means for comparing the mcr associated with a pointer read from said traffic shaping buffer means with said allocated output cell rate, and means for transmitting cells from each of said cell buffer means to another controller via said switch fabric when the mcr associated with a pointer read from said traffic shaping buffer is greater than said allocated output cell rate. 2. an atm network switch according to claim 1, wherein: each controller further includes means for determining a peak rate for abr traffic, means for determining if said peak rate has been exceeded, means for delaying said onward transmission time when said peak rate has been exceeded. 3. an atm network switch according to claim 2, wherein: each controller further includes means for determining an average rate for abr traffic, means for determining if said average rate has been exceeded, means for delaying said onward transmission time when said average rate has been exceeded. 4. an atm network switch according to claim 1, wherein: each controller further includes means for determining an er based on said allocated output cell rate. 5. an atm network switch according to claim 1, wherein: each controller further includes means for creating an arbitration pointer to each of said cell buffer means, arbitration buffer means for buffering said arbitration pointers to said cell buffer means, means for reading arbitration pointers from said arbitration buffer means, and means for transmitting cells from each of said cell buffer means to another controller via said switch fabric according to arbitration pointers read from said arbitration buffer means. 6. an atm network switch according to claim 5, wherein: each controllers further includes means for determining a priority level for each vc, said arbitration buffer means comprises a separate arbitration buffer for each priority level, and said means for reading arbitration pointers includes means for ordering the reading of said separate arbitration buffers. 7. an atm network switch according to claim 6, wherein: said arbitration buffer means includes an abr arbitration buffer for abr arbitration pointers, said means for reading arbitration pointers includes means for reading abr arbitration pointers, means for comparing the mcr associated with an abr arbitration pointer with said allocated output cell rate, and means for transmitting cells from a cell buffer means pointed to by said abr arbitration pointer to another controller via said switch fabric when the mcr associated with a pointer read from said traffic shaping buffer is less than said allocated output cell rate. 8. a method of controlling abr traffic in an atm network switch, comprising: a) determining the vc for each abr cell; b) storing each abr cell in a respective vc buffer for each abr vc; c) determining the mcr for each abr vc; d) storing the mcr for each abr vc in a look-up table; e) creating a pointer to each abr cell, the pointer including an onward transmission time; f) storing the pointers in a pointer buffer; g) determining available output bandwidth for abr traffic; h) calculating an allocated output cell rate for each abr vc, i) reading pointers from the pointer buffer in order of onward transmission time; j) comparing the mcr associated with a pointer with the allocated output cell rate; and k) transmitting the cell associated with the pointer when the mcr associated with the pointer is greater than the allocated output cell rate. 9. a method according to claim 8, further comprising: 1) determining a peak rate for abr traffic; m) determining if the peak rate has been exceeded; n) delaying the onward transmission time when the peak rate has been exceeded. 10. a method according to claim 9, further comprising: 0) determining an average rate for abr traffic; p) determining if the average rate has been exceeded; q) delaying the onward transmission time when the average rate has been exceeded. 11. a method according to claim 8, further comprising: 1) determining an er for each abr vc based on the allocated output cell rate. 12. a method according to claim 11, further comprising: m) adjusting the er for each abr vc based on the number of cells in a respective abr vc buffer. 13. an atm network switch, comprising: a) at least one switch fabric; and b) a plurality of controllers, each controller having, an input link and an output link to said switch fabric, at least one external link to an atm network, means for receiving atm cells from the atm network, means for determining whether each cell received from the atm network is an abr cell, means for determining the mcr for each abr vc, means for determining available output bandwidth for abr traffic, buffer means for buffering abr cells, means for comparing the mcr associated with a pointer read from said traffic shaping buffer means with said allocated output cell rate, and means for transmitting abr cells from said buffer means to another controller via said switch fabric based on a comparison of mcr and available output bandwidth for abr traffic. 14. an atm network switch according to claim 13, wherein: each controller further includes means for determining a peak rate for abr traffic, means for determining if said peak rate has been exceeded, means for delaying transmission of abr cells when said peak rate has been exceeded. 15. an atm network switch according to claim 14, wherein: each controller further includes means for determining an average rate for abr traffic, means for determining if said average rate has been exceeded, means for delaying transmission of abr cells when said average rate has been exceeded. 16. an atm network switch according to claim 13, wherein: each controller further includes means for determining an er based on said available output bandwidth for abr traffic. 17. an atm network switch according to claim 16, wherein: each controller further includes means for determining the number of abr cells in said buffer means, and means for adjusting said er based on the number of abr cells in said buffer means. 18. a method of controlling the flow of cells on an abr connection at a buffering point in an atm network switch, comprising using a traffic shaping process to guarantee a minimum cell rate for the abr vc. 19. a method according to claim 18, which also comprises using an arbitration process to ensure a fair distribution of bandwidth through all the vcs on the switch. 20. a method according to claim 18, wherein the traffic shaping process comprises a leaky bucket process comprising: timing the arrival of each cell on the abr; storing a predetermined regular bucket increment, a current bucket level value, a bucket maximum value, being the maximum capacity of the bucket, and an onward transmission time for the previous cell on the same vc; calculating the time difference between the arrival time of the cell and the stored onward transmission time for the preceding cell on the same vc; calculating a new bucket level from the time difference, the current bucket level, and the bucket increment; subtracting the maximum level from the new level to give an over flow value and, if the overflow value is negative, setting the value of the overflow to zero; and adding the overflow value to the current time to give the onward transmission time for the cell. 21. a method according to claim 19, comprising for each abr cell arriving at the buffering point: (a) storing the cell in a buffer for that particular vc and storing in an arbitration fifo a pointer to the cell address; (b) monitoring the input cell rate on the abr connection; (c) determining from the input rate the onward transmission time for the cell and storing in a traffic shaping fifo at an address corresponding to the onward transmission time a pointer to the cell address; (d) monitoring the onward cell rate for the abr connection and determining an average; (e) when the next cell transmission pointer emerges from the traffic shaping fifo, obtaining from storage means the mcr for that vc and comparing the mcr with the average onward cell rate (ocr) determined in step (d) and, only if the ocr<mcr, outputting the cell to which the pointer refers; and (f) when the next cell transmission pointer for that vc emerges from the arbitration fifo, obtaining from said storage means the mcr for that vc and comparing the mcr with the ocr determined in step (d) and, if ocr>mcr, outputting the cell to which the pointer refers, and then reintroducing the pointer into the bottom of the arbitration fifo. 22. an atm network switch comprising cell buffering means, the buffering means comprising traffic shaping means for guaranteeing a minimum cell rate for each abr vc configured on the switch. 23. a switch according to claim 22, also comprising arbitration means for ensuring a fair distribution of bandwidth through all the vcs on the switch. 24. a switch according to claim 23, comprising: a separate fifo for each vc configured through the switch; and control means arranged to store each incoming cell in the appropriate fifo; wherein the arbitration means is arranged to determine which of the fifos is to send the next cell to be transmitted onward from the buffering means, and the traffic shaping means is arranged to regulate the onward transmission time of abr cells according to the rate of output of the abr cells from the buffering means . 25. a switch according to any of claim 22, wherein the traffic shaping means comprises at least one leaky bucket processor, the or each leaky bucket processor comprising: timer means for timing the arrival of each atm cell at the buffering means; memory means for storing a predetermined regular bucket increment, a current bucket level value, a bucket maximum value, being the maximum capacity of the bucket, and an onward transmission time for the previous cell on the same vc; calculating means for calculating the time difference between the arrival time of the cell and the stored onward transmission time for the preceding cell on the same vc, and for calculating a new bucket level from the time difference, the current bucket level and the bucket increment; means for subtracting the maximum level from the new level to give an overflow value and, if the overflow value is negative, for setting the value of the overflow to zero; and adding means for adding the overflow value to the current time to give the onward transmission time for the cell and for storing said time in the memory means.
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controlled available bit rate service in an atm switch background of the invention this application is related to co-owned international application number pct/us96/05606 and co-owned international application number pct/us96/15737, the complete disclosures of which are hereby incorporated by reference herein. 1. field of the invention the invention relates to an asynchronous transfer mode (atm) network switch. more particularly, the invention relates to an atm switch having cell buffers for each available bit rate (abr) virtual connection (vc) and means for outputting cells which conforms to a minimum cell rate (mcr) for each abr vc and which fairly allocates bandwidth to all vcs on the switch. 2. state of the art in atm data transmission, cells of data conventionally comprising fifty-three bytes (forty-eight bytes carrying data and the remaining five bytes defining the cell header, the address and related information) pass through the network on a virtual connection at an agreed upon rate related to the available bandwidth and the level or service paid for. the agreed upon rate will relate not only to the steady average flow of data, but will also limit the peak flow rates. over an extensive network, cells on a virtual connection can become bunched together with different cells having different delays imposed upon them at different stages, so that the cell flow on a vc then does not conform with the agreed upon rates. to prevent rates being exceeded to the detriment of other vcs in the network, the network will include, for example at the boundary between different networks, means for policing the flow. the flow policing means typically includes a "leaky bucket" device which assesses the peak and average flow rates of cells on a vc and if required either downgrades the cells' priority or discards cells. since policing can result in the discarding of cells which should not be discarded, it is desirable to effect "traffic shaping" to space out the cells on a vc sufficiently so as to ensure that they meet the agreed upon rates, and in particular the peak rates. a problem with traffic shaping is that it is desirable to delay the transmission of cells by variable amounts in an attempt to avoid cell loss. in practice, however, variable cell delay has been difficult to implement. co-owned international application number pct/us96/05606 discloses an atm switch with a traffic shaping mechanism which delays the transmission of incoming cells by varying amounts of time and which accounts for both peak and average cell flow rates. the traffic shaping mechanism broadly comprises means for determining for each cell received an onward transmission time dependent upon the time interval between the arrival of the cell and the time of arrival of the preceding cell on the same vc, buffer means for storing each new cell at an address corresponding to the onward transmission time, and means for outputting cells from the buffer means at a time corresponding to the address thereof. the traffic shaping mechanism results in cells being output at a rate which is related to the rate at which they are received which eliminates or minimizes bunching. different virtual connections may have different priority levels. presently, the atm standard provides for several different priority levels. these include "constant bit rate" (cbr) service, which is the highest priority level, two "variable bit rate" (vbr) services, and available bit rate (abr) service, which is the lowest priority level. as traffic passes through an atm switch, it is important to handle the cells according to their level of priority. co-owned international application number pct/us96/15737 discloses an atm switch which includes a plurality of slot controllers each having at least one external network link and a link to a switch fabric, the slot controllers receiving atm cells from the network and transmitting cells to other slot controllers via the switch fabric and receiving cells from the switch fabric and transmitting cells onto the network. each slot controller is provided with a plurality of fifo buffers, one cell fifo for each vc established on the switch and one arbitration fifo for each priority level, and a fifo controller. when a cell enters a slot controller, the cell header is examined to determine the vcl and the priority level. the slot controller examines the switch fabric to find a path for the vc, selects a vc fifo for the vc, pushes the cell into the vc fifo, increments a counter for the vc fifo, and, if the vc fifo was previously empty, writes a pointer to the arbitration fifo for the priority level of the cell fifo. the arbitration fifos are examined according to a schedule and cells are popped from vc fifos according to priority for exit from the slot controller. according to one disclosed embodiment, the highest priority arbitration fifo is always examined first and none of the lower priority arbitration fifos are examined unless the highest priority arbitration fifo is empty. according to another embodiment, timers are set for the lower priority arbitration fifos and if a timer expires for a lower priority arbitration fifo, it is examined regardless of the contents of the highest priority arbitration fifo. according to still another embodiment, the slot controllers are coupled to two switch fabrics and two sets of arbitration fifos are used, one set for each switch fabric. prior to popping a cell from a fifo into the switch fabric, the switch fabric is examined to determine if the path is broken and whether an alternate path exists through the second switch fabric. if an alternate path is available, the cell is not sent, but the pointer for the vc fifo is pushed into the corresponding arbitration fifo for the second switch fabric. the system described provides efficient handling of all priority levels, but is not specifically mindful of the needs of abr traffic. abr service is intended to make the best use of any remaining available bandwidth in an atm switch after providing for the higher priority services. abr service is suitable for data transmission which is not time sensitive, but which may be cell loss sensitive. abr service is generally implemented by buffering data at the ingress of an atm switch and releasing the data from the buffer into the switch core only when some available bandwidth is not being used by a higher priority connection. clearly, in order for this approach to function correctly without an unacceptable level of cell loss, the source of the data must transmit data at a rate ("cell rate") which does not cause the buffer to overflow. according to presently utilized techniques, abr service is managed through the use of special atm cells which are known as rm cells. r cells are sent from the source through the destination and return to the source with information about the congestion level in the atm switches which form the abr vc between the source and the destination. the source is then able to modify its transmission cell rate to avoid cell loss due to congestion. as presently implemented, rm cells include fields for indicating the current cell rate (ccr) , the minimum cell rate (mcr) , and the explicit rate (er) . the ccr is the rate at which the source is presently transmitting atm cells. the mcr is a rate which is established at the time the vc is set up and indicates the minimum rate at which the source may always transmit cells without cell loss. the er is the new rate to which the source should adjust cell transmission due to the level of congestion in the switches which form the abr vc. the er is set by the switches which form the abr vc and may be a rate which is higher than or lower than the ccr. however, the er may not be set lower than the mcr. various algorithms are utilized in atm switches to set the er for an abr vc. several difficulties have been encountered with the implementation of abr service. many of the algorithms used to determine the er are not equipped to deal with the situation when the calculated er is less than the mcr. for example, most algorithms assume that all abr vcs through the switch have the same mcr and that the er for any abr vc will be applied to all abr vcs through the switch. in reality, different abr vcs have different mcrs. if the calculated er is lower than some of the actual mcrs of the abr vcs through the switch, these abr vcs will not be reduced to the calculated er even though the algorithm assumes that they will. thus, the algorithm will assume that congestion has been accounted for when, in reality some of the abr vcs will continue to operate at a ccr which is too high for the congestion on the vcs. summary of the invention it is therefore an object of the invention to provide an atm switch with means for controlling the flow of abr cells through the switch. it is also an object of the invention to provide an atm switch with means for controlling the flow of abr cells through the switch which guarantees the mcr bandwidth for all abr vcs. it is another object of the invention to provide an atm switch with means for controlling the flow of abr cells through the switch which provides an accurate and fair er for each abr vc. in accord with these objects which will be discussed in detail below, an atm switch according to the invention includes a plurality of slot controllers each having at least one external network link and a link to a switch fabric, the slot controllers receiving atm cells from the network and transmitting cells to other slot controllers via the switch fabric and receiving cells from the switch fabric and transmitting cells onto the network. each slot controller is provided with an input cell processor, an output cell processor, and a plurality of fifo buffers, one cell fifo for each vc established on the switch, one arbitration fifo for each priority level, and a traffic shaping fifo. the traffic shaping fifo is preferably configured as a leaky bucket and is provided with a look-up table for storing the mcrs of the abr vcs. according to the methods of the invention, when a cell enters a slot controller, the cell header is examined to determine the vcl and the priority level. the slot controller examines the switch fabric to find a path for the vc, selects a vc fifo for the vc, pushes the cell into the vc fifo, increments a counter for the vc fifo, and, if the vc fifo was previously empty, writes a pointer to the arbitration fifo for the priority level of the cell fifo. the arbitration fifos are examined according to a schedule and cells are popped from vc fifos according to priority for exit from the slot controller as described in co-owned international application number pct/us96/15737. according to the invention, an onward transmission time for each abr cell is calculated according to the methods described in co-owned international application number pct/us96/05606 and address pointers to abr cells are stored in the traffic shaping fifo as well as in an arbitration fifo. the input cell processor monitors the peak cell flow rate for each abr vc on the switch according to a leaky bucket process and determines for each cell whether the peak cell flow rate has been exceeded. if the peak rate has been exceeded, such that the leaky bucket overflows, the amount of overflow is added to the current time as the address for the cell in the vc fifo so that the onward transmission of the cell is delayed by the amount of the overflow. the abr cells are thus output from the vc fifos in the order of time slots stored in the traffic shaping fifo. in order to assure that the mcr is maintained for each abr vc, the cell processor monitors the output bandwidth of all abr traffic and calculates an average over a predetermined period of time. the output bandwidth per abr vc, the output cell rate (ocr) is determined by dividing the average output bandwidth of all abr traffic by the number of pointers in the traffic shaping fifo. when a pointer is popped from the traffic shaping fifo, the current value of the ocr is determined and the mcr for the abr vc is looked up. if the ocr is greater than the mcr, the pointer from the traffic shaping fifo is discarded and the cell is output according to the arbitration fifo scheduling, i.e. the cell is temporarily left in the vc fifo. if the ocr is less than the mcr, the pointer from the traffic shaping fifo is used immediately to output a cell from the appropriate vc fifo. when pointers from arbitration fifos are used, the ocr is also compared to the mcr. if the ocr is greater than the mcr, the pointer is used to .output the cell and the pointer is pushed back to the bottom of the arbitration fifo. if the ocr is less than the mcr, the cell is left in the vc fifo. in addition, according to the invention, an er value is set at or just below the ocr and is signalled back to the source for each abr vc. the er for individual abr vcs may be fine tuned according to the factor vccount ^ maxcount ) where vccount is the number of cells in a particular vc fifo and maxcount is a configurable parameter for each particular abr vc. additional objects and advantages of the invention will become apparent to those skilled in the art upon reference to the detailed description taken in conjunction with the provided figures. brief description of the drawings figure 1 is a high level schematic diagram of an atm switch according to the invention; figure 2 is a high level schematic diagram of a slot controller according to a first embodiment of the invention; figure 3 is a high level schematic diagram of a cell buffering system according to one embodiment of the invention; figure 4 is a schematic flow chart of how all cells entering the buffering system are handled; figure 5 is a schematic flow chart of how abr cells entering the buffering system are handled; figure 6 is a schematic flow chart of how all cells exiting the buffering system are handled; and figure 7 is a schematic flow chart of how abr cells exiting the buffering system are handled. detailed description of the preferred embodiments referring now to figure 1, an atm switch 10 according to the invention includes a plurality of controllers (which are often called "slot controllers" or "link controllers") 12a-12g and two dynamic crosspoint switch fabrics 14, 14' . each slot controller has at least one external link lβa-16h to an atm network (not shown), an input link 18a-18h to the switch fabric 14, an output link 20a-20h from the switch fabric 14, an input link 18'a-18'h to the switch fabric 14', and an output link 20'a-20'h from the switch fabric 14 ' . this general arrangement is described in co- owned uk patent application no. 9507454.8 and uk patent application no. 9505358.3 which are hereby incorporated by reference herein in their entireties. as shown generally in figure 2, each slot controller 12 has an input cell processor 22, an output cell processor 24, and a cell buffering system 26. according to a presently preferred embodiment of the invention, the cell buffering system 26 is coupled to the input cell processor 22 for buffering cells received from the atm network before they pass through the switch 10. in this embodiment of the invention, the output cell processor 24 is conventional and handles such functions as writing cell headers with new vpi/vci information before passing cells onto the network. the input cell processor 22 is unconventional in that it controls the buffering system 26 in addition to other conventional functions such as reading cell headers and routing cells through the switch fabric to another slot controller. turning now to figure 3, the buffering system 26 generally includes a plurality of vc fifos 30a, 30b, 30c, ..., 30n , a plurality of priority level arbitration fifos 32a-32d, 32'a-32'd, a traffic shaping fifo 34, and an mcr look-up table 36. the fifos are coupled to the input cell processor and controlled by the input cell processor as described below with reference to figures 4 and 5. according to the presently preferred embodiment of the invention, the vc fifos are not individual hardware components but are rather dynamically configured in ram as needed. the number of fifos created depends on the number of vcs being handled by the particular slot controller. according to the invention, when a cell is inspected by the cell processor 22 to determine the vcl of the cell, a fifo is created for that vc (if one does not already exist) . typically, each vc fifo would be a 64k fifo, although fifos of different sizes could be used depending on the number of cells expected for a particular vc. the arbitration fifos are preferably also dynamically configured in ram. the number of arbitration fifos corresponds to the number of priority levels for vcs through the switch. as shown in figure 3, there are four arbitration fifos representing the current atm priority levels of "0" through "3" ("0" being the highest priority and "3" being abr) . in the presently preferred embodiment, a separate set of arbitration fifos is used for each switch fabric. thus, as shown in figure 3, fifos 32a-32d would be used for switch fabric 14 (figure 1) and fifos 32'a-32'd would be used for switch fabric 14' . the traffic shaping fifo 34 and the mcr look-up table 36 are also preferably dynamically configured in ram. the size of the traffic shaping fifo and the mcr look-up table is related to the number of abr vcs being handled by a particular slot controller and the mcr for each abr vc. the operation of the buffering system 26 is further illustrated with reference to figures 4-7 where figures 4 and 5 illustrate cells entering the buffer system and figures 6 and 7 illustrate cells exiting the buffer system. turning now to figure 4, when a cell enters the input cell processor, the header is examined at 50 and the vcl and priority level are determined at 52. if it is determined at 53 that the cell is an abr cell, leaky bucket processing is performed at 55 (described in more detail below with reference to figure 5) and the next cell is then examined at 50. if the cell is not an abr cell, the cell processor inspects the switch fabric at 54 to determine whether a path is available for the vc. if, at 56, it is determined that no path exists for the vc, the cell is discarded at 58. if a path does exist, the cell processor pushes the cell into vc fifo(n), where "n" represents the vc, and increments a cell counter for vc fifo(n) at 60. if it is determined at 62 that the cell count for vc fifo (n) is "1", i.e. that the fifo was previously empty, a pointer pointing to vc fifo(n) is written and pushed at 64 into the appropriate arbitration fifo depending on the priority level of the cell which was determined at 52. the cell processor then returns to 50 to examine the next cell received from the network. if it is determined at 62 that the vc fifo was not previously empty, no pointer is written and the cell processor returns to 50 to examine the next cell received from the network. this process is repeated for each cell received by the input cell processor and new vc fifos are created as needed for new vcs. similarly, empty vc fifos are released from ram so that ram is made available for new vc fifos. turning now to figure 5, and with reference to figure 4, if it is determined at 53 that the cell is an abr cell, the leaky bucket processing begins at 150 as shown in figure 5. for each abr cell received, it is determined at 152 whether the peak cell flow rate for the cell's vc has been exceeded. as described in previously incorporated international application number pct/us96/05606, this determination is based upon a number of operations not illustrated in figure 5 herein. in particular, the leaky bucket processor times the arrival of each abr cell and calculates the time difference between the arrival of cells for each vc. each time difference is compared to a stored bucket level and bucket increment and the bucket level and bucket increment are adjusted accordingly. a stored maximum bucket level is then subtracted from the adjusted bucket level to provide a current overflow level. if the overflow level is less than or equal to zero, the peak rate has not been exceeded and the processing of the cell continues at 154 in figure 5. the cell is pushed into the appropriate vc fifo and a pointer to the cell is pushed into the traffic shaping buffer at 154. preferably, prior to pushing the cell into the vc fifo, the switch fabric is examiner to determine whether a path is available and the cell is discarded if there is no available path. the pointer pushed into the traffic shaping buffer includes the onward transmission time for the cell. if, on the other hand, it is determined at 152 that the peak rate has been exceeded, the overflow value is added to the onward transmission time at 156 before the cell is buffered and the pointer is written at 154. in this case, the pointer will include the sum of the onward transmission time plus the overflow value. the cell is then treated like all other cells so that a pointer is placed in the arbitration buffer at 160 if it is determined at 158 that this is the first cell entering the buffer. the leaky bucket processing of incoming cells then returns at 162 to examine the next cell at 50 in figure 4. according to a presently preferred embodiment of the invention, two leaky bucket processors are operated in parallel, one for monitoring peak flow rates and the other for monitoring average flow rates. overflow values from the two buckets are compared and the greater of the two values is used to increment the time pointer for the abr cell. as the above described processes continue, the cell processor outputs cells to the switch fabric from the vc fifos according to a selected procedure. figures 6 and 7 show a presently preferred procedure with optional portions shown in phantom lines and phantom line boxes. turning now to figure 6, the basic output procedure for all cells starts at 70. according to the essential principles of the invention, the arbitration fifos are examined to determine whether they contain pointers to vc fifos. in a simplified embodiment of the invention, the highest priority fifo(0) is always examined first at 72. if the fifo is not empty, the top pointer in the fifo is popped at 74. at 76, the vc fifo to which the pointer points is popped and the cell count for the vc fifo is decremented. if it is determined at 78 that the cell count of the vc fifo is zero, the procedure returns to the start 70 and examines the arbitration fifo(0) again at 72. if it is determined at 78 that the cell count of the vc fifo is not zero, the pointer to the vc fifo is pushed back into the arbitration fifo(0) at 80 and the procedure then returns to start 70 and examines the arbitration fifo(0) again at 72. according to this simplified embodiment of the invention, none of the other arbitration fifos are examined until the fifo (0) is empty as determined at 72. if it is determined at 72 that the arbitration fifo(o) is empty, the procedure goes to 82 and examines the contents of arbitration fifo(l) . if the arbitration fifo(l) is determined at 82 to contain pointers, the top pointer is popped at 84, the corresponding vc fifo is popped at 86, the pointer is pushed back into fifo(l) at 90 if it is determined at 88 that the vc fifo is not empty, and the procedure returns to the start at 70. only if it is determined at 82 that the arbitration fifo(l) is empty, will the procedure go to 92 to examine the contents of arbitration fifo (2) . if, at 82, it is determined that the arbitration fifo(l) is empty, the procedure described above is repeated at 92-100 with respect to the arbitration fifo (2) . only if it is determined at 92 that the arbitration fifo(2) is empty, will the procedure go to 102 to examine the contents of arbitration fifo (3) which, as shown in figure 6, is the abr arbitration fifo. if, at 92, it is determined that the arbitration fifo (2) is empty, the procedure described above is repeated at 102-110 with respect to the arbitration fifo (3) with one exception. prior to popping the abr cell from the vc fifo, a determination is made at 105 whether the ocr is greater than the mcr for this particular vc; and the cell is popped only if ocr>mcr. the calculation of ocr is described in more detail below with reference to figure 7. the above simplified embodiment of the invention may be enhanced by setting a timer for each of the three lower level arbitration fifos. according to a second embodiment of the invention, after the procedure starts at 70, timers are examined at 112-116 before examining the arbitration fifo(0) . in particular, the timer for arbitration fif0(1) is examined at 112 and if it has expired the procedure goes to 82 where the arbitration fifo(l) is examined as described above. in addition, the timer for arbitration fif0(1) is reset at 118 before the procedure returns to start at 70. if the timer for arbitration fifo(l) has not expired as determined at 112, the timer for arbitration fifo (2) is examined at 114 and if it has expired the procedure goes to 92 where the arbitration fifo (2) is examined as described above. in addition, the timer for arbitration fifo(2) is reset at 120 before the procedure returns to start at 70. if the timer for arbitration fifo (2) has not expired as determined at 114, the timer for arbitration fifo (3) is examined at 116 and if it has expired the procedure goes to 102 where the arbitration fifo (3) is examined as described above. in addition, the timer for arbitration fifo(3) is reset at 122 before the procedure returns to start at 70. in this embodiment, the decisions at 82, 92, and 102 may be modified such that upon determining that an arbitration fifo is empty, the procedure returns to start, rather than to examine the next arbitration fifo. in addition to the above, the procedure may be further enhanced by testing whether paths through the switch fabric have broken. for example, after the vc pointer is popped at 74, but before the cell is popped from the vc fifo into the switch, the cell processor determines at 124 if the switch fabric path for this vc is broken. if it is, the cell processor determines at 126 whether an alternate path is available through the second switch fabric. if an alternative path is available, the cell processor pushes the pointer at 128 into the appropriate arbitration fifo for the second switch fabric and then returns to start at 70. if the path is broken and no alternative path is available, the cell is discarded at 130. it will be appreciated that this testing of the switch fabric may be implemented for each arbitration fifo. therefore, the routines at 82-90, 92-100, and 102-110 would be modified to include the same steps as described with reference to 124-130. those skilled in the art will appreciate that the pointers stored in the arbitration fifos preferably include information for output port number, switch fabric preference, and priority, in addition to the vc information. according to still another embodiment of the invention, the arbitration of the buffering system can be further enhanced to deal with "blocked ports". according to this embodiment, another arbitration fifo is created for pointers to vcs having blocked ports. the blocked port arbitration fifo is then given the highest priority. since the presence of a single blocked port could, under this system, prevent all cells from being transmitted until a particular port becomes un-blocked, the pointers in the blocked port arbitration fifo are preferably recycled each time a pointer encounters a blocked port . in other words, when a pointer is popped from a blocked port arbitration fifo, the pointer is pushed back to the bottom of the fifo if it points to a vc which continues to have a blocked port. according to a presently preferred implementation, a separate blocked port fifo is provided for each priority arbitration fifo so that the blocked ports are also dealt with according to priority level. in order to assure that the mcr for each abr vc is maintained, the leaky bucket processing according to the invention monitors the abr traffic through the switch and makes certain adjustments to the flow of abr traffic as illustrated in figure 7. turning now to figure 7, the cell processor monitors the output bandwidth for all abr traffic over time and determines an average value periodically at 200. each time a pointer is popped from the traffic shaping fifo at 202, the mcr for the vc corresponding to the pointer is looked up in the look-up table. it will be recalled that pointers are popped from the traffic shaping fifo according to the time stamp contained in the pointers which were assigned as described herein above with reference to figure 5. upon a pointer being popped from the traffic shaping fifo, the cell processor divides the current average output bandwidth by the number of pointers remaining in the traffic shaping buffer in order to determine an output cell rate (ocr) per abr vc. the ocr is compared to the mcr at 206 and if the ocr is greater than the mcr for this particular vc, the pointer is discarded and the forwarding of cells for this vc is left to be accomplished by the arbitration buffer as described above with reference to figure 6. if, on the other hand, the ocr is not greater than the mcr, the cell pointed to by the pointer is popped from the vc fifo and the cell count for the vc fifo is decremented at 210 before the pointer is discarded at 208. from the foregoing, it will be appreciated that the output bandwidth available for abr traffic is allocated fairly among abr vcs with due consideration being given to the mcr for each vc. in addition, according to the invention, the calculated ocr can be used to provide a new er which is signalled back to the source for each abr vc handled by the switch. according to a presently preferred embodiment, the er is set equal to or slightly below the ocr with a lower threshold being provided so that the fifo does not empty. in addition, it is preferable to set the er based on one or more de-rating factors which may be global throughout the network or individual for each port. moreover, the er for each vc may be customized based on the number of cells in the fifo for each vc according to formula (1) given below where vccount is the number of cells in a particular vc fifo and maxcount is a configurable parameter for each particular abr vc. er= f {ι - ma a c x°c u o n u t nt j ) χ θcr ( 1 ) utilizing formula (1) , the er will be reduced as the number of cells in the vc fifo increases. there have been described and illustrated herein several embodiments of a atm switch with vc priority buffers and abr traffic shaping. while particular embodiments of the invention have been described, it is not intended that the invention be limited thereto, as it is intended that the invention be as broad in scope as the art will allow and that the specification be read likewise. thus, while particular numbers and types of fifo buffers have been disclosed, it will be appreciated that other numbers and types of fifos could be utilized. also, while particular procedures have been shown for reading the arbitration buffers, it will be recognized that other types of procedures could be used. in addition, while a specific leaky bucket traffic shaping method has been disclosed, other traffic shaping methods may be utilized to adjust the rate of traffic based on the input and output rates as measured. also, while the abr traffic shaping has been disclosed in conjunction with a particular priority buffering system, the abr traffic shaping may be used alone or in conjunction with other buffering schemes moreover, while particular configurations have been disclosed in reference to the operations of the input and output cell processors, it will be appreciated that other configurations could be used as well. for example, the management of the arbitration, traffic shaping, and vc fifos could be accomplished at either the input cell processor or the output cell processor or by a separate processor and not delegated to the input and/or output cell processors. furthermore, while the atm switch has been disclosed as having eight slot controllers and the slot controllers have been shown with eight data links, it will be understood that different numbers of slot controllers and data links can be used. it will therefore be appreciated by those skilled in the art that yet other modifications could be made to the provided invention without deviating from its spirit and scope as so claimed.
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050-406-191-382-690
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US
|
[
"US"
] |
H04W4/021,G05B15/02,H04M3/42,H04W52/02,H04W88/02
| 2015-12-09T00:00:00 |
2015
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[
"H04",
"G05"
] |
user or automated selection of enhanced geo-fencing
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this disclosure relates to a mobile device that is suitable for detect geofence crossing events. in some instances, the mobile device can detect geofence crossing events using a lower power algorithm or a higher power algorithm. the mobile device may allow a user of the mobile device to specify whether a lower power algorithm or a higher power algorithm is to be used when detecting geofence crossing events. in some instances, the mobile device may automatically change from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. in some instances, the user may be prompted to confirm automatically changing from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events.
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1. a non-transitory computer-readable storage medium with an executable program stored thereon, wherein the executable program is configured to instruct a mobile device, having a user interface with a display, and location services that include cell tower triangulation and a global position system (gps), to perform the following: store information pertaining to a geo-fence, the geo-fence defined by a size about a location; with the aid of the location services of the mobile device, detect a geofence crossing when the mobile device crosses the geo-fence, and if a geofence crossing is detected, transmit a geofence crossing event to a remote location via a transmitter of the mobile device; wherein the detection of the geofence crossing uses either a lower power algorithm or a higher power algorithm, wherein the lower power algorithm consumes less power from the mobile device than the higher power algorithm; wherein the lower power algorithm uses cell tower triangulation of the location services of the mobile device, and the higher power algorithm uses the gps of the location services of the mobile device; allowing a user to specify via the user interface of the mobile device whether the lower power algorithm or the higher power algorithm is to be used when detecting for geofence crossings; using the user specified lower power or higher power algorithm when detecting geofence crossings. 2. the non-transitory computer-readable storage medium of claim 1 , wherein the higher power algorithm uses cell tower triangulation and the gps of the location services of the mobile device. 3. the non-transitory computer-readable storage medium of claim 1 , wherein the lower power algorithm uses the gps of the location services of the mobile device, where the gps is turned on and sampled at a first rate, and the higher power algorithm uses the gps of the location services of the mobile device, where the gps is turned on and sampled at a second higher rate. 4. the non-transitory computer-readable storage medium of claim 1 , wherein the lower power algorithm and the higher power algorithm both use the gps of the location services of the mobile device, wherein the lower power algorithm turns the gps on less often than the higher power algorithm. 5. the non-transitory computer-readable storage medium of claim 1 , wherein the lower power algorithm and the higher power algorithm both use the gps of the location services of the mobile device, wherein the lower power algorithm obtains a less precise gps location than the higher power algorithm. 6. the non-transitory computer-readable storage medium of claim 1 , wherein the mobile device displays on the display a slider button, and the user specifies whether the lower power algorithm or the higher power algorithm is to be used by sliding the slider button to a desired setting. 7. the non-transitory computer-readable storage medium of claim 1 , wherein the mobile device displays on the display a first user selectable option that corresponds to the lower power algorithm and a second user selectable option that corresponds to the higher power algorithm, and the user specifies whether the lower power algorithm or the higher power algorithm is to be used by selecting either the first user selectable option or the second user selectable option. 8. the non-transitory computer-readable storage medium of claim 1 , wherein the detection of the geofence crossing uses either the lower power algorithm, the higher power algorithm, or an intermediate power algorithm, wherein the intermediate power algorithm consumes more power from the mobile device than the lower power algorithm and less power from the mobile device than the higher power algorithm, and wherein the user is allowed to specify via the user interface of the mobile device whether the lower power algorithm, the intermediate power algorithm or the higher power algorithm is to be used when detecting geofence crossings. 9. a non-transitory computer-readable storage medium with an executable program stored thereon, wherein the executable program is configured to instruct a mobile device, having a user interface with a display, and location services that include cell tower triangulation and a global position system (gps), to perform the following: store information pertaining to a geo-fence, the geo-fence defined by a size about a location; with the aid of the location services of the mobile device, detect a geofence crossing when the mobile device crosses the geo-fence, and if a geofence crossing is detected, transmit a geofence crossing event to a remote location via a transmitter of the mobile device; wherein the detection of the geofence crossing uses either a lower power algorithm or a higher power algorithm, wherein the lower power algorithm consumes less power from the mobile device than the higher power algorithm, and wherein the lower power algorithm uses cell tower triangulation of the location services of the mobile device, and the higher power algorithm uses the gps of the location services of the mobile device; and change from the lower power algorithm to the higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. 10. the non-transitory computer-readable storage medium of claim 9 , wherein the predetermined abnormality comprises more than a threshold number of detected geofence crossing events even while the mobile device remains in the user's home. 11. the non-transitory computer-readable storage medium of claim 9 , wherein the predetermined abnormality comprises not detecting one or more geofence crossings. 12. the non-transitory computer-readable storage medium of claim 9 , wherein the executable program instructs the mobile device to determine if the predetermined abnormality is present in the detected geofence crossing events. 13. the non-transitory computer-readable storage medium of claim 9 , wherein the executable program instructs the mobile device to receive via a receiver of the mobile device if the predetermined abnormality is present in the detected geofence crossing events. 14. the non-transitory computer-readable storage medium of claim 9 , wherein the executable program instructs the mobile device to automatically change from the lower power algorithm to the higher power algorithm if the predetermined abnormality is found to be present in the detected geofence crossing events. 15. the non-transitory computer-readable storage medium of claim 9 , wherein if the predetermined abnormality is found to be present in the detected geofence crossing events, the executable program instructs the mobile device to gain permission from a user via the user interface of the mobile device before changing from the lower power algorithm to the higher power algorithm. 16. a mobile device comprising: a user interface with a display; a location service that can determine a location of the mobile device using each of cell tower triangulation and gps; a memory for storing information pertaining to a geo-fence, the geo-fence defined by a size about a geo-fenced location; a transmitter; a battery; a controller operatively coupled to the user interface, the location service, the memory, the transmitter, and the battery, the controller configured to: with the aid of the location service of the mobile device, detect a geofence crossing when the mobile device crosses the geo-fence, and if a geofence crossing is detected, transmit a geofence crossing event to a remote location via the transmitter of the mobile device; wherein the detection of the geofence crossing uses either a lower power algorithm or a higher power algorithm, wherein the lower power algorithm consumes less power from the battery than the higher power algorithm, and wherein the lower power algorithm uses cell tower triangulation and the higher power algorithm uses gps; and change from the lower power algorithm to the higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. 17. the mobile device of claim 16 , wherein the predetermine abnormality comprises detecting too many geofence crossings and/or detecting too few geofence crossings.
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technical field the disclosure relates generally to building automation, and more particularly to building automation systems with geo-fencing capabilities. background building automation systems are often used to control safety, security and/or comfort levels within a building or other structure. illustrative but non-limiting examples of building automation systems include heating, ventilation and/or air conditioning (hvac) systems, security systems, lighting systems, fire suppression systems and/or the like. in some cases, a building automation system may enter an unoccupied mode when the building is expected to be unoccupied and an occupied mode when the building is expected to be occupied. for example, when the building automation system includes an hvac system, the building automation system may set a temperature set point of the hvac system to a more energy efficient setting when in an unoccupied mode and a more comfortable setting when in an occupied mode. in another example, when the building automation system includes a security system, the building automation system may set the security system to a locked or away state when in an unoccupied mode and an unlocked or home state when in an occupied mode. summary the present disclosure pertains generally to geo-fencing and, more particularly, to improvements in the accuracy and robustness of geo-fencing. an example of the disclosure may be found in a mobile device with a display, a memory and location services. the mobile device may store information pertaining to a geofence in the memory. with the aid of the location services of the mobile device, a geofence crossing may be detected when the mobile device crosses the geo-fence and, if a geofence crossing is detected, the mobile device may transmit a geofence crossing event to a remote location such as a remote server via a transmitter of the mobile device. the mobile device may detect the geofence crossing events using different algorithms. the different algorithms can use the same or different locations services hardware and/or may include different algorithm settings. the different algorithms may include a lower power algorithm and a higher power algorithm, wherein a lower power algorithm consumes less power from the mobile device than a higher power algorithm. in some cases, the mobile device may allow a user of the mobile device to specify whether a lower power algorithm or a higher power algorithm is to be used when detecting geofence crossing events. in some cases, the mobile device may, sometimes with permission from the user, automatically change from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. in some instances, such functionality may be programmed into the mobile device by an executable program stored on a non-transitory computer-readable storage medium. the preceding summary is provided to facilitate an understanding of some of the features of the present disclosure and is not intended to be a full description. a full appreciation of the disclosure can be gained by taking the entire specification, claims, drawings, and abstract as a whole. brief description of the drawings fig. 1 is a schematic view of an illustrative building automation system; fig. 2 is a schematic view of another illustrative building automation system; fig. 3 is a schematic view of another illustrative building automation system; fig. 4 is a schematic view of an illustrative mobile device; fig. 5 is a schematic view of an illustrative building automation server; fig. 6 is a schematic view of an example geofencing scenario; fig. 7 is a schematic view of another example geofencing scenario; fig. 8 is an illustrative query that may be displayed on the mobile device soliciting information from the user of the mobile device regarding whether the user of the mobile device would like to improve geofencing or not improve geofencing; and fig. 9 is an illustrative query allowing the user of the mobile device to select on a sliding scale between “maximum accuracy” of the geofencing experience and “maximum battery life”. description the following description should be read with reference to the drawings wherein like reference numerals indicate like elements. the drawings, which are not necessarily to scale, are not intended to limit the scope of the disclosure. in some of the figures, elements not believed necessary to an understanding of relationships among illustrated components may have been omitted for clarity. all numbers are herein assumed to be modified by the term “about”, unless the content clearly dictates otherwise. the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include the plural referents unless the content clearly dictates otherwise. as used in this specification and the appended claims, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise. it is noted that references in the specification to “an embodiment”, “some embodiments”, “other embodiments”, etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. moreover, such phrases are not necessarily referring to the same embodiment. further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is contemplated that the feature, structure, or characteristic may be applied to other embodiments whether or not explicitly described unless clearly stated to the contrary. the present disclosure is directed generally at building automation systems. building automation systems are systems that control one or more operations of a building. building automation systems can include hvac systems, security systems, fire suppression systems, energy management systems and/or any other suitable systems. while hvac systems are used as an example below, it should be recognized that the concepts disclosed herein can be applied to building control systems more generally. a building automation system may include a controller, computer and/or other processing equipment that is configured to control one or more features, functions, systems or sub-systems of a building. in some cases, devices that can be used by individuals to communicate with the controller, computer and/or other processing equipment. in some cases, a building automation system may include a plurality of components that, in combination, perform or otherwise provide the functionality of the building automation system. a building automation system may be fully contained within a single building or may include components that are spread between multiple housings and/or across multiple locations. in some embodiments, a building automation system, regardless of the physical location(s) of the components within the building automation system, may control one or more building systems within a single building. in some cases, a building automation system, regardless of the physical location(s) of the components within the building automation system, may control one or more building systems within a plurality of buildings, optionally in accordance with a common operating procedure and/or distinct operating procedures for each building as desired. fig. 1 is a schematic view of an illustrative building automation system 10 . the illustrative building automation system 10 includes a server 12 that may be configured to communicate with a mobile device 14 and with a building controller 16 . it will be appreciated that for simplicity, only a single mobile device 14 is shown, while in many cases the server 12 may be configured to communicate directly or indirectly with any number of mobile devices 14 . similarly, while a single building controller 16 is illustrated, in many cases the server 12 may be configured to communicate directly or indirectly with any number of building controllers 16 , located in a single building or distributed throughout a plurality of buildings. the server 12 is illustrated as a single, cloud-based server. in some cases, the server 12 may be a single server. in some instances, the server 12 may generically represent two, three or more servers commonly located or spread between two or more physical locations. in some cases, the server 12 handles communication with both the mobile device 14 and the building controller 16 . in some instances, as shown for example in fig. 2 , distinct servers may carry out each communications protocol if desired. in some cases, the mobile devices 14 may communicate with the server 12 at least partially through a network such as the internet, sometimes using a cell phone network, wifi network and/or any other suitable network. likewise, it is contemplated that the building controller 16 may communicate with the server 12 at least partially through a network such as the internet, sometimes using a cell phone network, wifi network and/or any other suitable network. in some cases, the mobile device 14 may be a smartphone, a smart watch, a smart ring, a tablet computer, a laptop computer and/or any other suitable device. fig. 2 is a schematic illustration of another illustrative building automation system 20 . the illustrative building automation system 20 includes a first server 22 that may be configured to communicate with a mobile device 14 (or multiple mobile devices 14 ) and a second server 24 that may be configured to communicate with a building controller 16 (or multiple building controllers 16 ). the first server 22 may be configured to receive data from the mobile device 14 , process the data, and send data to the mobile device 14 and/or to the second server 24 . the second server 24 may be configured to receive data from the first server 22 and/or the building controller 16 , process the data, and send data to the building controller 16 and/or to the first server 22 . in some instances, the first server 22 may be configured to permit data from the mobile device 14 to pass directly through to the building controller 16 . in some cases, the second server 24 may be configured to permit data from the building controller 16 to pass directly through to the mobile device 14 . the first server 22 and the second server 24 may be configured to communicate with each other. in some cases, each of the first server 22 and the second server 24 may perform a defined function. it will be appreciated that for simplicity, only a single mobile device 14 is shown, while in many cases the first server 22 may be configured to communicate directly or indirectly with any number of mobile devices 14 . similarly, while a single building controller 16 is illustrated, in many cases the second server 24 may be configured to communicate directly or indirectly with any number of building controllers 16 , located in a single building or distributed throughout a plurality of buildings. the first server 22 is illustrated as a single, cloud-based server. in some cases, the first server 22 may be a single server. in some instances, the first server 22 may generically represent two, three or more servers commonly located or spread between two or more physical locations. the second server 24 is illustrated as a single, cloud-based server. in some cases, the second server 24 may be a single server. in some instances, the second server 24 may generically represent two, three or more servers commonly located or spread between two or more physical locations. in some cases, the first server 22 and the second server 24 may, in combination, be considered as representing or forming a building automation server 26 . fig. 3 is a schematic illustration of a building automation system 30 in which a building automation server 26 is configured to communicate with a plurality of buildings 32 as well as a plurality of mobile devices 34 . it is contemplated that the building automation server 26 may include a single server or two or more distinct servers at one or several locations. the building automation system 30 may serve any desired number of buildings. as illustrated, the plurality of buildings 32 includes a building one, labeled as 32 a, a building two, labeled as 32 b, and so on through a building “n”, labeled as 32 n. it will be appreciated that the building automation system 30 may include a large number of buildings, each in communication with a central (or distributed) building automation server 26 . in some cases, each building may be associated with a unique customer account, as further described below. as illustrated, each of the plurality of buildings 32 includes a building controller and one or more pieces of building equipment. the building equipment may, for example, be hvac equipment, security equipment, lighting equipment, fire suppression equipment, and/or the like. in particular, the building 32 a includes a building controller 36 a and building equipment 38 a, the building 32 b includes a building controller 36 b and building equipment 38 b, and so on through the building 32 n, which includes a building controller 36 n and building equipment 38 n. it will be appreciated that while each building is illustrated as having a single building controller and single building equipment controlled by the single building controller, in some cases a building may have multiple related or unrelated building controllers and/or multiple pieces of related or unrelated building equipment. the plurality of mobile devices 34 may be considered as being divided into a set of mobile devices each associated with a corresponding building. in the example shown, the plurality of mobile devices 34 may be considered as being divided into a set of mobile devices 40 a that are associated with the building 32 a, a set of mobile devices 40 b that are associated with the building 32 b, and so on through a set of mobile devices 40 n that are associated with the building 32 n. as illustrated, the set of mobile devices 40 a includes a first mobile device 42 a, a second mobile device 44 a and a third mobile device 46 a. the set of mobile devices 40 b includes a first mobile device 42 b, a second mobile device 44 b and a third mobile device 46 b and so on through the set of mobile devices 40 n, which includes a first mobile device 42 n, a second mobile device 44 n and a third mobile device 46 n. this is merely illustrative, as any number of mobile devices, such as smartphones or tablets, may be associated with a particular building as desired. each user or occupant of a building may have an associated mobile device or may have several associated mobile devices. in some cases, a user or occupant may have a mobile device associated with several different locations such as a home, a cabin or a place of work. associating a mobile device with a particular building generally involves the individual who uses the particular mobile device. in the example shown in fig. 3 , a mobile device can communicate with the building automation server 26 and may cause the building automation server 26 to provide instructions to the building controller that is associated with the particular mobile device. for example and, in some instances, a mobile phone with location services activated can be used to inform the building automation server 26 as to the whereabouts of the user relative to a geofence defined for the associated building, and in some cases an estimate of how long before the user will arrive at the associated building. the building automation server 26 may send a command to the building controller of the associated building to operate the building equipment in an energy savings manner when all of the users that are associated with a particular building are determined to be away from the building (e.g. the building is unoccupied). the building automation server 26 may send a command to the building controller of the associated building to operate the building equipment in a comfort mode when all of the users that are associated with a particular building are determined or deemed not to be away from the building (e.g. the building is occupied). fig. 4 is a schematic diagram of the illustrative mobile device 14 , as previously referenced in figs. 1 and 2 . the illustrative mobile device 14 has location services 53 for determining a location of the mobile device 14 , and includes a user interface 48 with a display 49 , a memory 50 , a communications module 51 , and a controller 52 that is operably coupled to the user interface 48 , the memory 50 and the communications module 51 . the location services 53 may include, for example, cellular triangulation (ct), global position system (gps), wifi based positioning (wps), and/or any other suitable location service. the communications module 51 may include a wired and/or wireless transceiver. in some cases, the communications module 51 may communicate using cellular communication, wifi communication, bluetooth communication, zigbee communication, wimax communication, and/or any other suitable communication protocol or system as desired. it is contemplated that the memory 50 may be a non-transitory computer-readable storage medium, and in some cases a non-volatile memory. in some cases, the memory 50 may be configured to store an executable program as well as information pertaining to a geofence that is assigned to a building that is associated with the mobile device 14 . in some instances, the memory 50 may also store a geofence log that logs one or more detected geofence crossing events. in some cases, the controller 52 may be configured to upload the geofence log to a remote server, such as the building automation server 26 ( figs. 2 and 3 ) from time to time, upon request, or in response to a detected event. in some instances, with the aid of the location services 53 , the controller 52 of the mobile device 14 may detect a geofence crossing when the mobile device 14 crosses a geofence that is assigned to the building associated with the mobile device 14 . the mobile device 14 may detect the geofence crossing events using different algorithms. the different algorithms can use the same or different location services hardware and/or may include different algorithm settings. the different algorithms may consume different power levels from the mobile device 14 . in some cases, the mobile device may select between a lower power algorithm and a higher power algorithm, wherein a lower power algorithm consumes less power from the mobile device 14 than a higher power algorithm. in one example, in a lower power algorithm, the location services 53 of the mobile device 14 may use cellular triangulation (ct) when detecting geofence crossing events, and may not use the more power hungry global position system (gps) hardware at all. in a higher power algorithm, the location services 53 of the mobile device 14 may use the more power hungry global position system (gps) hardware exclusively and continuously to detect geofence crossing events. the mobile device adopts other algorithms with varying power levels. in one example, to reduce the power consumption of the higher power algorithm described above, the mobile device 14 may adopt an algorithm that does not continuously activate the more power hungry global position system (gps) hardware to detect geofence crossing events. instead, the algorithm may temporarily activate the global position system (gps) hardware to determine if a geofence crossing event has occurred. in some cases, the global position system (gps) hardware may be activated at a certain maximum sample rate, such as 1 reading per minute, 1 reading per 5 minutes, or any other suitable sample rate. in some cases, the sample rate may be set by the mobile device 14 based on the distance that the mobile device 14 is from the geofence, with an increasing sample rate as the mobile device 14 gets closer to the geofence. in some cases, the algorithm may activate the global position system (gps) hardware for a longer or a shorter period of time during each gps sample to increase or decrease the horizontal accuracy, or hdop, of the gps reading. a longer sample period may result in a higher accuracy reading, but will consume more power. in another example algorithm, the location services 53 of the mobile device 14 may use cellular triangulation (ct) or wps to initially detect a geofence crossing event and then temporarily activate the more power hungry global position system (gps) hardware to confirm/deny the initially detected geofence crossing event. this algorithm may be higher power than the algorithm described above that does not use the global position system (gps) hardware at all, but may be lower power than the algorithm that uses the global position system (gps) hardware exclusively and continuously to detect geofence crossing events. in another example algorithm, the location services 53 of the mobile device 14 may use cellular triangulation (ct) or wps to detect a geofence crossing event, and when the cell tower detects that the user is moving, to then activate the more power hungry gps more frequently, for example, such as 1 reading per minute, 1 reading per 5 minutes, or any other suitable sample rate. in some cases, and to reduce the power consumption, not every initially detected geofence crossing event may be confirmed/denied by the global position system (gps) hardware. instead, the algorithm may only confirm/deny the initially detected geofence crossing events at a maximum confirm/deny rate of once per minute, once per five minutes, or any other suitable maximum confirm/deny rate. thus, if the cellular triangulation (ct) or wps detects a series of initially detected geofence crossing events close in time (e.g. due to a low horizontal accuracy of the cellular triangulation), the algorithm may temporarily activate the more power hungry global position system (gps) hardware to confirm/deny only some of the initially detected geofence crossing events, such as one every minute, one every five minutes, or the like. in some cases, the global position system (gps) hardware may be activated for a longer or shorter time period when confirming/denying an initially detected geofence crossing event to increase or decrease the horizontal accuracy, or hdop, of the gps reading. as can be seen from these examples, the mobile device 14 may adopt a wide variety of algorithms that span across a wide range of power consumption levels. in some cases, the mobile device 14 may allow a user of the mobile device 14 to specify whether a lower power algorithm or a higher power algorithm is to be used when detecting geofence crossing events. in some cases, the mobile device may, sometimes with permission from the user, automatically change from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. in some instances, such functionality may be programmed into the mobile device 14 by an executable program stored on a non-transitory computer-readable storage medium. fig. 5 is a schematic view of an illustrative building automation server 26 , as previously referenced in figs. 2 and 3 . the building automation server 26 may be configured for servicing a user's building and, in some cases, other buildings as well. the building automation server 26 may include a memory 54 , a communications module 56 and a controller 58 that is operably coupled to the memory 54 and to the communications module 56 . the memory 54 may be configured for storing a geofence that defines a region about a user's building, and in some cases a log of geofence crossing events received from the user's mobile device. the memory may be ram memory, optical storage, hard disk storage, and/or any other suitable memory. the communications module 56 may be configured to communicate with the user's mobile device 14 . for example, the communications module 56 may receive geofence crossing events from a user's mobile device 14 . in some cases, a geofence crossing event includes a geofence crossing type of inbound or outbound, a timestamp, and/or any other suitable information. in some cases, the communications module 56 of the building automation server 26 may also send information to the user's mobile device 14 . in some instances, this information may include whether a predetermined abnormality is suspected and/or present in the detected geofence crossing events, an adjusted geofence size, and/or any other suitable information. the communications module 56 of the building automation server 26 may also be configured to communicate with an hvac controller that is controlling an hvac system within the user's building. the building automation server 26 may send one or more commands to the hvac controller such that the hvac controller controls the hvac system based at least in part in accordance with the detected geofence crossing events. for example, the building automation server 26 may send a command that causes the hvac controller to enter a more energy efficient away mode (e.g. unoccupied mode) when an outbound geofence crossing event is detected, and to enter a more comfortable home mode (e.g. occupied mode) when an inbound geofence crossing event is detected. this is just one example, in some cases, the mobile device 14 (see fig. 4 ) may be configured to store the geofence associated with the building and to identify when the mobile device 14 crosses the geofence. the communications module 56 of the building automation server 26 may be configured to receive the indications of the geofence crossing events from the mobile device 14 and store them in the memory 54 , sometimes in a geofence crossing log. in some cases, the memory 54 may be configured to store a plurality of logs each associated with a corresponding mobile device 14 , and the controller 58 may be configured to analyze the plurality of logs to determine if a predetermined abnormality is suspected and/or present. if a predetermined abnormality is suspected and/or present, the controller 58 may communicate the suspected abnormality to the mobile device via the communications module 56 . alternatively, or in addition, some or all of the geofence crossing events may be analyzed by the mobile device 14 rather than the building automation server 26 . in some cases, the mobile device 14 may execute an executable program stored in memory 50 that is configured to instruct the mobile device 14 , having a user interface 48 with a display 49 and location services 53 , to store information pertaining to a geofence defined by a size about a location, and with the aid of the location services 53 of the mobile device 14 , to detect a geofence crossing when the mobile device 14 crosses the geofence, and if a geofence crossing is detected, transmit a geofence crossing event to a remote location, such as a remote building automation server 26 . in some cases, the detection of the geofence crossing uses either a lower power algorithm or a higher power algorithm, wherein the lower power algorithm consumes less power from the mobile device 14 than the higher power algorithm. in some cases, a user is allowed to specify via the user interface 48 of the mobile device 14 whether a lower power algorithm or a higher power algorithm is to be used when detecting geofence crossing events, and then the mobile device 14 may adapt to such a lower power or a higher power algorithm when detecting subsequent geofence crossings. in some cases, a lower power algorithm uses cell tower triangulation of the location services 53 of the mobile device 14 , and a higher power algorithm uses the gps of the location services 53 of the mobile device 14 . in some cases, the algorithm uses cell tower triangulation and the gps of the location services 53 of the mobile device 14 , as described above. in some cases, a lower power algorithm uses the gps of the location services 53 of the mobile device 14 where the gps is turned on and sampled at a first rate, and a higher power algorithm uses the gps of the location services 53 of the mobile device 14 where the gps is turned on and sampled at a second higher rate. in some cases, the lower power algorithm and the higher power algorithm may both use the gps of the location services 53 of the mobile device 14 , wherein the lower power algorithm turns the gps on less often than the higher power algorithm. in some cases, the lower power algorithm and the higher power algorithm both use the gps of the location services 53 of the mobile device 14 , and the lower power algorithm obtains a less precise gps location than the higher power algorithm. in some cases, the mobile device 14 displays on the display 49 a slider button, and the user specifies a desired power level for the algorithm along a range of available power level algorithms (see, fig. 9 ). alternatively, or in addition, the mobile device 14 may display on the display 49 a first user selectable option (e.g. radio button) that corresponds to a lower power algorithm and a second user selectable option (e.g. radio button) that corresponds to the higher power algorithm, and the user specifies whether the lower power algorithm or the higher power algorithm is to be used by selecting either the first user selectable option or the second user selectable option. these are just some example input mechanisms. in some cases, detection of the geofence crossing uses either the lower power algorithm, the higher power algorithm, or an intermediate power algorithm, wherein the intermediate power algorithm consumes more power from the mobile device 14 than the lower power algorithm (e.g. is a higher power algorithm to the lower power algorithm) and less power from the mobile device 14 than the higher power algorithm (e.g. is a lower power algorithm to the higher power algorithm). in some cases, the user may be allowed to indicate via the user interface of the mobile device 14 whether the lower power algorithm, the intermediate power algorithm or the higher power algorithm is to be used when detecting geofence crossings. it is contemplated that a user specifying whether a lower power algorithm or a higher power algorithm is to be used does not mean that the user must identify a particular lower power algorithm or a particular higher power algorithm. rather, the user may merely specify a preference along a range of power levels (e.g. see, fig. 9 ), and the mobile device 14 and/or building automation server 26 may identified a suitable power algorithm for use during subsequent geofencing. in some cases, the user may be allowed to set a desired tradeoff between geofence performance and battery life of the mobile device 14 , which is then used by the mobile device 14 and/or building automation server 26 to identify a suitable power algorithm for use during subsequent geofencing. in some instances, the mobile device 14 may, sometimes with permission from the user, automatically change from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. for example, the mobile device 14 may change from using a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. in one example, a predetermined abnormality that may trigger such an algorithm change may include the detection of more than a threshold number of detected geofence crossing events while the mobile device 14 remains at the user's home (e.g. more than zero detected events). in another example, a predetermined abnormality that may trigger such an algorithm change may include the detection of less than a threshold number of detected geofence crossing events when the user leaves home and goes to work (less than 1 detected event). in some cases, if a predetermined abnormality is found, the mobile device 14 may gain permission from a user via the user interface 48 of the mobile device 14 before changing from a lower power algorithm to a higher power algorithm, or vice-versa. it is contemplated that the mobile device 14 may determine if one or more predetermined abnormalities are present in the detected geofence crossing events. in some cases, a remote building automation server 26 or the like may determine if one or more predetermined abnormalities are present in the detected geofence crossing events, and the mobile device simply receives from the remote building automation server 26 whether one or more predetermined abnormalities are present in the detected geofence crossing events. in some cases, the mobile device 14 and a remote building automation server 26 or the like may collectively determine if one or more predetermined abnormalities are present in the detected geofence crossing events. fig. 6 is a schematic view of an example geofencing scenario. in the scenario shown, if the user of the mobile device 14 is located in a region with poor cellular triangulation, such as a rural location 63 a, but the location is known to be remote from a user's home 60 , the user and/or mobile device 14 may elect to use cellular triangulation and conserve battery life of the mobile device 14 . cellular triangulation, especially in a rural location 63 a, may have a relatively low horizontal accuracy, such as illustrated by the relative large horizontal accuracy region 66 . in fig. 6 , horizontal accuracy region 66 represents a statistical measure of the horizontal accuracy (e.g. within 1 standard deviations) of the location reported by the location services of the mobile device 14 . as the user of the mobile device 14 moves closer to the user's home 60 , as shown at 63 b, the horizontal accuracy region 66 of the cellular triangulation may cross into the geofence 62 . when this occurs, the variability in the location provided by cellular triangulation may result in detection of an inbound geofence crossing event even though the actual location of the mobile device 14 remains well outside of the geofence 62 . to help improve the geofencing experience of the user, the user and/or mobile device 14 may elect to switch location services 53 to gps, which may be more power hungry but may have a smaller horizontal accuracy region 68 . in some cases, the user and/or mobile device 14 may temporarily switch location services 53 to gps in order to confirm or deny whether the inbound geofence crossing event detected using cellular triangulation was in fact a valid inbound geofence crossing event. in fig. 6 , and at location 63 b, the gps determines that the mobile device 14 remains well outside of the geofence 62 of the home and that the inbound geofence crossing event was invalid. once the user of the mobile device 14 arrives and stays at home 60 , as shown at 63 c, the user and/or mobile device 14 may switch location services 53 back to cellular triangulation with the larger horizontal accuracy region in order to preserve battery life. this is just one example of a geofence algorithm that provides a balance between power and accuracy. fig. 7 is a schematic view of another example geofencing scenario. in this example, if the mobile device 14 is determined to be in a region with poor cellular triangulation, such as at a rural location 67 a, the user and/or mobile device 14 may switch location services 53 to gps. as noted above, gps may have a relatively small horizontal accuracy region 69 a. in this example, it is contemplated that the gps may be temporarily turned on to detect the current location and to determine if the geofence 62 of the home 60 has been crossed. then the gps may be turned off. in fig. 7 , the gps is turned on at location 67 a to determine if the geofence 62 of the home 60 has been crossed. the gps is then turned off. as can be seen, at location 67 a, the geofence 62 of the home 60 has not been crossed. the mobile device 14 then travels to a location 67 b, where the gps is turned on to determine if the geofence 62 of the home 60 has been crossed. the gps is then turned off. as can be seen, at location 67 b, the geofence 62 of the home 60 has not been crossed. next, the mobile device 14 travels to location 67 c, which is at the home 60 , and then the gps is turned on to determine if the geofence 62 of the home 60 has been crossed. the gps is then turned off. as can be seen, at location 67 c, the geofence 62 of the home 60 has been crossed. the sample rate of gps readings may be set based on the power versus accuracy setting selected by the user (e.g. see fig. 9 ). for example, if the user elects to favor battery life over the geofencing experience, the sample rate of gps readings may be decreased. the sample rate of gps readings is an example algorithm setting that may be changed based on the power versus accuracy setting specified by the user. in some cases, the sample rate of gps readings may be dynamic. for example, the sample rate of gps readings may be based on the distance that the mobile device 14 is currently away from the geofence 62 of the home 60 . for example, if the mobile device 14 is currently one-half hour from the geofence 62 of the home 60 , the sample rate may be set to 1 reading every 20 minutes. if the mobile device 14 is currently five minutes from the geofence 62 of the home 60 , the sample rate may be set to 1 reading per minute. in some cases, the user of the mobile device 14 may be able to select the type of location services 53 based on the current location of the mobile device. for example, for a rural setting, the user of the mobile device 14 may select cellular triangulation to conserve battery life, or the user may select to use a combination of gps and cellular triangulation, or gps alone. for an urban setting, the user of the mobile device 14 may select cellular triangulation, perhaps in combination with wifi based positioning (wps). the mobile device 14 may change the type of location services used based on the current location of the mobile device 14 (e.g. rural settings versus urban setting). in some cases, a rural setting may be identified by predetermined geographic boundaries (e.g. county, city, zip code, etc.) or may be dynamically determined by, for example, monitoring when the horizontal accuracy of cellular triangulation falls below a threshold value. fig. 8 is an illustrative query that may be displayed on the mobile device soliciting information from the user of the mobile device regarding whether the user of the mobile device would like to improve geofencing or not improve geofencing. in the example shown, the mobile device 14 (sometimes in combination with a building automation server 26 ) may determine if the geofence experience is likely to be less than desirable. if so, the mobile device 14 may display the screen 80 on the display 49 of the user interface 48 of the mobile device 14 . this screen 80 seeks permission from the user to automatically change the geofencing settings to improve the geofencing experience. one such settings may be to change from a lower power algorithm to a higher power algorithm if a predetermined abnormality is found to be present in the detected geofence crossing events. other setting changes are also contemplated, including any of those described herein. fig. 9 is an illustrative query allowing the user of the mobile device 14 to select on a sliding scale between “maximum accuracy” of the geofencing experience and “maximum battery life”. the mobile device 14 may display the screen 90 on the display 49 of the user interface 48 of the mobile device 14 , and the user may slide the slider 92 to a desired setting. the mobile device may adjust the algorithm used for geofencing based on the setting selected by the user. for example, if the user slides the slider 92 all the way to the left (maximum accuracy), the mobile device 14 may use the more power hungry global position system (gps) hardware exclusively and continuously to detect geofence crossing events. if the user slides the slider 92 all the way to the right (maximum battery life), the mobile device 14 may use cellular triangulation (ct) or wps when detecting geofence crossing events, and may not use the more power hungry global position system (gps) hardware at all. if the user moves the slider in between these two settings, the mobile device 14 may use an algorithm for geofencing that strikes the selected balance between accuracy and power. those skilled in the art will recognize that the present disclosure may be manifested in a variety of forms other than the specific embodiments described and contemplated herein. accordingly, departure in form and detail may be made without departing from the scope and spirit of the present disclosure as described in the appended claims.
|
051-354-877-256-802
|
US
|
[
"WO",
"ES",
"AU",
"JP",
"US",
"EP",
"DE",
"AT"
] |
A61B17/00,A61B17/072,A61B17/11,A61B17/115,A61B17/10,A61B17/34
| 2000-02-22T00:00:00 |
2000
|
[
"A61"
] |
a fluid delivery device
|
a fibrin injection mechanism for use in combination with an anastomosing and stapling attachement for an electromechanical device driver comprises a cylindrical dispensing chamber (95) adjacent the cylindrical blade (75) of the attachement and containing a sac (100) filled with fibrin, a plurality of channels extending (90) within the blade (75) communicating between the dispensing chamber (95) and the cutting edge (75) of the blade, such that when the turning drive shaft is activated, the staple driver (65) of the attachment moves forward to push a plurality of staples (60) through corresponding staple ports (55) and against the anvil (20) of the attachment to pass through and staple together the target tissue, while the blade driver (75) of the attachment moves forward to cut the unwanted residual tissue (post stapling), while a plunger (delivery) driver (110) moves forward through the dispensing chamber (95) to compress the sac (100) to its break point, releasing the fluid medication into the dispensing chamber (95), and eventually pushing the medication through the channels (90) to deliver the fibrin to the cutting edge of the blade (75) and thus to the site of the newly stapled target tissue to accelerate the healing process.
|
what is claimed is: 1. a fluid dehvery device, compnsing: a dispensmg chamber containing a fluid; a channel communicatmg between a treatment site and said dispensmg chamber; a dehvery dπver traveling withm said dispensmg chamber with a force equal to or greater than the force needed to push said fluid through said channel. 2. the device of claim 1, further compnsing a sac withm said dispensmg chamber and enclosmg said fluid; and wherem said dehvery driver is traveling with a force equal to or greater than the force needed to compress and break said sac withm said dispensmg chamber. 3. the device of claim 1, wherem said channel communicates also with a cuttmg edge of a blade. 4. the device of claim 3, wherem said dispensmg chamber is adjacent said blade. 5. the device of claim 4, wherem said dehvery dπver is rigid and said blade is driven by a blade driver havmg a compressible portion. 6. the device of claim 5, wherem said compressible portion comprises a sprmg. 7. the device of claim 4, wherem said dehvery driver is rigid and said blade is dπven by a blade driver havmg a break-away portion havmg a rigidity that is less than the πgidity of said delivery driver. 8. the device of claim 3, wherem said channel extends withm said blade. 9. the device of claim 1, wherem said channel communicates also with a stapling surface of a stapler. 10. the device of claim 3, wherem said dispensmg chamber is adjacent said stapler. 11. the device of claim 10, wherem said delivery dπver is πgid and said stapler is driven by a staple driver havmg a compressible portion. 12. the device of claim 11, wherein said compressible portion compπses a sprmg 13 the device of claim 10, wherein said delivery dπver is ngid and said stapler is driven by a staple driver havmg a break-away portion havmg a πgidity that is less than the πgidity of said delivery dπver 14 the device of claim 3, wherem said channel extends withm said stapler. 15 the device of claim 4, wherem said blade is adjacent a stapler havmg a staphng surface, said blade havmg a cuttmg edge which travels adjacent said stapling surface, and wherem said channel communicates also with said cutting edge of said blade. 16 the device of claim 15, wherein said delivery dπver is πgid, said blade is dπven by a blade driver connected to said delivery dπver, and said stapler is dπven by a staple dπver connected to said dehvery driver. 17 the device of claim 16, wherem at least one of said blade dπver and said staple driver has a compressible portion 18. the device of claim 16, wherem at least one of said blade dπver and said staple dπver has a break-away portion havmg a rigidity that is less than the rigidity of said dehvery driver. 19 the device of claim 16, wherein said blade, said blade driver, said stapler, said staple dπver, said dispensmg chamber, and said dehvery driver, are cylindrical and share a common cyhndrical axis. 20. the device of claim 19, further compπsmg a sac withm said dispensmg chamber and enclosmg said fluid medication; and wherem said dehvery driver is travelmg with a force equal to or greater than the force needed to compress and break said sac within said dispensmg chamber.
|
a fluid delivery device for use with anastomosing, stapling, and resecting instruments background of the invention field of the invention the present invention relates generally to a fluid delivery device for use with anastomosing, stapling, and resecting surgical tools, and more specifically to a fibrin injection mechanism by which such tools may deliver fibrin to the stapling and cutting site of a resected colon. descπption of the prior art upon identification of cancerous or other anomalous tissue in the gastrointestinal tract, surgical intervention is often prescπbed. the field of cancer surgery, and more specifically, the surgical procedure by which a section of the gastrointestinal tract which includes cancerous or anomalous tissue is resected, mcludes a number of uniquely designed instruments in combination with a descπption of the present instrumentation and their functions, a description of the state of the art in this surgical procedure shall also be provided. the first question which must be answered when determining how to treat gastrointestinal cancer relates to the specific location of the cancerous tissue. this is very important insofar as the instruments which are provided in the present art have limitations relating to how far they may be inserted into the gastrointestinal tract. if the cancerous tissue is too far up the colon, for example, then the standard instrumentation provided is unusable, thus requiring special accommodations. these accommodations generally increase the πsk of contamination of the surrounding tissues with bowel contents, increase the length of the surgery and the corresponding need for anesthesia, and eliminate the benefits of precise anastomosing and stapling which comes from utilizing a mechanized device. more specifically, in the event that the cancerous tissue is located at a position in the colon which is accessible by the present instrumentation, the patient's abdomen is initially opened to expose the bowel. the surgeon then utilizes a linear cutter and stapling device which cuts the tube of the colon on either side of the cancerous tissue, thereby creating two stapled ends of the bowel (a distal end which is directed toward the anus, and the proximal end which is closest to the small intestine) this is done in order to temporarily minimize contamination more particularly, referring to fig 1, the bowel is placed between the scissoring elements 1, 2 at the tip of the linear stapling instrument 5 by squeezing the tπgger 3 in the handle 4 of the device, the surgeon causes the scissoring elements 1, 2 to come together a second trigger (or a secondary action of the same tngger) is then actuated to drive a seπes of staples 6 through the clamped end of the colon, thereby closing and transecting the ends the surgeon then partially opens the proximal end and inserts the removable anvil portion of an anastomosing and stapling instrument into the exposed proximal end this step, as well as those of the remainder of the surgical procedure, are related to the functioning of this surgical instrument more particularly, and with respect to fig 2, the surgeon begins by taking the instrument 7 and manually turning the dial 8 at the base of the handle 9 which causes the anvil head 10 at the opposite end to advance forward the surgeon continues to turn the dial 8 until the anvil head 10 advances to its most extreme extended position this manual turning requires nearly thirty full rotations once fully extended, the anvil head of the instrument is decoupled therefrom and is inserted into the partial opening of the proximal end such that the coupling post extends outwardly therethrough this partial opening of the proximal end is then sutured closed the extending shaft 11 of the anastomosing and stapling instrument 7 is then inserted and advanced into the lower colon, transanally, until the coupling stem 12 thereof extends through the stapled distal end the surgeon then joins the coupling ends of the anvil and shaft together and begins to manually rotate the dial in the handle again, this tune bringing the anvil head closer to the end 13 of the shaft once the anvd head and shaft are brought close together, after the surgeon has manually rotated the dial another thirty times, a grip-style trigger 14 in the handle is manually actuated this actuation causes a circular blade 15 to advance axially out from the tip of the shaft, and into contact with the opposing face 16 of the anvil 10 the blade cuts through the stapled-closed ends of the proximal and distal ends of the colon, thereby also cutting a new pair of ends of the proximal and distal portions of the colon the tissue which has been severed is held in an interior volume at the end of the shaft in lock step with the cutting, the freshly opened ends are joined together by a seπes of staples 17 which are advanced through holes in the perimeter of the tip of the shaft (being pressed against and closed by the opposing face of the anvil). the coupled shaft and anvil are then withdrawn from the patient. as with many such devices of the pπor art, all of the above devices are considered fully disposable, and are, in fact, thrown away after a single use. they are complicated devices, having multiple moving parts, requiring substantial structural integπty and, therefore, expense in manufacturing. the fact that they are used only once, and no part can be used again render the use of such devices expensive and wasteful of resources. in addition to this failure, as can be readily observed from the preceding descriptions, the prior art devices suffer from numerous other limitations which would be desirable to overcome. these include the requirement that the surgeon manually actuate a number of different functions (including those associated with the dial and tπgger of the anastomosing and stapling instrument and the multiple triggers of the cutting and stapling instrument). another failure is that the prior art devices provide no means to allow the delivery of fluid to the site of the freshly cut tissue. medicme or other substances which accelerate the healing process, if dehvered to the site simultaneous with or subsequent to the stapling and cutting process, could speed hea ng of the tissue or perform other medical functions. one such substance is fibrin, which is the principal protein component of connective tissue, and serves as the fundamental element of the tissue- mending process, specifically the process of scar formation at the joining of two previously separate tissues. therefore, the ability to inject such a substances at the site of the freshly stapled and cut tissue would provide an advantage over the prior art devices, which make no provision for such delivery. therefore, it is a principal object of the present invention to provide a fluid delivery device which can effect such medicine delivery at the stapling and cutting site of targeted tissue. it is also a principal object of the present invention to provide such a fluid delivery device in a form integral with an instrument for cutting, anastomosing, and stapling, which reduces the waste of resources by permitting the reuse of portions thereof. it is further an object of the present invention to provide such a fluid dehvery device which reduces the requirements for the surgeon to manually actuate different components and mechanisms. other objects of the present invention shall be recognized in accordance with the descπption thereof provided hereinbelow, and in the detailed descπption of preferred embodiments in con j unction with the remaining figures summary of the invention the preceding objects of the invention are provided by a fluid dehvery mechanism which is integral with an anastomosing and stapling attachment of an electromechanical driver assembly which couples to the anastomosing and stapling attachment. more particularly, the present invention compπses a dispensing chamber containing a fluid, a channel communicating between a treatment site and the dispensing chamber, and a delivery or plunger driver traveling within the dispensing chamber with a force equal to or greater than the force needed to push the fluid through the channel. in the preferred embodiment, the present invention is used in combination with an anastomosing and stapling attachment of an electromechanical device driver. it comprises a cylindrical dispensing chamber adjacent the cy ndπcal blade of the attachment. the dispensing chamber contains a sac filled with fibπn. a plurality of channels extend within the blade and communicate between the dispensing chamber and the cutting edge of the blade. a turning drive shaft of the attachment which is connected to the electromechanical driver dπves a staple driver, a blade driver, and a dehvery (plunger) dπver. when the turning drive shaft is activated (via the trigger on the electromechanical dπver handle), the staple driver moves forward to push a plurality of staples through corresponding staple ports and against the anvil of the attachment to pass through and staple together the target tissue. meanwhile, by the same activating mechanism, the blade driver of the attachment moves forward to cut the unwanted residual tissue (the tissue which is no longer needed). also meanwhile, the plunger dπver moves forward through the dispensing chamber to compress the sac to its break point. when the sac breaks, the fluid is released into the dispensing chamber. the plunger dπver continues forward, pushing the fluid into and through the channels in the blade, delivering the medicme to the cutting edge of the blade and thus to the site of the newly stapled target tissue to begin acceleration the heahng process. specifically, with respect to the electromechanical dπver, the driver is shown in fig. 3 and has a handle 150 and a flexible dnve shaft 155. the handle 150 has a pistol gπp-styled design, having one or more, and preferably two, finger triggers 160 which are independently coupled to at least one, and preferably two separate motors 165 which each turn separate flexible dπve shafts 170 (descπbed more fully, herembelow) the motors 165 are each dual direction motors, and are coupled to a manual dnve switch 172 to the top of the handle, by which the user can selectively alter the turning direction of each motor. this dual direction capacity may be most simply achieved by selecting motors which turn in a direction corresponding to the direction of current, and actuation of the dπve switches alters the direction of the current accordingly. in this example, the power source 175 supplying the motors must be a direct current source, such as a battery pack (and most desirably, a rechargeable battery pack). in the event that the device should be useable with an alternating current, either a transformer can be included, or a more sophisticated intermediate gearing assembly may be provided. in conjunction with the present description, the embodiments of the present invention which will be descπbed utilize a rechargeable battery pack providing a direct current. in addition to the motor components, the handle further includes several other features, including a remote status indicator 180, a shaft steering means 185, and an on/ off switch (not shown). first, the remote status indicator may comprise an lcd (or similar read out device) by which the user may gain knowledge of the position of components (for example whether a clamping element is in the proper position pπor to the dnving of the staples). second, the handle also includes a manually actuateable steering means, for example, a joystick or track ball, for directing the movement of the flexible shaft (by means of steering wires implanted in the shaft portion described more fully hereinbelow). finally, the handle may include an additional electrical power supply and an on/ off switch for selectively supplying electrical power to the attachments. more particularly, with respect to the flexible shaft, the shaft comprises a tubular sheath 195, preferably formed of a simple elastomeπc material which is tissue compatible and which is stenlizable (1 e , is sufficiently rugged to withstand an autoclave) various lengths of this shaft mav be provided the flexible shaft and the handle portions can be separable if separable, the interface between the proximal end of the shaft and the distal end of the handle should mclude a coupling means for the dπve components specifically regarding the drive components of the shaft, within the elastomeπc sheath are a pair of smaller fixed tubes 215 which each contain a flexible drive shaft 220 which is capable of rotating within the tube the flexible dπve shaft, itself, translates a torque from the motor in the handle to the distal end of the shaft, but is flexible enough to be bent, angled, curved, etc as the surgeon deems necessary to "snake" through the colon of the patient in order for the distal end of the dπve shaft to couple with an attachment, such as the anastomosing and stapling attachment discussed herein, however, the distal tips of the drive shafts must have a conformation which permits the continued translation of torque for example, the distal tips 200 of the dπve shafts may be hexagonal, thereby fitting into a hexagonal recess in the coupling interface of the attachment appropriate gearing mechanisms may be provided at the distal end of the shaft, or in the interfacing portion of the attachment, to ensure that the appropriate torque is provided to the attachment as suggested above, in conjunction with the manually actuateable steering means mounted to the handle, the sheath further includes at least two steering wires 205 which are flexible, but are coupled to the inner surface of the sheath near the distal end thereof the steering wires may be axially translated relative to one another by actuation of the steering means, which action causes the sheath to bend and curve accordingly also as suggested above, in conjunction with the lcd indicator of the handle, the shaft further contains an electrical lead 210 for coupling to the attachments this electrical lead channels a signal from the attachment to the handle for indicating the status of the attachment (for example, whether the anvil portion is in close proximity to the sbr portion, so that the surgeon knows it is safe to staple) similarly, a second electrical lead may be provided to supply power to separate aspects of the attachment if so required referring now to the fluid dehvery device of the present invention, descπbed here in con j unction with an anastomosing and stapling attachment, a preferred embodiment and an alternative embodiment are described herembelow as examples of the different variations which could be constructed for the equivalent purpose. the anastomosing and stapling attachment compπses an anvil portion, and a staple, blade and reservoir portion (sbr portion), which includes a pair of turning dπve shafts which are coupleable to the drive components of the shaft element descπbed above, and a corresponding pair of advancing and retracting nuts mounted to the turning drive shafts, but which are prevented from rotating and therefore nearly advance and retract along the shafts when they turn. the anvil portion is bullet shaped, having a blunt nosed top portion, a flat cutting support surface on the bottom, and a freely rotating coupling post extending axially from the bottom surface. this coupling post is designed to be selectively coupleable and removable from the corresponding nut mounted to one of the turning dπve shafts. the sbr portion is cylindrical in shape, forming a housing which has a hollow inteπor. it is this hollow interior which forms the reservoir. on the axially outward facmg surface of the cy ndπcal wall of the housing are a series of staple ports, through which the staples of the device are discharged. a seπes of staple drivers are mounted within the cy ndπcal walls, beneath the staple ports, for driving the staples therethrough. more accurately, the staple drivers are a series of protuberances on the outer edge of a single cyhndπcal component which seats in the wall of the sbr portion. the staples, prior to being discharged, are mounted in the holes, and they are advanced through the holes by the forward motion of the staple driver and the protuberances thereof. the blade is similarly cylindrical, and seats in the inside of the housing, against the inner surface of the wall thereof. both the blade and the staple driver are mounted to the second nut, which is, in turn, mounted to the other turning dπve shaft. as the tuning drive shaft rotates, the nut (which is constrained against rotating) advances along the shaft, thus linearly advancmg the blade and staple driver. the blade and the staple driver are, therefore, selectively advanceable axially outward from the housing, in accordance with actuation of the appropπate trigger on the handle. in order to accelerate the hea ng process, the attachment is fitted with the present invention, i.e., a mechanism for delivering fluid, medicme or a hea ng substance such as fibrin at the cutting and stapling site, immediately after the cutting and stapling action descπbed above. this mechanism can take on any of several embodiments, two of which are descnbed herembelow as examples. generally, the fibπn is contained withm a sac formed by a than skin or membrane. the sac is contained within a dispensing chamber through which travels a dehvery or plunger dπver. once the blade and the staple driver reach the anvil, the blade and staple driver are stopped by the anvil, simultaneously performing the stapling and cutting actions descπbed above. the dehvery or plunger driver, coupled to the second nut along with the blade and the staple dπver, continues on, dnven axially outward from the housmg, compressing the sac, causmg pressure to build in the sac. once the pressure reaches the break pomt of the membrane, the fibrm is released and is transferred from the sac to the cutting and stapling site via channels m the blade. in practice, this attachment is utilized once the section of the colon which is to be removed has been resected (but pπor to the hnear clamping and staplmg step is complete), m the following manner. the surgeon begins by coupling the anastomosing and stapling attachment to the electromechanical driver and advancmg the anvil portion to its fullest extent. the anvd head is then removed and inserted mto the exposed proximal end. this proximal end is then stapled closed (with the coupling post protruding from the stapled proximal end). the surgeon then advances the shaft and the sbr portion of the attachment up the colon until it extends through the stapled distal end of the colon. the surgeon then couples the anvil to the advancmg and retracting nut of the coπesponding dπve shaft. subsequent tπggermg of the motor m the handle causes the anvil to retract toward the sbr portion. when the anvil portion and the sbr portion have come close enough to dπve the blade and staple driver, subsequent actuation of the other trigger on the handle causes the correspondmg other turning drive shaft to advance the blade and staple dπver toward the flat cutting support surface of the anvil portion. the blade cuts through the stapled-closed ends of the colon, leavmg the tissue which has been severed in the mteπor reservoir. simultaneous with the cutting, the freshly opened ends are joined together by the seπes of staples which are advanced through holes m the perimeter edge of the sbr (being pressed against and closed by the opposing face of the anvd). shortly thereafter, as descnbed above, the plunger dπver advances, increasing pressure m the membrane which contams the fibπn. once the membrane breaks, the hbπn is released and transferred to the cutting and stapling site through holes in the blade. the attachment and the flexible shaft are then withdrawn from the patient. it should be noted that the present invention may be used in conjunction with a staphng attachment only, such that the dispensing chamber is adjacent the stapler, and the channels extend withm or adjacent the stapler to deliver the medicme or heahng substance such as fibrin to the staphng site. this may be used if the cutting action is not needed. inasmuch as the present mvention can be used for applications and m conjunction with devices not related to the anastomosmg and staphng attachment, or even colon resecting tools, but rather can be used for apphcations involving and m conjunction with other surgical devices, the present mvention can be used alone, or with a blade, or with a stapler, or with other devices or combinations of devices. a brief description of the drawings fig. 1 is a side perspective view of a linear clamping and stapling instrument of the pπor art; fig. 2 is a side perspective view of an anastomosmg and staphng instrument of the pπor art; fig. 3 is a side view of a handle and flexible shaft of an electromechanical device dπver which is used to dπve the anastomosmg and stapling attachment descπbed herein; fig. 4 is a perspective view of an anastomosmg and staphng attachment having an integrated medicme dehvery device of the present mvention; fig. 5 is a side cutaway view of a first embodiment of the medicme delivery device of the present mvention mtegral with an anastomosing and staphng attachment; and fig. 6 is a side cutaway view of a second embodiment of the medicme dehvery device of the present mvention mtegral with an anastomosmg and staphng attachment. a detailed description of the preferred embodiment while the present mvention will be descπbed more fully hereinafter with reference to the accompanying drawmgs, in which particular embodiments are shown, , it is to be understood at the outset that persons skilled m the art may modify the mvention herem described while achievmg the functions and results of this mvention. accordingly, the descπptions which follow are to be understood as illustrative and exemplary of specific structures, aspects and features withm the broad scope of the present mvention and not as limiting of such broad scope like numbers refer to similar features of like elements throughout. a preferred embodiment of the fluid dehvery device for an anastomosmg and staphng attachment accordmg to the present mvention is illustrated in figs. 4-6. more particularly, referrmg now to fig. 4, a perspective exterior view of an anastomosmg and staphng attachment m an extended position is shown the anvil portion 20 and the staple, blade, and reservoir (sbr) portion 25 are connected by a coupling post 30 which extends from the flat cuttmg support surface 35 of the anvil portion 20 and is selectively coupleable and removable from the corresponding nut mounted to one of the turning drive shafts 40 of the sbr portion 25. referrmg now also to fig. 5, a cutaway view of the interior of the sbr portion 25 is shown the sbr portion 25 is cylindrical in shape, and has a hollow intenor, or reservoir 45. a stapling surface 50 faces axially outward toward the cuttmg support surface 35 of the anvil portion 20, and contams a seπes of staple ports 55, through which staples 60 are discharged. a series of staple dπvers 65 are mounted withm a staple driver shaft 80, behind correspondmg staple ports 55, for driving the staples 60 therethrough. more accurately, the staple drivers 65 are a seπes of protuberances on the outer edge of a dπvmg cylinder 70 which seats m the sbr portion 25 and which is connected to the second drive shaft (not shown) of the sbr portion 25 the staples 60, prior to being discharged, are mounted behind the staple ports 55 as shown and are advanced through the ports 55 by the forward motion of the staple drivers 65 and the protuberances thereof. the blade 75 is similarly cyhndπcal, and seats in the sbr portion adjacent the staple dπver shaft 80. both the blade 75 and the staple drivers 65 are mounted via semirigid springs 85 to the dπvmg cylinder 70 as shown, which is connected to the second drive shaft (not shown) of the sbr portion 25. the nature of the semi-πgidity of the springs 85 will be explamed below. the blade 75 further has a seπes of channels 90 communicating with a dispensmg chamber 95. the chamber 95 extends from the inner side of the blade 75 and spans the circumference of the blade 75, while the channels 90 are tubular m nature and are positioned at mtervals along the length of the blade 75, so as to maintain the structural integrity of the blade 75 while it is being used for cuttmg. withm the chamber 95 is contamed a sac 100 formed by a sealed membrane 105 and which contams fibπn (not noted). immediately behmd the sac 100 is positioned a plunger dπver 110 which is mounted to the dπvmg cylinder 70 as shown. referrmg now to fig. 6, the preferred embodiment of the fluid dehvery device of an anastomosmg and stapling attachment accordmg to the present mvention is illustrated. all components are as described above for fig. 5, however, the staple drivers 65 and blade 75 are mounted to the dπvmg cylinder 70 not by sprmgs 85, but rather by a break-away extension 115 as shown shade. in operation (operation of both embodiments will be described below), the attachment is utilized once the section of the colon which is to be removed has been resected (but prior to the linear clamping and staphng step is complete) the surgeon begins by coupling the anastomosmg and staplmg attachment to the electromechanical driver and advancmg the anvil portion 20 to its fullest extent via a triggering of the motor (not shown) m the handle (not shown). the anvil portion 20 is then decoupled from the electromechanical dπver and inserted into the exposed proximal end. this proximal end is then stapled closed (with the coupling post 30 protruding from the stapled proximal end). the surgeon then advances the first turning drive shaft 40 and the sbr portion 25 of the attachment up the colon until it extends through the stapled distal end of the colon. the surgeon then re-couples the anvil portion 20, via the coupling post 30, to the first turning drive shaft 40. subsequent reverse tπggeπng of the motor (not shown) m the handle (not shown) causes the anvil portion 20 to retract toward the sbr portion 25, thus bringing the stapled-closed proximal and distal ends of the colon together when the anvil portion 20 and the sbr portion 25 have come close enough to drive the blade 75 and staple driver 65, subsequent actuation of a second tπgger (not shown) on the handle (not shown) causes the correspondmg second turning dπve shaft (not shown) to advance the blade 75 and staple driver 65 toward the flat cuttmg support surface 35 of the anvil portion 25. once the blade 75 reaches the flat cuttmg support surface 35 of the anvil portion 25, the blade 75 cuts through the stapled- closed proximal and distal ends of the colon, leavmg the now-severed tissue m the reservoir 45. meanwhile, the staple drivers 65 (which have been advancmg with the blade 75, yet positioned slightly behmd the plane of the blade 75 as shown, m order to correctly time the stapling action to come immediately after the cutting action) reach the butts of the staples 60, and contmue forward to push the staples 60 through the staple ports 55 and toward the staphng surface 50 and finally agamst the flat cuttmg support surface 35, which action bends the staple prongs to close the staples 60, thereby joining together the freshly cut-open proximal and distal ends of the colon. meanwhile, the plunger dπver 110 (which has been advancmg with the blade 75 and staple dnvers, yet positioned shghtly behind the plane of the staple drivers 65 as shown, in order to coπectly time the plunging action to come immediately after the stapling action) advances, reachmg the sealed membrane 105 as the stapling action is completed. in the fust embodiment described above, thereafter the semi-πgid sprmgs 85 (shown in fig. 5) of the blade 75 and staple dπvers 65 begm to compress from the forward motion of the second turning drive shaft (not shown). this allows the plunger driver 110 to continue its forward motion as well, and to thereby begin compression of the sealed membrane 105, thereby mcreasmg pressure m the sealed membrane 105 which contams the fibπn (not noted). it should be noted that this embodiment allows re-use of the attachment, as the sprmgs 85 will decompress after the pressure on the staple dπvers 65 is released by retracting the second turning drive shaft. once a new sac 100 is placed m the dispensmg chamber 95, the attachment is ready for the next operation (assuming proper sterilization procedures have been followed). alternatively, m the second (preferred) embodiment described above, after the stapling action is completed, the break away extension 115 (shown m fig. 6), from which extend the blade 75 and staple drivers 65, snaps off and its remnants are trapped withm the body of the attachment as the forward motion of the second turning drive shaft (not shown) continues to move the plunger driver 110 forward. the forward motion of the plunger driver 110 begins compression of the sealed membrane 105, thereby mcreasmg pressure m the sealed membrane 105 which contams the fibrm (not noted). it should be noted that the destruction of the break away extension 115 does not allow this attachment to be re-used. once the plunger dπver 110 has compressed the membrane 105 to its maximum stress limit, the membrane 105 breaks, the fibπn is released, and passes through the channels 90 m the blade 75, and is thereby transferred to the cuttmg and staphng site (the freshly cut tissue) the blade 75, staple dπvers 65, and plunger dπver 110 can be withdrawn by reverse triggering the second turning dπve shaft (not shown). the attachment and the flexible shaft are then withdrawn from the patient. while there has been descπbed and illustrated specific embodiments of new and novel fluid dehvery devices, it will be apparent to those skilled in the art that vaπations and modifications are possible without deviating from the broad spiπt and principle of the present mvention which shall be limited solely by the scope of the claims appended hereto
|
051-900-523-974-714
|
US
|
[
"US"
] |
B65D85/00,A45C11/00
| 2012-08-02T00:00:00 |
2012
|
[
"B65",
"A45"
] |
mobile device enclosure system
|
a mobile device enclosure system is an apparatus that is provided as a means to protect a mobile device from the wear and tear of daily usage without limiting the portability of the mobile device or the accessibility of said mobile device's hardware keys or charging ports. the apparatus accomplishes this through the use of an inner sleeve and an outer case. the inner sleeve is enclosed within the outer case. the inner sleeve houses the mobile device and protects it from everyday wear and tear while the outer case houses both the inner sleeve and the mobile device protecting them from accidental damage. additionally, the configuration of the inner sleeve and the outer case permits the mobile device to be particularly oriented and positioned in order to conform to a tradition landscape and portrait display view as well as alternative configurations.
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1. a mobile device enclosure system comprises: an inner sleeve; an outer case; the inner sleeve comprises a front panel, a rear panel, a side wall, an inner sleeve opening, a side strap, and a plurality of port openings; the outer case comprises a first outer flap, a second outer flap, and a sleeve fold; the front panel comprises an open viewing area; the rear panel comprises an outer case coupler, a hand strap, and a kickstand; the side wall comprises the inner sleeve opening; the first outer flap, the second outer flap, and the sleeve fold each comprise an interior face side; the kickstand comprises a recessed flap and a hinge; the interior face side of the second outer flap comprises an inner sleeve mount; the inner sleeve being rotatably coupled to the outer case; and the inner sleeve being detachably coupled between the first outer flap and the second outer flap. 2. the mobile device enclosure system as claimed in claim 1 comprises: the sleeve fold being positioned between the first outer flap and the second outer flap; the first outer flap being pivotally coupled to the second outer flap by way of the sleeve fold; the interior face side of the first outer flap, being coincident with the interior face side of the sleeve fold, and the interior face side of the second outer flap; the inner sleeve being peripherally surrounded by the interior face side of the first outer flap, the interior face side of the sleeve fold, and the interior face side of the second outer flap; and the rear panel being detachably coupled to the interior face of the second outer flap. 3. the mobile device enclosure system as claimed in claim 1 , wherein the interior face side of the first outer flap comprises a plurality of accessory pockets. 4. the mobile device enclosure system as claimed in claim 3 , wherein the interior face side of the sleeve fold comprises an accessory mount. 5. the mobile device enclosure system as claimed in claim 3 comprises: the inner sleeve mount being pivotably coupled to the interior face side of the second outer flap; the outer case coupler being detachably engaged to the inner sleeve mount; and the outer case coupler being rotatably attached to the inner sleeve mount. 6. the mobile device enclosure system as claimed in claim 1 comprises: the plurality of port opening being particularly positioned on the front panel, the rear panel, and the side wall; the open viewing area centrally traverses the front panel; the front panel being juxtaposed parallel to the rear panel; the front panel being flexibly coupled to the rear panel by way of the side wall; the front panel being perimetrically engaged to the side wall; the rear panel being perimetrically engaged to the side wall opposite the front panel; the inner sleeve opening traverses the side wall between the front panel and the rear panel; the side strap being flexibly coupled to the front panel; the side strap being detachably coupled to the rear panel; and the side strap spans across the inner sleeve opening, wherein the side strap spans across the inner sleeve opening from the front panel to the rear panel. 7. the mobile device enclosure system as claimed in claim 1 comprises: the outer case coupler being centrally positioned on the rear panel opposite the front panel; the outer case coupler being positioned between the hand strap and the kick stand; the hand strap and the kick stand being positioned flush with the rear panel; the recessed flap being pivotally engaged to the rear panel by way of the hinge; and the recessed flap being positioned between the hinge and the outer case coupler. 8. a mobile device enclosure system comprises: an inner sleeve; an outer case; the inner sleeve comprises a front panel, a rear panel, a side wall, an inner sleeve opening, a side strap, and a plurality of port openings; the outer case comprises a first outer flap, a second outer flap, and a sleeve fold; the front panel comprises an open viewing area; the rear panel comprises an outer case coupler, a hand strap, and a kickstand; the side wall comprises the inner sleeve opening; the first outer flap, the second outer flap, and the sleeve fold each comprise an interior face side; the kickstand comprises a recessed flap and a hinge; the interior face side of the second outer flap comprises an inner sleeve mount; the inner sleeve being rotatably coupled to the outer case; the inner sleeve being detachably coupled between the first outer flap and the second outer flap; the plurality of port opening being particularly positioned on the front panel, the rear panel, and the side wall; the open viewing area centrally traverses the front panel; the front panel being juxtaposed parallel to the rear panel; the front panel being flexibly coupled to the rear panel by way of the side wall; the front panel being perimetrically engaged to the side wall; and the rear panel being perimetrically engaged to the side wall opposite the front panel. 9. the mobile device enclosure system as claimed in claim 8 comprises: the sleeve fold being positioned between the first outer flap and the second outer flap; the first outer flap being pivotally coupled to the second outer flap by way of the sleeve fold; the interior face side of the first outer flap, being coincident with the interior face side of the sleeve fold, and the interior face side of the second outer flap; the inner sleeve being peripherally surrounded by the interior face side of the first outer flap, the interior face side of the sleeve fold, and the interior face side of the second outer flap; and the rear panel being detachably coupled to the interior face of the second outer flap. 10. the mobile device enclosure system as claimed in claim 9 , wherein the interior face side of the first outer flap comprises a plurality of accessory pockets. 11. the mobile device enclosure system as claimed in claim 9 , wherein the interior face side of the sleeve fold comprises an accessory mount. 12. the mobile device enclosure system as claimed in claim 9 comprises: the inner sleeve mount being pivotably coupled to the interior face side of the second outer flap; the outer case coupler being detachably engaged to the inner sleeve mount; and the outer case coupler being rotatably attached to the inner sleeve mount. 13. the mobile device enclosure system as claimed in claim 8 comprises: the inner sleeve opening traverses the side wall between the front panel and the rear panel; the side strap being flexibly coupled to the front panel; the side strap being detachably coupled to the rear panel; the side strap spans across the inner sleeve opening, wherein the side strap spans across the inner sleeve opening from the front panel to the rear panel; the outer case coupler being centrally positioned on the rear panel opposite the front panel; the outer case coupler being positioned between the hand strap and the kick stand; the hand strap and the kick stand being positioned flush with the rear panel; the recessed flap being pivotally engaged to the rear panel by way of the hinge; and the recessed flap being positioned between the hinge and the outer case coupler. 14. a mobile device enclosure system comprises: an inner sleeve; an outer case; the inner sleeve comprises a front panel, a rear panel, a side wall, an inner sleeve opening, a side strap, and a plurality of port openings; the outer case comprises a first outer flap, a second outer flap, and a sleeve fold; the front panel comprises an open viewing area; the rear panel comprises an outer case coupler, a hand strap, and a kickstand; the side wall comprises the inner sleeve opening; the first outer flap, the second outer flap, and the sleeve fold each comprise an interior face side; the kickstand comprises a recessed flap and a hinge; the interior face side of the second outer flap comprises an inner sleeve mount; the inner sleeve being rotatably coupled to the outer case; the inner sleeve being detachably coupled between the first outer flap and the second outer flap; the plurality of port opening being particularly positioned on the front panel, the rear panel, and the side wall; the open viewing area centrally traverses the front panel; the front panel being juxtaposed parallel to the rear panel; the front panel being flexibly coupled to the rear panel by way of the side wall; the front panel being perimetrically engaged to the side wall; the rear panel being perimetrically engaged to the side wall opposite the front panel; the inner sleeve opening traverses the side wall between the front panel and the rear panel; the side strap being flexibly coupled to the front panel; the side strap being detachably coupled to the rear panel; the side strap spans across the inner sleeve opening, wherein the side strap spans across the inner sleeve opening from the front panel to the rear panel; the outer case coupler being centrally positioned on the rear panel opposite the front panel; the outer case coupler being positioned between the hand strap and the kick stand; the hand strap and the kick stand being positioned flush with the rear panel; the recessed flap being pivotally engaged to the rear panel by way of the hinge; and the recessed flap being positioned between the hinge and the outer case coupler. 15. the mobile device enclosure system as claimed in claim 14 comprises: the sleeve fold being positioned between the first outer flap and the second outer flap; the first outer flap being pivotally coupled to the second outer flap by way of the sleeve fold; the interior face side of the first outer flap, being coincident with the interior face side of the sleeve fold, and the interior face side of the second outer flap; the inner sleeve being peripherally surrounded by the interior face side of the first outer flap, the interior face side of the sleeve fold, and the interior face side of the second outer flap; and the rear panel being detachably coupled to the interior face of the second outer flap. 16. the mobile device enclosure system as claimed in claim 15 , wherein the interior face side of the first outer flap comprises a plurality of accessory pockets. 17. the mobile device enclosure system as claimed in claim 15 , wherein the interior face side of the sleeve fold comprises an accessory mount. 18. the mobile device enclosure system as claimed in claim 15 comprises: the inner sleeve mount being pivotably coupled to the interior face side of the second outer flap; the outer case coupler being detachably engaged to the inner sleeve mount; and the outer case coupler being rotatably attached to the inner sleeve mount.
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the current application claims a priority to the u.s. provisional patent application ser. no. 61/678,941 filed on aug. 2, 2012. field of the invention the present invention relates generally to an apparatus enclosure, more specifically to a mobile device enclosure that is configurable in a manner that allows for various viewable orientations of the enclosed mobile device while additionally providing protection form wear and tear. background of the invention with the advent of new technology, people have become more reliant on mobile devices to enhance and facilitate their daily activities. many of these mobile devices, such as tablet pcs, combine the function of several electronic devices into a singular device with a wide range of functionality. while these mobile devices have become essential for managing the daily lives of many people, their daily usage will oftentimes cause wear and tear on the device itself. in most situations, the signs of wear are merely cosmetic but if a user were to drop the device, irreparable damage can be caused the mobile device. this can oftentimes lead to expensive repair costs but more commonly will result in the device having to be completely replaced. although there exist several systems and methods for protecting these mobile devices from normal wear and tear and accidental damage, these systems often times limit the functionality of the mobile device. these existing system are generally designed to be external enclosures that envelope the mobile device, functioning as a protective barriers. the disadvantage with these systems is that they generally end up limiting the portability of the mobile device as well as the accessibility of charging ports and hardware keys. furthermore, these existing systems make it difficult to utilize the mobile devices in alternative capacities, such as a stand along touch screen keyboards and viewing platforms due to the protective cover enclosing particular design features of the mobile device. it is therefore the object of the present invention, to provide a mobile device enclosure system that is able to protect a mobile device from the wear and tear of daily usage without limiting the portability of the mobile device or the accessibility of said mobile device's hardware keys or charging ports. the present invention accomplishes this through the use of an inner sleeve and an outer case. the inner sleeve is enclosed within the outer case. the inner sleeve houses the mobile device and protects it from everyday wear and tear while the outer case houses both the inner sleeve and the mobile device protecting them from accidental damage. additionally, the configuration of the inner sleeve and the outer case permits the mobile device to be particularly oriented and positioned in order to conform to alternative configurations and a display states if necessary. brief descriptions of the drawings fig. 1 is a perspective view displaying the inner sleeve attached to the outer case as per the current embodiment of the present invention. fig. 2 is a top elevational view displaying the inner sleeve attached to the outer case as per the current embodiment of the present invention. fig. 3 is a top elevational view displaying the inner sleeve as per the current embodiment of the present invention. fig. 4 is a bottom elevational view displaying the inner sleeve as per the current embodiment of the present invention. fig. 5 is a bottom elevational view displaying the outer case as per the current embodiment of the present invention. fig. 6 is a perspective view displaying the outer case without as per the current embodiment of the present invention. fig. 7 is a perspective view displaying the inner sleeve mounted to the outer case in a portrait configuration as per the current embodiment of the present invention. fig. 8 is a perspective view displaying the inner sleeve mounted to the outer case in a landscape configuration as per the current embodiment of the present invention. detail descriptions of the invention all illustrations of the drawings are for the purpose of describing selected versions of the present invention and are not intended to limit the scope of the present invention. referencing fig. 1 and fig. 2 , the mobile device enclosure system is a provided as a housing that protects a mobile device for the wear and tear associated with everyday usage without limiting said neither mobile device's portability or the inhibiting access to said mobile devices hardware keys and charging ports. in the current embodiment of the present invention, the mobile device enclosure comprises an inner sleeve 1 and an outer case 14 . the inner sleeve 1 functions as a primary enclosure that retains the mobile device and protects said mobile device from minor wear and tear. it should be noted that minor wear and tear is used to describe wear and tear to a mobile device that would result in cosmetic damage. the outer case 14 functions as a secondary enclosure which houses the inner sleeve 1 and the mobile device protecting both from major wear and tear as well as accidental damage. it should be noted that major wear and tear and accidental damage is used to describe serious damage to said mobile device requiring repair or replacement of components in order to allow the device to function properly. in order to provide this protection, the inner sleeve 1 is found detachably engaged within the outer case 14 . the detachable engagement between the inner sleeve 1 and the outer case 14 additionally provides a rotatable coupling permitting the mobile device to be particularly arranged in alternative configurations for displaying videos in a landscape, horizontal orientation, or vertical, portrait orientation. referencing fig. 3 , fig. 4 , and fig. 8 , the inner sleeve 1 is provided as the primary enclosure that protects the mobile device from minor wear and tear. in the current embodiment of the present invention, the inner sleeve 1 comprises a front panel 2 , a rear panel 4 , a side wall 10 , an inner sleeve opening 11 , a side strap 12 , and a plurality of port openings 13 . the front panel 2 is provided as the portion of the inner sleeve 1 that is coincident with the display screen of a mobile device. the rear panel 4 is provided as the portion of the inner sleeve 1 that is coincident with the rear section of a mobile device. the side wall 10 is provided as a flexible member that perimetrically couples the front panel 2 and the rear panel 4 together. the side wall 10 juxtaposes the front panel 2 and the rear panel 4 parallel to one another, forming an interstitial space that is appropriately sized for housing a mobile device. the inner sleeve opening 11 is provided as the entrance that permits access to the interstitial space between the front panel 2 and the rear panel 4 . the side strap 12 is provided as a means of securing the mobile device within the interstitial space by spanning the inner sleeve opening 11 and inhibiting the mobile device exiting the inner sleeve 1 . the plurality of port openings 13 are provided as a mean of accessing the mobile devices hardware keys and charging ports, but can additionally allow access to the mobile devices camera lens. the plurality of port openings 13 are found particularly positioned on the front panel 2 , the rear panel 4 , and the side wall 10 , wherein the particular positioning of the plurality of port openings 13 is provided in order to enable access to hardware keys, camera lenses, and various ports present on a particular mobile device. the front panel 2 is found juxtaposed parallel to the rear panel 4 . the front panel 2 is flexibly coupled to the rear panel 4 by way of the side wall 10 . the inner sleeve opening 11 traverses the side wall 10 between the front panel 2 and the rear panel 4 . the side strap 12 is found flexibly coupled to the front panel 2 , wherein the side strap 12 is affixed to the front panel 2 but permitted to flex in order to span across the inner sleeve opening 11 and detachably couple the rear panel 4 . in the current embodiment of the present invention, the front panel 2 comprises an open viewing area 3 . the open viewing area 3 centrally traverses the front panel 2 . the positioning of the open viewing area 3 to the front panel 2 provides a frame configuration to the front panel 2 when aligned with the display portion of the mobile device. referencing fig. 3-4 , and fig. 7-8 , the rear panel 4 is the portion of the inner sleeve 1 that is coincident with the rear section of the mobile device. in the current embodiment of the present invention, the rear panel 4 comprises an outer case coupler 5 , a hand strap 6 , and a kickstand 7 . the outer case coupler 5 is a complimenting component to a component on the outer case 14 that enables a detachable and rotatable coupling between inner sleeve 1 and the outer case 14 . the hand strap 6 is provided as an integrated user maniputable engagement that facilitates holding and mobile device while housed within the inner sleeve 1 . the kickstand 7 is an integrated component that is provided as means of inclining the mobile device housed within the inner sleeve 1 in order to function, exclusively, as a touch screen keyboard, wherein deployment of the kickstand 7 angles the mobile device in manner permitting a user's fingers facilitated engagement of the touch screen keys. the outer case coupler 5 is centrally positioned on the rear panel 4 opposite the front panel 2 . the outer case coupler 5 is found positioned between the hand strap 6 and the kickstand 7 . both the hand strap 6 and the kickstand 7 are positioned flush with the rear panel 4 , wherein both the hand strap 6 and the kickstand 7 do not protrude from the rear panel 4 in their resting state. in the current embodiment of the present invention, the kickstand 7 comprises a recessed flap 8 and a hinge 9 . the recessed flap 8 is the structural portion of the kickstand 7 that pivots about the hinge 9 becoming perpendicular with the horizontal in order to incline the inner sleeve 1 . the hinge 9 is the portion of the kickstand 7 that permits the hinge 9 to pivot. the hinge 9 is found integrally coupled to the rear panel 4 and the recessed flap 8 . the thing is positioned opposite the outer case coupler 5 across the recessed flap 8 . referencing fig. 5 and fig. 6 , the outer case 14 is provided as the secondary enclosure that protects the mobile device housed within the inner sleeve 1 from major wear and tear as well as accidental damage. in the current embodiment of the present invention, the outer case 14 comprises a first outer flap 15 , a second outer flap 18 , and a sleeve fold 20 . the first outer flap 15 and the second outer flap 18 are provided as functionally similar components that are pivotally coupled to each other through the sleeve fold 20 . the first outer flap 15 and the second outer flap 18 are both rigid padded panels that protect the mobile device from major damage. the sleeve fold 20 is positioned between the first outer flap 15 and the second outer flap 18 . in the current embodiment of the present invention, the first outer flap 15 , the second outer flap 18 , and the sleeve fold 20 each comprise an interior face side 16 . the interior face side 16 of the first outer flap 15 , the interior face side 16 of the second outer flap 18 , and the interior face side 16 of the sleeve fold 20 are found positioned coincident to each other. the interior face side 16 is the side face of the first outer flap 15 , the second outer flap 18 , and the sleeve fold 20 that is positioned proximal to the inner sleeve 1 . when the inner sleeve 1 is found removeably coupled within the outer case 14 , the interior face side 16 of the first outer flap 15 , the interior face side 16 of the second outer flap 18 and the interior face side 16 of the sleeve fold 20 peripherally surround the inner sleeve 1 . it should be noted that in the current embodiment of the present invention, the first outer flap 15 and the second outer flap 18 are engage by a peripherally positioned coupler which engages the first outer flap 15 and the second outer flap 18 opposite the positioning of the sleeve fold 20 , in order to provide a more secure enclosure. referencing fig. 5 , fig. 6 , and fig. 7 , the second outer flap 18 is provided as a rigid padded panel that functions in conjunction with the first outer panel and the sleeve fold 20 in order to protect the mobile device enclosed within the inner sleeve 1 . in the current embodiment of the present invention, the interior face side 16 of the second outer flap 18 comprises an inner sleeve mount 19 . the inner sleeve mount 19 is an engageable flap that is pivotably coupled to the interior face side 16 of the second outer flap 18 . the inner sleeve mount 19 is a complimenting component to the outer case coupler 5 on the rear panel 4 . the engagement between the outer case coupler 5 and the inner sleeve mount 19 enables a detachable and rotatable coupling between the rear panel 4 and the interior face side 16 of the second outer flap 18 . while the engagement mechanism of the outer case coupler 5 and the inner sleeve mount 19 are not explicitly described, it should be noted that both the outer case coupler 5 and the inner sleeve mount 19 could be provided as any engagement mechanism that detachably and rotatably couples the inner sleeve 1 to the outer case 14 . in the preferred embodiment of the present invention the outer case coupler 5 and the inner sleeve mount 19 are buckle fasteners. in the current embodiment of the present invention, the interior face side 16 of the first outer flap 15 comprises a plurality of accessory pockets 17 . the plurality of accessory pockets 17 function as a convenient storage location for accessories of the mobile device as well as an alternative storage location for anything the user wishes to store. in the current embodiment of the present invention, the interior face side 16 of the sleeve fold 20 comprises an accessory mount. the accessory mount functions as an attachment point for storing a stylus or another kind of cylindrical accessory. in the current embodiment of the present invention, the first outer flap 15 may additionally comprises a sleep mode activator. the sleep mode activator would provide the present invention with a means of putting the mobile device in sleep mode when the device is positioned within the outer case 14 . the sleep mode activator would be internally positioned within the first outer flap 15 and would activate sleep mode on a mobile device when the first outer flap 15 becomes parallel with the second outer flap 18 . the present invention is a mobile device enclosure system designed to protect mobile devices such as tablet computers, tablet pc, or any other tablet type electronic device including but not limited to various generations apple ipad, amazon kindle, nook, acer iconia tab tablet, samsung galaxy, asus transformer pad, lenovo ideapad k1, lenovo thinkpad 1838, lg g-slate 8.9, motorola droid, sony s1, and etc. the present invention protects the mobile device from damages and scratches by encasing the mobile devices in a protective case. the mobile device enclosure system acts as an impact absorber and prevents internal damage to the electronics of the mobile device. this is due to the fact that electronic components of a mobile device, may fail if they are subjected to heavy vibrations or sudden impulses. the present invention comprises an outer case 14 and an inner sleeve 1 . the inner sleeve 1 receives the mobile device. the present invention may utilize a plurality of velcro strips, a plurality of magnets, and a plurality of grooves on the inside of the outer case 14 , a zipper, a plurality of holders, and a stand on the back of the inner sleeve 1 . the present invention may have a logo that is preferably stamped on the outer case 14 , although any desired printing method may be used. the present invention is preferably constructed using genuine cowhide leather on the outside of the outer case 14 , although any desired material may be used. the interior face side 16 of the outer case 14 and the interior portion of the inner sleeve 1 are constructed of micro suede, although any desired material may be used. the micro suede material provides a smooth and soft cushion for the mobile device. the present invention utilizes a rigid internal material to create a structurally strong outer case 14 and inner sleeve 1 . the cowhide and micro suede are preferably stitched together and sandwich the rigid internal material in the middle to create a sturdy shape, although any desired means of attachment may be used. the outer case and the inner sleeve 1 comprise a plurality of port openings 13 that are strategically placed in conjunction with cameras, light sensors, and other ports on each specific mobile device. these ports include but are not limited to charging ports, headphone jacks, speaker ports, and etc. the plurality of port openings 13 allow the user to still utilize the camera and other ports on the mobile device without having to remove the inner sleeve 1 and outer case 14 . the sleeve fold 20 also comprises an accessory mount on the right flap to allow the user to attach and store a stylus or a pen. in an additional embodiment of the present invention comprises a built in stand features would be provided on the outer case 14 in order to allow the user to view the mobile device in multiple angles. the first outer flap 15 would comprise a plurality of grooves on the interior face side 16 that would permit the orientation of the mobile device into a plurality of different viewing angles. in an additional embodiment of the present invention, a large strip of velcro would be sewn into the interior face side 16 of the second outer flap 18 to attach the inner sleeve 1 in a landscape and/or a portrait view. the inner sleeve 1 rests on the grooves to provide a wide variety of viewing angles for the user. the different viewing angles may be adjusted by moving the inner sleeve 1 forwards or backwards along a groove plate until an edge of the inner sleeve 1 falls into one of the groove. in an additional embodiment of the present invention, the interior face side 16 of the second outer flap 18 would comprises a fold positioned below the large strip of velcro to convert the outer case 14 into a stand. the fold comprises stitching along the groove to provide a solid hold and prevents separation. in an additional embodiment of the present invention, the second outer flap 18 would comprise a plurality of folds permitting it to bends in the middle. the second outer flap 18 would be able to wrap around the back to create a folded down flat configuration for the user to view and use the mobile device. in an additional embodiment of the present invention, the inner sleeve 1 is constructed of genuine cowhide leather, although any desired material may be used. the interior portion of the inner sleeve 1 is lined with soft felt material to avoid scratching the device. the rear panel 4 of the inner sleeve 1 is lined with the same felt material to attach and detach from outer case for handheld operation and to manipulate the tablet in a portrait and/or a landscape view. in an additional embodiment of the present invention, the inner sleeve 1 comprises a sewn on leather flap that holds a strip of velcro hook and a velcro loop sewn on the interior portion of the inner sleeve 1 in order to secure the tablet while inside sleeve. in an additional embodiment of the present invention, a plurality of magnets are positioned underneath the suede like material on the peripheral edges of the first outer flap 15 and the second outer flap 18 . the magnetic flap closure would able to secure mobile device within the outer case 14 . the magnetic flap closure may also automatically sleeps and wakes the new ipad 2 and ipad 3 devices. in an alternative embodiment of the present invention, the an outer case 14 would utilize a dual zipper for easy access, a detachable inner sleeve 1 for handheld operation, a plurality of slots with accessory flaps, and a rear stand for comfortable viewing at a 45° degree angle. in the alternative embodiment of the present invention, a large strip of velcro would be sewn into the interior face side 16 of second outer flap 18 . the large strip of velcro would be used to attach the inner sleeve 1 case in landscape and/or portrait views. in the alternative embodiment of the present invention, the outer case 14 comprises a decorative stitching pattern to give the case a unique and attractive look. in an alternative embodiment of the present invention, the center portion of the outer case 14 comprises a sleeve fold 20 that bends in the middle to close the case. along with the sleeve fold 20 , the alternative embodiment comprises a dual zipper that secures the case and prevents any accidental separation. in an alternative embodiment of the present invention, the outer case 14 comprises a rear stand that is attached on the exterior side face of the second outer flap 18 to allow a 45° degree viewing angle. the rear stand comprises a strap that prevents the stand from separating from the case. the rear stand also comprises a plurality of magnets that are attached in the stand and the case to hold the stand in a flat configuration when the stand is not in use. in an alternative embodiment of the present invention, the inner sleeve 1 comprises a sewn on leather flap in order secure the mobile device while stored in the inner sleeve 1 . the inner sleeve 1 utilizes a plurality of port openings 13 that are purposefully placed in combination with cameras ports, light sensors, and other ports on each specific electronic device. although the invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.
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052-001-233-907-270
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US
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[
"US"
] |
A61B5/0476,A61B5/053,A61B5/055,A61B6/03,A61N1/36
| 2019-08-14T00:00:00 |
2019
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[
"A61"
] |
method for desynchronizing pathological neural oscillations
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a method for desynchronizing a pathological neural oscillations, includes identifying a first subpopulation of the neurons involved in the pathological neural oscillation that are in alignment with each other within a predetermined angular stimulation range, and a second subpopulation that are both (a) in alignment with each other within the predetermined angular stimulation range, and (b) out of alignment with the first neurons by at least the predetermined angular stimulation range, and applying electrical stimuli to the first and second subpopulations through scalp electrodes, the electrical stimuli being out of phase with the pathological neural oscillations for desynchronizing the pathological neural oscillations.
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1. a method for desynchronizing a pathological neural oscillation in the brain of a subject, the brain having a cortex and the neurons involved in the pathological neural oscillation extending to the cortex, the method comprising: identifying a first contiguous subset of the cortex wherein first neurons involved in the pathological neural oscillation are (a) in alignment with each other within a predetermined angular stimulation range; identifying a second contiguous subset of the cortex, distinct from the first contiguous subset of the cortex, wherein second neurons that are also involved in the pathological neural oscillation are both (a) in alignment with each other within the predetermined angular stimulation range, and (b) out of alignment with the first neurons by at least said predetermined angular stimulation range; applying, through a first set of scalp electrodes, a first electrical stimulus to the first subset of the cortex that is in alignment with the first neurons within said predetermined angular range, and which is out of phase with the pathological neural oscillation; and applying, through a second set of scalp electrodes, a second electrical stimulus to the second subset of the cortex that is in alignment with the second neurons within said predetermined angular range, and which is out of phase with the pathological neural oscillation, wherein the steps of applying the first and second stimuli are sufficient to desynchronize the pathological neural oscillation. 2. the method of claim 1 , wherein the second electrical stimulus is out of phase with the first electrical stimulus. 3. the method of claim 1 , wherein the first and second electrical stimuli are applied during overlapping times. 4. the method of claim 1 , at least one of said steps of identifying contiguous subsets of the cortex comprises obtaining an electroencephalographic signature of the pathological neural oscillation. 5. the method of claim 1 , further comprising creating a model of electrical properties of the subject's head, and utilizing the model for determining at least one of the first and second electrical stimuli. 6. the method of claim 5 , wherein said step of creating a model of electrical properties of the subject's head comprises combining data obtained from magnetic resonance imaging, x-ray computed tomography, and electrical impedance tomography performed on the subject's head. 7. the method of claim 1 , further comprising obtaining a magnetic resonance image of the subject's head, and utilizing the magnetic resonance image for predetermining, relative to said step of applying the first electrical stimulus, whether the first neurons satisfy criterion (a). 8. the method of claim 6 , further comprising utilizing the magnetic resonance image for predetermining, relative to said step of applying the second electrical stimulus, whether the second neurons satisfy both criteria (a) and (b).
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field of invention the present invention relates to non-invasive methods for desynchronizing pathological neural oscillations in the brain, such occur in parkinson's disease. background pathological neural oscillations in the brain have been successfully disrupted in the prior art by stimulating nerve endings outside of the brain, such as by tactile stimulation of the fingertips, visual stimulation of the optic nerves, or acoustic stimulation of the auditory nerves. such disruptions have also been achieved in the prior art by use of current-injecting electrodes implanted in the subthalamic nucleus (stn) of the brain. synchronous oscillations of a global or “target” population of neurons are disrupted by differentially stimulating subsets or “subpopulations” of the target. more specifically, each of at least two subpopulations is stimulated to oscillate in synchrony with an applied stimulus that is desynchronized (typically by being out of phase) with the target as well as with the stimuli applied to the other subpopulations being (or to be) stimulated. the stimuli are typically applied to the at least two subpopulations in a repetitive temporal sequence to produce a desynchronization of the target that is semi-permanent. it is an object of the invention to provide an alternative and potentially less invasive and more effective method for achieving such desynchronization. summary disclosed is a method for desynchronizing a pathological neural oscillation in the brain of a subject. the basic method includes identifying a first contiguous subset of the cortex wherein first neurons involved in the pathological neural oscillation are in alignment with each other within a predetermined angular stimulation range; identifying a second contiguous subset of the cortex, distinct from the first contiguous subset of the cortex, wherein second neurons that are also involved in the pathological neural oscillation are both (a) in alignment with each other within the predetermined angular stimulation range, and (b) out of alignment with the first neurons by at least the predetermined angular stimulation range; applying, through a first set of scalp electrodes, a first electrical stimulus to the first subset of the cortex that is in alignment with the first neurons within the predetermined angular range, and which is out of phase with the pathological neural oscillations; and applying, through a second set of scalp electrodes, a second electrical stimulus to the second subset of the cortex that is in alignment with the second neurons within the predetermined angular range, and which is out of phase with the pathological neural oscillations, wherein the steps of applying the first and second stimuli are sufficient to desynchronize the pathological neural oscillation. optionally, the second electrical stimulus may be out of phase with the first electrical stimulus. optionally, the first and second electrical stimuli may be applied during overlapping times. optionally, at least one of the steps of identifying contiguous subsets of the cortex may include obtaining an electroencephalographic signature of the pathological neural oscillation. optionally, the method may include creating a model of electrical properties of the subject's head, and utilizing the model for determining at least one of the first and second electrical stimuli. optionally, the step of creating a model of electrical properties of the subject's head may include combining data obtained from magnetic resonance imaging, x-ray computed tomography, and electrical impedance tomography performed on the subject's head. optionally, the method may include obtaining a magnetic resonance image of the subject's head, and utilizing the magnetic resonance image for predetermining, relative to the step of applying the first electrical stimulus, whether the first neurons satisfy criterion (a). optionally, the magnetic resonance image may also be used for predetermining, relative to the step of applying the second electrical stimulus, whether the second neurons satisfy both criteria (a) and (b). it is to be understood that this summary is provided as a means of generally determining what follows in the drawings and detailed description and is not intended to limit the scope of the invention. objects, features and advantages of the invention will be readily understood upon consideration of the following detailed description taken in conjunction with the accompanying drawings. brief description of drawings fig. 1 is a schematic diagram of a system for performing transcranial electrical stimulation of a subject's brain, such as is ordinarily provided in the prior art, and which may be used for practicing methods according to the present invention. fig. 2 is an isometric view of a brain, showing a portion of the cortex that is involved in a pathological neural oscillation and identified as a target for stimulation, for desynchronizing the pathological neural oscillation according to the invention. fig. 3 is a simplified side elevation of the brain of fig. 2 located beneath the subject's scalp, showing the portion of the cortex in section. description of preferred embodiments the present invention provides a method for disrupting pathological neural oscillations in the brain, such as occur in parkinson's disease, that makes use of what is known in the art of neuroscience as transcranial electrical stimulation (“tes”). referring to fig. 1 , tes is well known prior art and need not be discussed in great detail. basically, it employs electrodes 12 placed in electrical contact with the skin of a subject or patient's scalp, for non-invasively injecting electrical currents into the subject's head 1 for stimulating the subject's brain 2 . specifically, for each of a number of different pairs of scalp electrodes, an electrical current “j” flows from one of the electrodes 12 a held at a first electrical potential “v 1 ,” to another of the electrodes 12 b held at a second electrical potential “v 2 ,” first through the subject's scalp 3 , thence through the subject's skull 5 , thence through the subject's cerebrospinal fluid 7 , and thence through the subject's cortex 9 . the electrical potentials v 1 and v 2 may be produced by a system 15 comprising a standard multi-channel voltage source 14 a (each pair of electrodes defining a channel, the other channels and connections to the electrodes 12 not shown) controlled (arrow “a”) by a controller 16 which may be a standard programmable computer such as a pc or macintosh. figs. 2 and 3 show a portion of the subject's cortex which has been identified as a desired target 18 for desynchronization according to the invention. such a target may be identified in any manner known in the art, such as from electroencephalographic (“eeg”) signatures and/or a priori anatomical knowledge. with particular reference to fig. 3 , for obtaining eeg signatures, the same electrodes 12 that are used for stimulation can be used as sensors of the electrical potentials generated by the brain as is known in the art. in such case, the system 15 would include a standard multi-channel voltage measuring device 14 b , and the controller 16 may be adapted accordingly for controlling the voltage measuring device to measure electrical potentials (arrow “b”) sensed by the electrodes 12 , and to send the measured data (arrow “c”) to the controller 16 , so that the controller 16 may analyze the measured data and/or output the data (arrow “d”) for analysis by another device (e.g., a separate computer). the identified target may further be imaged by any means known in the art, such as by magnetic resonance imaging (“mri”). the image may be used to conceptually subdivide the target into a number of different subpopulations, such as those referenced as “sp 1 ” and “sp 2 ” in fig. 2 , and “a,” “b,” “c,” and “d” in fig. 3 . tes does not have a good capability to target specific locations in the brain for stimulation, due primarily to the fact that the stimulating current must pass through bone which is not very conductive. so in general, again referring particularly to fig. 3 , the target 18 would be too small for differential stimulation of the subpopulations a-d were it not for the fact that the cortex is wrinkled. the present inventors have recognized that cortical wrinkling allows for differential stimulation of subpopulations using tes, not by targeting specific locations in the cortex, but by targeting specific orientations of the cortical surface. further, this type of targeting is based on a recognition that any given neuron is most effectively stimulated when the stimulating current is injected normal to the cortical surface where the neuron is located, i.e., parallel to the neuron's dipolar axis, and that the neuron will not as a practical matter be effectively synchronized with an injected stimulating current that deviates from the surface normal by more than a predetermined amount. the maximum angle of misalignment or deviation between the cortical surface normal of a neuron and the direction a stimulating current is injected into the neuron will be referred to as the “angular stimulation range.” preferably, this range is less than or equal to 45 degrees; more preferably it is less than or equal to 30 degrees, and more preferably it is less than or equal to 20 degrees. the angular stimulation range can be used according to the invention for identifying potential subpopulations for selective synchronization or stimulation. subpopulations may be identified as being localized groups of neurons within which the surface normal vectors for all the neurons lie inside the angular stimulation range. to provide a simplified illustration of this, figs. 2 and 3 show aggregate surface normal vectors that are representative for the subpopulations shown; in fig. 2 , aggregate surface normal vectors “sn 1 ” and “sn 2 ” for the subpopulations sp 1 and sp 2 , and in fig. 3 , aggregate surface normals “sn a ” for the subpopulation a, “sn b ” for the subpopulation b, “sn c ” for the subpopulation c, and “sn d ” for the subpopulation d. it is to be understood that, since the cortical surface 18 a is not planar, the surface normal vectors for each infinitesimal or “differential” portion of the surface of even a relatively small subpopulation will not everywhere be parallel to the aggregate surface normal vectors. with particular reference to fig. 3 , examples of such differential surface normal vectors are shown as “dsn” in connection with the subpopulation a. the aggregate surface normal vectors may be an average, e.g., they may be a mean, median, or integral average, of the differential surface normal vectors dsn. according to the invention, if all the differential surface normal vectors of a contiguous surface area of the cortex are within the angular stimulation range, that surface area may be considered to define a subpopulation of neurons. fig. 3 also illustrates how to distinguish one subpopulation from another according to the invention. it shows aggregate surface normal vectors (again, as illustrative proxies for individual differential surface normal vectors) that make angles with each other that are outside of the angular stimulation range and which are therefore “distinct” from each other. more particularly, the aggregate surface normal vector sn a for the subpopulation a makes an angle θ ab , with the aggregate surface normal vector sn b for the subpopulation b, that is outside the preferred 20 degree angular stimulation range. likewise the angles θ ac , θ ad , θ bd , and θ cd are substantially greater than 20 degrees. by contrast, the aggregate surface normal vectors (not shown) for the subpopulations labeled “e” and “f” in fig. 3 are nearly parallel to each other as well as to the aggregate surface normal vector for the subpopulation c, and are therefore well within the angular stimulation range and not distinct from each other. stimulating any one of these subpopulations will stimulate the other two, and the three subpopulations can be considered for purposes herein as being the same. the identified subpopulations form a pool, from which at least two subpopulations having distinct differential surface normal vectors may be selected, for selective synchronization with targeted stimulating currents. the stimulating currents would preferably be targeted to align with the aggregate surface normal vectors na for the selected subpopulations. the source currents used for stimulating the at least two selected subpopulations may be applied over the same periods of time, or during different periods of time, or any desired combination of the two. moreover, the source current(s) used for stimulating a given selected subpopulation may be applied repetitively, and/or in either a regular or a randomized sequence with the source current(s) used for stimulating the remaining ones of the selected subpopulations. it has so far been assumed that the pattern and density of the electrodes 12 will allow for differentially stimulating the selected subpopulations, i.e., by injecting one or more currents within the angular stimulation range for a given one of the selected subpopulations, and outside the angular stimulation ranges of the remaining ones of the selected subpopulations. but this may not be the case. the pattern and density of the electrodes will in general be a constraint on the selection of the subpopulations to be stimulated, and may be a constraint on the initial identification of potential subpopulations for stimulation. to account for this, methods according to the invention may include constructing an electrical head model for the subject, and using the electrical head model to predict current injection paths for different pairings of the electrodes provided in a given pattern and density, to determine pairings of electrodes that can be used to optimally differentially stimulate the greatest number of distinct subpopulations, and/or to optimally define a pattern and density of electrodes to be used. as is typical in the art, the head model may be obtained by combining mri, x-ray computed tomography (“ct”), and electrical impedance tomography (“eit”) of the subject's head. it is to be understood that, while a specific method for desynchronizing pathological neural oscillations has been shown and described as preferred, other configurations and methods could be utilized, in addition to those already mentioned, without departing from the principles of the invention. the terms and expressions which have been employed in the foregoing specification are used therein as terms of description and not of limitation, and there is no intention in the use of such terms and expressions to exclude equivalents of the features shown and described or portions thereof, it being recognized that the scope of the invention is defined and limited only by the claims which follow.
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054-201-322-455-869
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US
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E04F15/02,E04F15/04,E04F15/10,E04B5/02,E04F13/08,E04F15/18,F16B5/00,E04B2/00,F16B5/06,F16B5/10,E04C2/38,E04F15/16,E04F/,E04B2/20,E04C3/00,E04B5/00,E04B1/38,E04C2/20,E04C2/22
| 2005-03-30T00:00:00 |
2005
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[
"E04",
"F16"
] |
mechanical locking system for panels and method of installing same
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floor panels are provided with a mechanical locking system including a flexible locking element in a locking groove which during a horizontal motion is displaced vertically. a panel system including a plurality of rectangular panels with long and short edges which are mechanically connectable to each other along at least one pair of adjacent edges, said panels each being provided with a tongue and groove formed in one piece with the panels for mechanically locking together said adjacent edges at right angles to the principal plane of the panels, thereby forming a vertical mechanical connection between the panels, said panels being provided with a first locking element at one first edge formed in one piece with the panel and a locking groove at an opposite second edge, the locking groove being open towards a rear side or a front side of the panel.
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1 . a panel system, comprising a plurality of rectangular panels with long and short edges which are mechanically connectable to each other along at least one pair of adjacent edges, said panels each being provided with a tongue and groove formed in one piece with the panels for mechanically locking together said adjacent edges at right angles to the principal plane of the panels, thereby forming a vertical mechanical connection between the panels, said panels being provided with a first locking element at one first edge formed in one piece with the panel and a locking groove at an opposite second edge, the locking groove being open towards a rear side or a front side of the panel, each panel being provided with a second locking element, formed of a separate material and connected to the locking groove, the first and second locking elements form a mechanical connection locking the panels to each other horizontally parallel to the principal plane and at right angles to the joint edges, the second locking element is flexible and resilient such that two panels, are adapted to be mechanically joined by displacement of said two panels horizontally towards each other, while at least a part of the second locking element at said second edge is resiliently displaced vertically, until said adjacent edges of the two panels are brought into engagement with each other horizontally and the second locking element at said second edge is displaced towards its initial position against the first locking element at the first edge. 2 . the panel system as claimed in claim 1 wherein the locking groove is open towards the rear side. 3 . the panel system as claimed in claim 1 , wherein the locking groove is open towards the front side. 4 . the panel system as claimed in claim 1 , wherein the first locking element is on a locking strip which is an extension of the lower part of the groove. 5 . the panel system as claimed in claim 1 wherein the second locking element has a groove portion located in the locking groove and a projecting portion located outside the locking groove which are displaced towards each other when the panels are displaced horizontally 6 . the panel system as claimed in claim 1 , wherein the displacement of the second locking element is not effected until a part of the tongue is in the groove. 7 . the panel system as claimed in claim 1 , wherein a part of the second locking element is displaced in the locking groove. 8 . a panel system as claimed in claim 7 , wherein the second locking element along its length has at least two sections and the displacement of one of the sections is larger than the displacement of the other one of the sections. 9 . the panel system as claimed in claim 8 , wherein said second locking element has a projecting portion which in connected state is located outside the locking groove and a groove portion in the locking groove such that the size of said projecting portion and/or the groove portion varies along the length of the flexible locking element. 10 . the panel system as claimed in claim 1 , wherein the flexible locking element is spaced from a corner portion. 11 . the panel system as claimed in claim 1 , wherein the second locking element is made of polymer material. 12 . the panel system as claimed in claim 11 , wherein the second locking element is made of a molded or extruded polymer material reinforced with glass fiber.
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cross reference to related applications the present application is a continuation of u.s. application ser. no. 15/148,820, filed on may 6, 2016, which is a continuation of u.s. application ser. no. 14/730,691, filed on jun. 4, 2015, now u.s. pat. no. 9,359,774, which is a continuation of u.s. application ser. no. 14/138,385, filed on dec. 23, 2013, now u.s. pat. no. 9,068,360, which is a continuation of u.s. application ser. no. 13/758,603, filed on feb. 4, 2013, now u.s. pat. no. 8,677,714, which is a continuation of u.s. application ser. no. 13/253,283, filed on oct. 5, 2011, now u.s. pat. no. 8,387,327, which is a continuation of u.s. application ser. no. 12/962,341, filed on dec. 7, 2010, now u.s. pat. no. 8,079,196, which is a continuation of u.s. application ser. no. 11/822,723, filed on jul. 9, 2007, now u.s. pat. no. 7,866,110, which is a continuation of u.s. application ser. no. 11/092,748, filed on mar. 30, 2005, now u.s. pat. no. 7,841,144. the entire contents of each of u.s. application ser. no. 15/148,820, u.s. application ser. no. 14/730,691, u.s. pat. no. 9,359,774, u.s. application ser. no. 14/138,385, u.s. pat. no. 9,068,360, u.s. application ser. no. 13/758,603, u.s. pat. no. 8,677,714, u.s. application ser. no. 13/253,283, u.s. pat. no. 8,387,327, u.s. application ser. no. 12/962,341, u.s. pat. no. 8,079,196, u.s. application ser. no. 11/822,723, u.s. pat. no. 7,866,110, u.s. application ser. no. 11/092,748, and u.s. pat. no. 7,841,144 are hereby incorporated herein by reference. technical field the invention generally relates to the field of mechanical locking systems for floor panels and building panels. field of application of the invention the present invention is particularly suitable for use in floating floors, which are formed of floor panels which are joined mechanically with a locking system integrated with the floor panel, i.e., mounted at the factory, are made up of one or more upper layers of veneer, decorative laminate or decorative plastic material, an intermediate core of wood-fiber-based material or plastic material and preferably a lower balancing layer on the rear side of the core. the following description of known techniques, problems of known systems and objects and features of the invention will therefore, as a non-restrictive example, be aimed above all at this field of application and in particular laminate flooring formed as rectangular floor panels with long and short sides intended to be mechanically joined on both long and short sides. the long and short sides are mainly used to simplify the description of the invention. the panels could be square. it should be emphasized that the invention can be used in any panel and it could be combined with all types of known locking systems, where the floor panels are intended to be joined using a mechanical locking system connecting the panels in the horizontal and vertical directions on at least two adjacent sides. the invention can thus also be applicable to, for instance, solid wooden floors, parquet floors with a core of wood or wood-fibre-based material and a surface of wood or wood veneer and the like, floors with a printed and preferably also varnished surface, floors with a surface layer of plastic or cork, linoleum, rubber. even floors with hard surfaces such as stone, tile and similar are included and floorings with soft wear layer, for instance needle felt glued to a board. the invention can also be used for joining building panels which preferably contain a board material for instance wall panels, ceilings, furniture components and similar. background of the invention laminate flooring usually comprises a core of a 6-12 mm fibre board, a 0.2-0.8 mm thick upper decorative surface layer of laminate and a 0.1-0.6 mm thick lower balancing layer of laminate, plastic, paper or like material. a laminate surface comprises melamine impregnated paper. the most common core material is fibreboard with high density and good stability usually called hdf—high density fibreboard. sometimes also mdf—medium density fibreboard—is used as core. traditional laminate floor panels of this type have been joined by means of glued tongue-and-groove joints. in addition to such traditional floors, floor panels have been developed which do not require the use of glue and instead are joined mechanically by means of so-called mechanical locking systems. these systems comprise locking systems, which lock the panels horizontally and vertically. the mechanical locking systems are usually formed by machining of the core of the panel. alternatively, parts of the locking system can be formed of a separate material, for instance aluminium or hdf, which is integrated with the floor panel, i.e., joined with the floor panel in connection with the manufacture thereof. the main advantages of floating floors with mechanical locking systems are that they are easy to install. they can also easily be taken up again and used once more at a different location. definition of some terms in the following text, the visible surface of the installed floor panel is called “front side”, while the opposite side of the floor panel, facing the sub floor, is called “rear side”. the edge between the front and rear side is called “joint edge”. by “horizontal plane” is meant a plane, which extends parallel to the outer part of the surface layer. immediately juxtaposed upper parts of two adjacent joint edges of two joined floor panels together define a “vertical plane” perpendicular to the horizontal plane. by “locking systems” are meant co-acting connectors which connect the floor panels vertically and/or horizontally. by “mechanical locking system” is meant that joining can take place without glue. mechanical locking systems can in many cases also be joined by gluing. by “integrated with” means formed in one piece with the panel or a separate material factory connected to the panel. known techniques and problems thereof for mechanical joining of long sides as well as short sides in the vertical and horizontal direction (direction d 1 , d 2 ) several methods could be used. one of the most used methods is the angle-snap method. the long sides are installed by angling. the panel is than displaced in locked position along the long side. the short sides are locked by horizontal snapping as shown in figs. 1a - 1 c. the vertical connection is a tongue 10 and a groove 9 during the horizontal displacement, a strip 6 with a locking element 8 is bent and when the edges are in contact, the strip springs back and a locking element 8 enters a locking groove 14 and locks the panels horizontally. the vertical displacement of the locking element during the snapping action is caused by the bending of the strip. such a snap connection is complicated since a hammer and a tapping block is frequently used to overcome the friction between the long edges and to bend the strip during the snapping action. the friction on the long side could be reduced and the panels could be displaced without tools. the snapping resistance is however considerable, especially in locking systems made in one piece with the core. wood based materials are generally difficult to bend. cracks in the panel may occur during snapping and the locking element must be rather small in the vertical direction in order to allow snapping. it is known that a snap system could have a separate plastic strip 6 ′, integrated with the panel and with a resilient part as shown in figs. 1d - 1 f. such a locking system could be locked with less resistance than the traditional one-piece snap system. this locking system has however several disadvantages. the plastic strip is used to replace both the tongue and the strip with a locking element. the material cost is therefore high and the locking system is generally not compatible with the locking system used in old panels. the groove 9 is difficult to produce since it must have a locking element 8 ′. in fact 4 locking elements, two flexible locking elements on the strip and two ( 8 , 8 ′) in the panel, must be used to lock in the horizontal direction. it is difficult to fix the plastic strip over the whole length of the short side. this means that corner portions will not have any tongue and this could cause problems in some applications. summary and objects a first overall objective of the present invention is to provide a locking system, which could be locked by horizontal snapping and with less snapping resistance than the known systems. the costs and functions should be favourable compared to known technology. an aspect of the overall objective is to improve the function and costs of those parts of the locking system that locks in the horizontal direction when panels are pushed against each other. more specifically an object is to provide a snap locking system where one or several of the following advantages are obtained. the floor panel should preferably be possible to displace and lock with such a low force that no tools will be needed. the locking function should be reliable and the vertical and horizontal locking should be strong and prevent that two locked panels will move when humidity is changing or when people walk on a floor. the locking system should be able to lock floor panels vertically with high precision so that the surfaces are essentially in the same plane. the locking system should be designed in such a way that the material and production costs could be low. another objective is to provide a snap locking system which could be compatible with traditional locking systems. according to a first embodiment, a flooring system is provided, comprising a plurality of rectangular floor panels with long and short edges, which are mechanically connectable to each other along one pair of adjacent edges. the floor panels are provided with tongue and groove formed in one piece with the panels for mechanically locking together said one pair of adjacent edges at right angles to the principal plane of the panels, thereby forming a vertical mechanical connection between the panels. the panels are provided with a first locking element at one first edge formed in one piece with the panel and a locking groove at an opposite adjacent second edge, the locking groove being open towards a rear side or a front side of the panel. each panel is provided with a second locking element, formed of a separate material and connected to the locking groove. the first and second locking elements form a mechanical connection locking the panels to each other horizontally parallel to the principal plane and at right angles to the joint edges. the second locking element is flexible and resilient such that two panels, can be mechanically joined by displacement of said two panels horizontally towards each other, while at least a part of the second locking element at said second edges is resiliently displaced vertically, until said adjacent edges of the two panels are brought into engagement with each other horizontally and the second locking element at said second edge is displaced towards its initial position against the first locking element at the first edge. although it is an advantage to integrate the flexible locking element with the panel at the factory, the invention does not exclude an embodiment in which flexible locking elements are delivered as separate components to be connected to the panel by the installer prior to installation. the embodiment allows horizontal and vertical locking of all sides of floor panels with for instance an angling of the long sides, a simple horizontal displacement along the long sides and snapping of the short sides. in this preferred embodiment the flexible locking element is on the short sides. it could be on the long side or on the long and short sides. the invention is especially suited for use in floor panels, which are difficult to snap for example because they have a core, which is not flexible, or strong enough to form a strong snap locking system. the invention is also suitable for wide floor panels, for example with a width larger than 20 cm, where the high snapping resistance is a major disadvantage during installation, in panels where parts of the locking system is made of a material with high friction, such as wood and in locking systems which are produced with tight fit or without play or even with pretension. especially panels with such pretension where the locking strip is bent in locked position and presses the panels together are very difficult to displace and snap. a locking system that reduces the snapping resistance will decrease the installation time of such panels considerably. brief description of the drawings figs. 1a-1f illustrate known systems. figs. 2a-2b illustrate two embodiments of the invention. figs. 3a-3c illustrate in several steps mechanical joining of floor panels according to an embodiment of the invention. figs. 4a-4d illustrate in several steps mechanical locking and unlocking of floor panels according to an embodiment of the invention. figs. 5a-5c illustrate in several steps mechanical locking of floor panels according to another embodiment of the invention. figs. 6a-6e show embodiments of the invention. figs. 7a-7h show different embodiments of a flexible locking element. figs. 8a-8c show locking systems on long and short sides according to embodiments of the invention. figs. 9a-9i show how known locking systems could be converted to a locking system according to an embodiment of the invention. figs. 10a-10d show how the flexible locking element could be used as a flexible tongue enabling a vertical connection according to embodiments of the invention. description of embodiments of the invention to facilitate understanding, several locking systems in the figures are shown schematically. it should be emphasized that improved or different functions can be achieved using combinations of the preferred embodiments. the inventor has tested all known and especially all commercially used locking systems on the market in all types of floor panels, especially laminate and wood floorings and the conclusion is that at least all these known locking systems which have one or more locking elements cooperating with locking grooves could be adjusted to a system with one or more flexible locking elements according to the invention. most of them could easily be adjusted in such a way that they will be compatible with the present systems. several flexible locking elements could be located in both adjacent edges, one over the other or side-by-side. the flexible locking element could be on long and/or short sides and one side with a flexible locking element could be combined with another side which could have all known locking systems, preferably locking systems which could be locked by angling or a vertical movement. the invention does not exclude floor panels with flexible locking elements on for example a long and a short side. such panels could be installed by the known snap-snap installation methods. a preferred embodiment is a floorboard with a surface layer of laminate, a core of hdf and a locking system with a flexible locking element on the short side allowing easy snapping combined with a one piece mechanical locking system on long side which could be locked by angling. the long side locking system could have a small play of some 0.01 mm between at least some surfaces which are active in the vertical or horizontal locking such as tongue/groove and or locking element/locking groove. this small play facilitates displacement. such a floorboard will be very easy to install with angling and snapping. angles, dimensions, rounded parts etc. are only examples and could be adjusted within the principles of the invention. a first preferred embodiment of a floor panel 1 , 1 ′ provided with a mechanical locking system according to the invention is now described with reference to figs. 2a - 2 b. fig. 2a illustrates schematically a cross-section of a joint preferably between a short side joint edge 5 a of a panel 1 and an opposite short side joint edge 5 b of a second panel 1 ′. the front sides of the panels may include one or more upper layers of a decorative plastic material 61 , and are essentially positioned in a common horizontal plane hp, and the upper parts of the joint edges 5 a, 5 b abut against each other in a vertical plane vp. the mechanical locking system provides locking of the panels relative to each other in the vertical direction d 1 as well as the horizontal direction d 2 . to provide joining of the two joint edges in the d 1 and d 2 directions, the edges of the floor panel have a locking strip 6 with a first locking element 8 , and a groove 9 made in one piece with the panel in one joint edge 5 a and a tongue 10 made in one piece with the panel at an opposite edge 5 b. the tongue 10 and the groove 9 and provide the vertical locking dl. the mechanical locking system comprises a separate flexible second locking element 15 connected into a locking groove 14 formed in the opposite edge 5 b of the panel. parts of the flexible locking element could bend in the length direction and could be displaced in the locking groove. the flexible locking element 15 has a groove portion p 1 that is located in the locking groove 14 and a projecting portion p 2 projecting outside the locking groove 14 . the projecting portion p 2 of the second flexible locking element 15 , made of a separate material, in one of the joint edges cooperates with a first locking element 8 made in one piece with the panel and formed in the other joint edge. in this embodiment, the panel 1 could for example have a body or core 60 of wood-fibre-based material such as hdf, plywood or solid wood, or plastic material. the panels 1 , 1 ′ could also be made of stone, metal or ceramic materials. these materials are not flexible. the tongue 10 and/or the strip 6 with the locking element 8 could also be made of a separate material connected to the panel. the flexible locking element 15 has a protruding part p 2 with a rounded outer part 31 and a sliding surface 32 which in this embodiment is formed like a bevel. the first locking element 8 has a first locking surface 20 which cooperates with a second locking surface 22 of the second flexible locking element 15 and locks the joint edges 5 a, 5 b in a horizontal direction d 2 . in this embodiment, the locking surfaces 20 , 22 are slightly angled (a) against the vertical plane vp. the second locking element 15 will therefore lock as a wedge and tolerances could be eliminated with vertical pre-tension caused by the vertical flexibility of the second flexible locking element. fig. 2b shows another embodiment. the inner part p 1 of the flexible locking element 15 is fixed in the locking groove 14 and the protruding part p 2 could flex vertically towards the locking groove 14 and the inner part p 1 and back again towards the first locking element. in this embodiment the bending of the protruding part p 2 takes place around a center point cp. the locking surfaces 20 , 22 are formed such that they meet each other when the protruding part p 2 snaps back towards its initial position. figs. 3a-3c show how the flexible locking element 15 is displaced in the locking groove 14 . the flexible locking element 15 is displaced vertically when the displacement surface 32 presses against the beveled part of the first locking element 8 as shown in fig. 3a . when the top edges of the panels 1 , 1 ′ are in contact or in the intended locked position, the flexible locking element 14 springs back and locks to the first locking element 8 as shown in fig. 3 c. figs. 4a-4c show that a locking system with a flexible locking element 15 could also be locked and unlocked with angling. fig. 4d shows that a locking system with a flexible locking element could be unlocked with a needle shaped tool 16 , which is inserted along the joint edge to push back the flexible locking element 14 and to unlock the locking system. such an unlocking could be used to unlock panels which are installed in a herringbone pattern long side to short side with angling of short sides and snapping of short sides to long side. figs. 5a-5c show locking according to the embodiment in fig. 2b . it is an advantage if the tip 11 of the tongue 10 is partly in the groove 9 when the sliding surface 32 is in contact with the locking element 8 . this facilitates snapping and installation of the panels. figs. 6a-6e show different embodiments of the invention. fig. 6a shows a system with two tongues 10 , 10 ′ and with a locking groove 14 open towards the front side. fig. 6b shows a system with the locking groove partly in the part of the tongue 10 which is outside the vertical plane vp. figs. 6c and 6d are similar to 6 a but these systems have only one tongue. fig. 6e shows an embodiment according to fig. 2b but with the locking groove open towards the front side. in this embodiment the floor panel is a parquet floor with a surface layer of wood and a lamella core. the flexible locking element 15 has a protrusion 36 to increase the friction between the flexible locking element 15 and the locking groove 14 . the flexible locking element 15 should preferably be connected to the locking groove with high precision, especially when parts of the flexible locking element 15 are displaced in the locking groove 14 during locking. depending on the compressibility and friction between the flexible locking element and the locking groove, the flexible locking element as whole or different parts could be connected with a small play, for example 0.01-0.10 mm, a precise fit or a pretension. wax or other friction reducing materials or chemicals could be applied in the locking groove and/or between the locking elements. even with a play, a precise fit between the upper joint edges could be accomplished. the protruding part p 2 could be formed to press against the locking surface 20 of the locking element 8 . for example the protruding part p 2 could be formed with a small angle to the vertical plane vp. the protruding part p 2 of the flexible tongue will tilt and press the edges together. the flexible locking element 15 could be formed to cause a permanent pressure force vertically in the locked position. this means that the flexible locking element 15 will only partly spring back to the initial position. the flexible locking element could optionally be designed with such dimensions that after locking it will move slightly towards its initial position. gradually a perfect connection will be accomplished. figs. 7a-7h shows different embodiments of the flexible locking element 15 . in fig. 7a the flexible locking element 15 is moulded and has on one of the edge sections es a friction connection 36 which could be shaped for instance as a local small protrusion. this friction connection keeps the flexible locking element in the locking groove 14 during installation, or during production, packaging and transport, if the flexible locking element is integrated with the floor panel at the factory. in fig. 7b the flexible locking element 15 is an extruded plastic section. fig. 7c shows a blank 50 consisting of several flexible locking elements 15 connected to each other. in this embodiment the flexible locking element 15 is made with moulding, preferably injection moulding. any type of polymer materials could be used to produce the flexible locking elements such as pa (nylon), pom, pc, pp, pet or pe or similar materials having the properties described above in the different embodiments. these plastic materials could be reinforced with for instance glass fibre. a preferred material is glass fiber reinforced pa. figs. 7d and 7e show a flexible locking element 15 with a length l, and a middle section ms and edge sections es along the length l. this flexible locking element could bend in the length direction and the protruding part p 2 could be displaced vertically in the locking groove if a force f is applied to the protruding part p 2 . fig. 7f shows a double tongue 15 . fig. 7g shows an extruded section with a resilient punched inner part p 1 . fig. 7h shows a flexible tongue 15 with protruding parts p 2 at the edge sections es. with these production methods and basic principles a wide variety of complex two and three-dimensional shapes could be produced at low cost. of course the flexible locking element 15 could be made from metal, preferably aluminium, but wood based sheet material such as hdf and compact laminate could also be used to form flexible locking elements with machining and punching and in combination with for example flexible rubber materials or similar. figs. 8a-8c show how the flexible locking element 15 is connected to a groove 14 at a short side 5 a of a floor panel. fig. 8a shows an embodiment with a flexible tongue as shown in fig. 7b and fig. 8b shows an embodiment according to fig. 7a . fig. 8c shows a floor panel with a flexible locking element on the short sides 5 a, 5 b and an angling system c, d on the long sides 4 a, 4 b. of course the long sides can also have one or several flexible locking elements. the flexible locking element 15 has in this embodiment a length l that is smaller than the width fl of the floor panel. as a non-restricting example it could be mentioned that sufficient locking strength could be achieved with a flexible locking element with a length l which is smaller than 0.8 times the floor width fw. even a length l of 0.5 times fw could be sufficient. such a flexible locking element could have a weight of about 1 gram and the material cost could be considerably lower than for other known technologies where separate materials are used. it is also very easy to connect to the locking element since it is not very important that the flexible locking element is connected at a precise distance from the corner portions 23 . a further advantage is that the tongue 10 extends along essentially the whole short side as in traditional floor panels. this gives a strong vertical connection especially at the corner portions 23 . of course the flexible locking element could cover essentially the whole width fw. the flexible locking element could be connected to the locking groove in several ways. a preferable method is that the flexible locking element is mechanically fixed. of course glue or mechanical devices can also be used. to simplify the understanding the panel is located with its rear side up and the flexible locking element is on the short side. the panel could also be turned with the front side up. the flexible locking element is separated from blanks 50 , if it is moulded, or from rolls if is extruded. it is then pressed or rolled into the locking groove when a short side of the panel is displaced under a fixing unit and the locking element is connected with friction. a lot of alternatives are possible within the main principles that the flexible locking element is separated and fixed with a friction force. figs. 9a to 9i are examples which show that known locking systems, especially traditional snap systems with a bendable strip ( 9 a - 9 c or 9 g - 9 i ) or lip 6 9 d - 9 f ) could be adjusted to a snap system with a flexible locking element 14 according to the invention. generally only a simple adjustment of the locking groove is necessary. it could be made in the same machine and with the same number of cutting tools. figs. 10a-10d show that the principles used in a locking system with a flexible locking element could also be used to replace the tongue 10 with a flexible tongue 30 in order to provide a locking system, which could be locked by vertical folding. one panel 1 ′ could be moved along the vertical plane vp vertically towards another panel 1 . the flexible tongue 30 is in this case displaced horizontally according to the same principles as described for the flexible locking element and all embodiments of the flexible locking element could be used. of course the flexible locking element could be combined with a flexible tongue. such a locking system could be locked with angling, snapping and vertical folding. fig. 10d shows that it is an advantage if the flexible tongue 30 on a short side is positioned between the upper and lower parts of the tongue 10 ′ and groove 9 ′ on the long sides. this gives a stronger locking at the corner portions. within the invention a lot of alternatives are possible to accomplish snapping with a flexible locking element. all features of the embodiment described above could be combined with each other or used separately. they could be used on long and/or short sides. the method to produce a separate locking element, which is inserted into a groove, could of course be used to improve friction properties and strength even if the locking element is not flexible or displaceable in the vertical direction. the methods and principles could also be used together with a flexible tongue that could be bent in horizontal direction during locking. the flexible locking element could also be combined with a strip 6 or lip which is partly bent during snapping. the degree of such a bending could be considerable smaller than in present known systems. the system could be used to connect tile shaped panels installed on a wall. the tiles could be connected to each other and to a locking member fixed to the wall. it will be apparent to those skilled in the art that various modifications and variations of the present invention can be made without departing from the spirit and scope of the invention. thus, it is intended that the present invention include the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
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054-370-330-539-330
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US
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[
"US"
] |
H01L51/54,C07F5/02,C09K11/02,C09K11/06,H01L51/00,H01L51/50
| 2016-01-04T00:00:00 |
2016
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[
"H01",
"C07",
"C09"
] |
organic electroluminescent materials and devices
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a compound containing five member ring fused b—n heterocycles is useful as host materials in oleds.
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1. a compound having a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof. 2. the compound of claim 1 , wherein y 1 is the same as y 2 . 3. the compound of claim 1 , wherein y 1 is different from y 2 . 4. the compound of claim 1 , wherein z 1 -z 8 are each a carbon. 5. the compound of claim 1 , wherein at least one of z 1 -z 8 is nitrogen. 6. the compound of claim 1 , wherein l 1 and l 2 are each independently selected from the group consisting of: 7. the compound of claim 1 , wherein ao, are and ar 3 are each independently selected from the group consisting of: 8. the compound of claim 1 , wherein the compound is selected from the group consisting of: 9. an organic light emitting device (oled) comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof. 10. the oled of claim 9 , wherein the organic layer is an emissive layer and the compound of formula i, or ii is a host. 11. the oled of claim 9 , wherein the organic layer further comprises a phosphorescent emissive dopant; wherein the emissive dopant is a transition metal complex having at least one ligand, or part of the ligand if the ligand is more than bidentate, selected from the group consisting of: wherein each x 1 to x 13 are independently selected from the group consisting of carbon and nitrogen; wherein x is selected from the group consisting of br′, nr′, pr′, o, s, se, c═o, s═o, so 2 , cr′r″, sir′r″, and ger′r″; wherein r′ and r″ are optionally fused or joined to form a ring; wherein each r a , r b , r c , and r d may represent from mono substitution to the possible maximum number of substitution, or no substitution; wherein r′, r″, r a , r b , r c , and r d are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substitutents of r a , r b , r c , and r d are optionally fused or joined to form a ring or form a multidentate ligand. 12. the oled of claim 9 , wherein the organic layer is a blocking layer and the compound of formula i, or ii is a blocking material in the organic layer. 13. the oled of claim 9 , wherein the organic layer is a transporting layer and the compound of formula i, or ii is a transporting material in the organic layer. 14. the oled of claim 9 , wherein the oled is incorporated into a device selected from the group consisting of a consumer product, an electronic component module, and a lighting panel. 15. a formulation comprising a compound having a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof.
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cross-reference to related applications this application claims priority under 35 u.s.c. § 119(e) to u.s. provisional application ser. no. 62/274,450, filed jan. 4, 2016, the entire contents of which is incorporated herein by reference. parties to a joint research agreement the claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: the regents of the university of michigan, princeton university, university of southern california, and the universal display corporation. the agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement. field the present invention relates to a compound containing five member ring fused b—n heterocycles useful as host materials in oleds. background opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. in addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. examples of organic opto-electronic devices include organic light emitting diodes/devices (oleds), organic phototransistors, organic photovoltaic cells, and organic photodetectors. for oleds, the organic materials may have performance advantages over conventional materials. for example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants. oleds make use of thin organic films that emit light when voltage is applied across the device. oleds are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. several oled materials and configurations are described in u.s. pat. nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety. one application for phosphorescent emissive molecules is a full color display. industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. in particular, these standards call for saturated red, green, and blue pixels. alternatively the oled can be designed to emit white light. in conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. the same technique can also be used with oleds. the white oled can be either a single eml device or a stack structure. color may be measured using cie coordinates, which are well known to the art. one example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted ir(ppy) 3 , which has the following structure: in this, and later figures herein, we depict the dative bond from nitrogen to metal (here, ir) as a straight line. as used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. small molecules may include repeat units in some circumstances. for example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. the core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. a dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of oleds are small molecules. as used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. there may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. for example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between. as used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form. a ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. a ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand. as used herein, and as would be generally understood by one skilled in the art, a first “highest occupied molecular orbital” (homo) or “lowest unoccupied molecular orbital” (lumo) energy level is “greater than” or “higher than” a second homo or lumo energy level if the first energy level is closer to the vacuum energy level. since ionization potentials (ip) are measured as a negative energy relative to a vacuum level, a higher homo energy level corresponds to an ip having a smaller absolute value (an ip that is less negative). similarly, a higher lumo energy level corresponds to an electron affinity (ea) having a smaller absolute value (an ea that is less negative). on a conventional energy level diagram, with the vacuum level at the top, the lumo energy level of a material is higher than the homo energy level of the same material. a “higher” homo or lumo energy level appears closer to the top of such a diagram than a “lower” homo or lumo energy level. as used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. on a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. thus, the definitions of homo and lumo energy levels follow a different convention than work functions. more details on oleds, and the definitions described above, can be found in u.s. pat. no. 7,279,704, which is incorporated herein by reference in its entirety. summary according to an embodiment, a novel compound is disclosed. the novel compound has a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof. according to another aspect of the present disclosure, an organic light emitting device (oled) is disclosed. the oled comprises an anode, a cathode, and an organic layer, disposed between the anode and the cathode, wherein the organic layer comprising the novel compound disclosed herein. according to another aspect of the present disclosure, a formulation comprising the novel compound is also disclosed. brief description of the drawings fig. 1 shows an organic light emitting device. fig. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer. detailed description generally, an oled comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. when a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). the injected holes and electrons each migrate toward the oppositely charged electrode. when an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. light is emitted when the exciton relaxes via a photoemissive mechanism. in some cases, the exciton may be localized on an excimer or an exciplex. non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable. the initial oleds used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in u.s. pat. no. 4,769,292, which is incorporated by reference in its entirety. fluorescent emission generally occurs in a time frame of less than 10 nanoseconds. more recently, oleds having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. baldo et al., “highly efficient phosphorescent emission from organic electroluminescent devices,” nature, vol. 395, 151-154, 1998; (“baldo-i”) and baldo et al., “very high-efficiency green organic light-emitting devices based on electrophosphorescence,” appl. phys. lett., vol. 75, no. 3, 4-6 (1999) (“baldo-ii”), are incorporated by reference in their entireties. phosphorescence is described in more detail in u.s. pat. no. 7,279,704 at cols. 5-6, which are incorporated by reference. fig. 1 shows an organic light emitting device 100 . the figures are not necessarily drawn to scale. device 100 may include a substrate 110 , an anode 115 , a hole injection layer 120 , a hole transport layer 125 , an electron blocking layer 130 , an emissive layer 135 , a hole blocking layer 140 , an electron transport layer 145 , an electron injection layer 150 , a protective layer 155 , a cathode 160 , and a barrier layer 170 . cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164 . device 100 may be fabricated by depositing the layers described, in order. the properties and functions of these various layers, as well as example materials, are described in more detail in u.s. pat. no. 7,279,704 at cols. 6-10, which are incorporated by reference. more examples for each of these layers are available. for example, a flexible and transparent substrate-anode combination is disclosed in u.s. pat. no. 5,844,363, which is incorporated by reference in its entirety. an example of a p-doped hole transport layer is m-mtdata doped with f 4 -tcnq at a molar ratio of 50:1, as disclosed in u.s. patent application publication no. 2003/0230980, which is incorporated by reference in its entirety. examples of emissive and host materials are disclosed in u.s. pat. no. 6,303,238 to thompson et al., which is incorporated by reference in its entirety. an example of an n-doped electron transport layer is bphen doped with li at a molar ratio of 1:1, as disclosed in u.s. patent application publication no. 2003/0230980, which is incorporated by reference in its entirety. u.s. pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as mg:ag with an overlying transparent, electrically-conductive, sputter-deposited ito layer. the theory and use of blocking layers is described in more detail in u.s. pat. no. 6,097,147 and u.s. patent application publication no. 2003/0230980, which are incorporated by reference in their entireties. examples of injection layers are provided in u.s. patent application publication no. 2004/0174116, which is incorporated by reference in its entirety. a description of protective layers may be found in u.s. patent application publication no. 2004/0174116, which is incorporated by reference in its entirety. fig. 2 shows an inverted oled 200 . the device includes a substrate 210 , a cathode 215 , an emissive layer 220 , a hole transport layer 225 , and an anode 230 . device 200 may be fabricated by depositing the layers described, in order. because the most common oled configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230 , device 200 may be referred to as an “inverted” oled. materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200 . fig. 2 provides one example of how some layers may be omitted from the structure of device 100 . the simple layered structure illustrated in figs. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. the specific materials and structures described are exemplary in nature, and other materials and structures may be used. functional oleds may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. other layers not specifically described may also be included. materials other than those specifically described may be used. although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. also, the layers may have various sublayers. the names given to the various layers herein are not intended to be strictly limiting. for example, in device 200 , hole transport layer 225 transports holes and injects holes into emissive layer 220 , and may be described as a hole transport layer or a hole injection layer. in one embodiment, an oled may be described as having an “organic layer” disposed between a cathode and an anode. this organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to figs. 1 and 2 . structures and materials not specifically described may also be used, such as oleds comprised of polymeric materials (pleds) such as disclosed in u.s. pat. no. 5,247,190 to friend et al., which is incorporated by reference in its entirety. by way of further example, oleds having a single organic layer may be used. oleds may be stacked, for example as described in u.s. pat. no. 5,707,745 to forrest et al, which is incorporated by reference in its entirety. the oled structure may deviate from the simple layered structure illustrated in figs. 1 and 2 . for example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in u.s. pat. no. 6,091,195 to forrest et al., and/or a pit structure as described in u.s. pat. no. 5,834,893 to bulovic et al., which are incorporated by reference in their entireties. unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. for the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in u.s. pat. nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (ovpd), such as described in u.s. pat. no. 6,337,102 to forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (ovjp), such as described in u.s. pat. no. 7,431,968, which is incorporated by reference in its entirety. other suitable deposition methods include spin coating and other solution based processes. solution based processes are preferably carried out in nitrogen or an inert atmosphere. for the other layers, preferred methods include thermal evaporation. preferred patterning methods include deposition through a mask, cold welding such as described in u.s. pat. nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and ovjp. other methods may also be used. the materials to be deposited may be modified to make them compatible with a particular deposition method. for example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing. devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. one purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. the barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. the barrier layer may comprise a single layer, or multiple layers. the barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. any suitable material or combination of materials may be used for the barrier layer. the barrier layer may incorporate an inorganic or an organic compound or both. the preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in u.s. pat. no. 7,968,146, pct pat. application nos. pct/us2007/023098 and pct/us2009/042829, which are herein incorporated by reference in their entireties. to be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. the weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. the polymeric material and the non-polymeric material may be created from the same precursor material. in one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon. devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. such electronic component modules can optionally include the driving electronics and/or power source(s). devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (pdas), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-d displays, vehicles, a large area wall, theater or stadium screen, or a sign. various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees c. to 30 degrees c., and more preferably at room temperature (20-25 degrees c.), but could be used outside this temperature range, for example, from −40 degree c. to +80 degree c. the materials and structures described herein may have applications in devices other than oleds. for example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. more generally, organic devices, such as organic transistors, may employ the materials and structures. the term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine. the term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. additionally, the alkyl group may be optionally substituted. the term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. additionally, the cycloalkyl group may be optionally substituted. the term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. preferred alkenyl groups are those containing two to fifteen carbon atoms. additionally, the alkenyl group may be optionally substituted. the term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. preferred alkynyl groups are those containing two to fifteen carbon atoms. additionally, the alkynyl group may be optionally substituted. the terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. additionally, the aralkyl group may be optionally substituted. the term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. hetero-aromatic cyclic radicals also means heteroaryl. preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. additionally, the heterocyclic group may be optionally substituted. the term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. the polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. additionally, the aryl group may be optionally substituted. the term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to five heteroatoms. the term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. additionally, the heteroaryl group may be optionally substituted. the alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be unsubstituted or may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. as used herein, “substituted” indicates that a substituent other than h is bonded to the relevant position, such as carbon. thus, for example, where r 1 is mono-substituted, then one r 1 must be other than h. similarly, where r 1 is di-substituted, then two of r 1 must be other than h. similarly, where r 1 is unsubstituted, r 1 is hydrogen for all available positions. the “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the c—h groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[fh]quinoxaline and dibenzo[fh]quinoline. one of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein. it is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). as used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent. according to an aspect, a compound is disclosed where the compound has a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof. in some embodiments of the compound defined above, y 1 is the same as y 2 . in some embodiments, y 1 is different from y 2 . in some other embodiments, z 1 -z 8 are each a carbon. in some other embodiments, at least one of z 1 -z 8 is nitrogen. in some embodiments of the compound, l 1 and l 2 are each independently selected from the group consisting of: in some embodiments of the compound, ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of: in some embodiments of the compound, the compound is selected from the group consisting of: according to another aspect, an oled is disclosed. the oled comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode. the organic layer comprises a compound having a formula selected from the group consisting of: wherein one of x 1 and x 2 is nitrogen, and the other one of x 1 and x 2 is boron; wherein y 1 and y 2 are each independently selected from the group consisting of o, s, and nar 3 ; wherein l 1 and l 2 are each independently selected from the group consisting of direct bond, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; wherein z 1 -z 8 are each independently selected from the group consisting of carbon and nitrogen; wherein ar 1 , ar 2 and ar 3 are each independently selected from the group consisting of hydrogen, deuterium, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof; wherein r 1 and r 2 each independently represent mono to maximum allowable substitutions, or no substitution; and wherein r 1 and r 2 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, halogen, alkyloxyl, aryl, heteroaryl, and combinations thereof. in some embodiments of the oled, the organic layer is an emissive layer and the compound of formula i, or ii is a host. in some embodiments of the oled, the organic layer further comprises a phosphorescent emissive dopant; wherein the emissive dopant is a transition metal complex having at least one ligand, or part of the ligand if the ligand is more than bidentate, selected from the group consisting of: wherein each x 1 to x 13 are independently selected from the group consisting of carbon and nitrogen; wherein x is selected from the group consisting of br′, nr′, pr′, o, s, se, c═o, s═o, so 2 , cr′r″, sir′r″, and ger′r″, wherein r′ and r″ are optionally fused or joined to form a ring; wherein each r a , r b , r c , and r d may represent from mono substitution to the possible maximum number of substitution, or no substitution; wherein r′, r″, r a , r b , r c , and r d are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substitutents of r a , r b , r c , and r d are optionally fused or joined to form a ring or form a multidentate ligand. in some embodiments of the oled, the emissive dopant is selected from the group consisting of: in some embodiments of the oled, the organic layer is a blocking layer and the compound of formula i, or ii is a blocking material in the organic layer. in some other embodiments, the organic layer is a transporting layer and the compound of formula i, or ii is a transporting material in the organic layer. in some embodiments, the oled is incorporated into a device selected from the group consisting of a consumer product, an electronic component module, and a lighting panel. according to another aspect, a formulation comprising a compound is disclosed, wherein the compound has a formula selected from the group consisting of: formula i, formula ii, formula ii, formula iv, formula v, and formula vi; as defined above. combination with other materials the materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. for example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. the materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination. conductivity dopants: a charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. the conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the fermi level of the semiconductor may also be achieved. hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer. non-limiting examples of the conductivity dopants that may be used in an oled in combination with materials disclosed herein are exemplified below together with references that disclose those materials: ep01617493, ep01968131, ep2020694, ep2684932, us20050139810, us20070160905, us20090167167, us2010288362, wo06081780, wo2009003455, wo2009008277, wo2009011327, wo2014009310, us2007252140, us2015060804 and us2012146012. hil/htl: a hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as pedot/pss; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as moo x ; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds. examples of aromatic amine derivatives used in hil or htl include, but are not limited to the following general structures: each of ar 1 to ar 9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. each ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. in one aspect, ar 1 to ar 9 is independently selected from the group consisting of: wherein k is an integer from 1 to 20; x 101 to x 108 is c (including ch) or n; z 101 is nar 1 , o, or s; ar 1 has the same group defined above. examples of metal complexes used in hil or htl include, but are not limited to the following general formula: wherein met is a metal, which can have an atomic weight greater than 40; (y 101 -y 102 ) is a bidentate ligand, y 101 and y 102 are independently selected from c, n, o, p, and s; l 101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal. in one aspect, (y 101 -y 102 ) is a 2-phenylpyridine derivative. in another aspect, (y 101 -y 102 ) is a carbene ligand. in another aspect, met is selected from ir, pt, os, and zn. in a further aspect, the metal complex has a smallest oxidation potential in solution vs. fc + /fc couple less than about 0.6 v. non-limiting examples of the hil and htl materials that may be used in an oled in combination with materials disclosed herein are exemplified below together with references that disclose those materials: cn102702075, de102012005215, ep01624500, ep01698613, ep01806334, ep01930964, ep01972613, ep01997799, ep02011790, ep02055700, ep02055701, ep1725079, ep2085382, ep2660300, ep650955, jp07-073529, jp2005112765, jp2007091719, jp2008021687, jp2014-009196, kr20110088898, kr20130077473, tw201139402, u.s. ser. no. 06/517,957, us20020158242, us20030162053, us20050123751, us20060182993, us20060240279, us20070145888, us20070181874, us20070278938, us20080014464, us20080091025, us20080106190, us20080124572, us20080145707, us20080220265, us20080233434, us20080303417, us2008107919, us20090115320, us20090167161, us2009066235, us2011007385, us20110163302, us2011240968, us2011278551, us2012205642, us2013241401, us20140117329, us2014183517, u.s. pat. no. 5,061,569, u.s. pat. no. 5,639,914, wo05075451, wo07125714, wo08023550, wo08023759, wo2009145016, wo2010061824, wo2011075644, wo2012177006, wo2013018530, wo2013039073, wo2013087142, wo2013118812, wo2013120577, wo2013157367, wo2013175747, wo2014002873, wo2014015935, wo2014015937, wo2014030872, wo2014030921, wo2014034791, wo2014104514, wo2014157018, ebl: an electron blocking layer (ebl) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. the presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, as compared to a similar device lacking a blocking layer. also, a blocking layer may be used to confine emission to a desired region of an oled. in some embodiments, the ebl material has a higher lumo (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the ebl interface. in some embodiments, the ebl material has a higher lumo (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the ebl interface. in one aspect, the compound used in ebl contains the same molecule or the same functional groups used as one of the hosts described below. additional hosts: the light emitting layer of the organic el device of the present invention preferably contains at least a metal complex as light emitting dopant material, and may contain one or more additional host materials using the metal complex as a dopant material. examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. any host material may be used with any dopant so long as the triplet criteria is satisfied. examples of metal complexes used as host are preferred to have the following general formula: wherein met is a metal; (y 103 -y 104 ) is a bidentate ligand, y 103 and y 104 are independently selected from c, n, o, p, and s; l 101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal. in one aspect, the metal complexes are: wherein (o—n) is a bidentate ligand, having metal coordinated to atoms o and n. in another aspect, met is selected from ir and pt. in a further aspect, (y 103 -y 104 ) is a carbene ligand. examples of other organic compounds used as additional host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. in one aspect, host compound contains at least one of the following groups in the molecule: wherein r 101 to r 107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. x 101 to x 108 is selected from c (including ch) or n. z 101 and z 102 is selected from nr 101 , o, or s. non-limiting examples of the additional host materials that may be used in an oled in combination with the host compound disclosed herein are exemplified below together with references that disclose those materials: ep2034538, ep2034538a, ep2757608, jp2007254297, kr20100079458, kr20120088644, kr20120129733, kr20130115564, tw201329200, us20030175553, us20050238919, us20060280965, us20090017330, us20090030202, us20090167162, us20090302743, us20090309488, us20100012931, us20100084966, us20100187984, us2010187984, us2012075273, us2012126221, us2013009543, us2013105787, us2013175519, us2014001446, us20140183503, us20140225088, us2014034914, u.s. pat. no. 7,154,114, wo2001039234, wo2004093207, wo2005014551, wo2005089025, wo2006072002, wo2006114966, wo2007063754, wo2008056746, wo2009003898, wo2009021126, wo2009063833, wo2009066778, wo2009066779, wo2009086028, wo2010056066, wo2010107244, wo2011081423, wo2011081431, wo2011086863, wo2012128298, wo2012133644, wo2012133649, wo2013024872, wo2013035275, wo2013081315, wo2013191404, wo2014142472, emitter: an emitter example is not particularly limited, and any compound may be used as long as the compound is typically used as an emitter material. examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., tadf (also referred to as e-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes. non-limiting examples of the emitter materials that may be used in an oled in combination with materials disclosed herein are exemplified below together with references that disclose those materials: cn103694277, cn1696137, eb01238981, ep01239526, ep01961743, ep1239526, ep1244155, ep1642951, ep1647554, ep1841834, ep1841834b, ep2062907, ep2730583, jp2012074444, jp2013110263, jp4478555, kr1020090133652, kr20120032054, kr20130043460, tw201332980, u.s. ser. no. 06/699,599, u.s. ser. no. 06/916,554, us20010019782, us20020034656, us20030068526, us20030072964, us20030138657, us20050123788, us20050244673, us2005123791, us2005260449, us20060008670, us20060065890, us20060127696, us20060134459, us20060134462, us20060202194, us20060251923, us20070034863, us20070087321, us20070103060, us20070111026, us20070190359, us20070231600, us2007034863, us2007104979, us2007104980, us2007138437, us2007224450, us2007278936, us20080020237, us20080233410, us20080261076, us20080297033, us200805851, us2008161567, us2008210930, us20090039776, us20090108737, us20090115322, us20090179555, us2009085476, us2009104472, us20100090591, us20100148663, us20100244004, us20100295032, us2010102716, us2010105902, us2010244004, us2010270916, us20110057559, us20110108822, us20110204333, us2011215710, us2011227049, us2011285275, us2012292601, us20130146848, us2013033172, us2013165653, us2013181190, us2013334521, us20140246656, us2014103305, u.s. pat. no. 6,303,238, u.s. pat. no. 6,413,656, u.s. pat. no. 6,653,654, u.s. pat. no. 6,670,645, u.s. pat. no. 6,687,266, u.s. pat. no. 6,835,469, u.s. pat. no. 6,921,915, u.s. pat. no. 7,279,704, u.s. pat. no. 7,332,232, u.s. pat. no. 7,378,162, u.s. pat. no. 7,534,505, u.s. pat. no. 7,675,228, u.s. pat. no. 7,728,137, u.s. pat. no. 7,740,957, u.s. pat. no. 7,759,489, u.s. pat. no. 7,951,947, u.s. pat. no. 8,067,099, u.s. pat. no. 8,592,586, u.s. pat. no. 8,871,361, wo06081973, wo06121811, wo07018067, wo07108362, wo07115970, wo07115981, wo08035571, wo2002015645, wo2003040257, wo2005019373, wo2006056418, wo2008054584, wo2008078800, wo2008096609, wo2008101842, wo2009000673, wo2009050281, wo2009100991, wo2010028151, wo2010054731, wo2010086089, wo2010118029, wo2011044988, wo2011051404, wo2011107491, wo2012020327, wo2012163471, wo2013094620, wo2013107487, wo2013174471, wo2014007565, wo2014008982, wo2014023377, wo2014024131, wo2014031977, wo2014038456, wo2014112450, a hole blocking layer (hbl) may be used to reduce the number of holes and/or excitons that leave the emissive layer. the presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. also, a blocking layer may be used to confine emission to a desired region of an oled. in some embodiments, the hbl material has a lower homo (further from the vacuum level) and or higher triplet energy than the emitter closest to the hbl interface. in some embodiments, the hbl material has a lower homo (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the hbl interface. in one aspect, compound used in hbl contains the same molecule or the same functional groups used as host described above. in another aspect, compound used in hbl contains at least one of the following groups in the molecule: wherein k is an integer from 1 to 20; l 101 is an another ligand, k′ is an integer from 1 to 3. etl: electron transport layer (etl) may include a material capable of transporting electrons. electron transport layer may be intrinsic (undoped), or doped. doping may be used to enhance conductivity. examples of the etl material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons. in one aspect, compound used in etl contains at least one of the following groups in the molecule: wherein r 101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as ar's mentioned above. ar 1 to ar 3 has the similar definition as ar's mentioned above. k is an integer from 1 to 20. x 101 to x 108 is selected from c (including ch) or n. in another aspect, the metal complexes used in etl include, but are not limited to the following general formula: wherein (o—n) or (n—n) is a bidentate ligand, having metal coordinated to atoms o, n or n, n; l 101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal. non-limiting examples of the etl materials that may be used in an oled in combination with materials disclosed herein are exemplified below together with references that disclose those materials: cn103508940, ep01602648, ep01734038, ep01956007, jp2004-022334, jp2005149918, jp2005-268199, kr0117693, kr20130108183, us20040036077, us20070104977, us2007018155, us20090101870, us20090115316, us20090140637, us20090179554, us2009218940, us2010108990, us2011156017, us2011210320, us2012193612, us2012214993, us2014014925, us2014014927, us20140284580, u.s. pat. no. 6,656,612, u.s. pat. no. 8,415,031, wo2003060956, wo2007111263, wo2009148269, wo2010067894, wo2010072300, wo2011074770, wo2011105373, wo2013079217, wo2013145667, wo2013180376, wo2014104499. wo2014104535, charge generation layer (cgl) in tandem or stacked oleds, the cgl plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. electrons and holes are supplied from the cgl and electrodes. the consumed electrons and holes in the cgl are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. typical cgl materials include n and p conductivity dopants used in the transport layers. in any above-mentioned compounds used in each layer of the oled device, the hydrogen atoms can be partially or fully deuterated. thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof. it is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. for example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. the present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. it is understood that various theories as to why the invention works are not intended to be limiting.
|
059-156-250-954-328
|
IE
|
[
"AU",
"EP",
"WO",
"IE"
] |
H01L21/60,H01L21/98,H01L23/367,H01L23/538,H01L25/065,H05K1/18
| 2002-07-22T00:00:00 |
2002
|
[
"H01",
"H05"
] |
electronics circuit manufacture
|
a circuit with embedding components (13) is produced by placing the components (13) on a substrate (14) and applying sheets (15) of prepreg. the prepreg sheets (15) have apertures to accommodate the -components, the number of sheets and arrangement of apertures being chosen to accommodate a variety of component x, y and z dimensions. a top layer with cu foil (16(b)) is applied. the assembly is pressed in an operation analogous to conventional multilayer board lamination pressing. this causes all of the prepreg resin to flow to completely embed the components without raids or damage. electrical connections are made by drilling and plating vias.
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1. a method of manufacturing a circuit comprising the steps of embedding a component between external layers and making at least one electrical connection to the component through an external layer, wherein the component is encapsulated by: providing an internal material around the component and between the external layers, causing the internal material to flow, and allowing the internal material to cure. 2. a method as claimed in claim 1, wherein the internal material is caused to flow by application of heat and external pressure on both sides. 3. a method as claimed in claim 2, wherein the internal material comprises a resin of the type which flows under application of heat and pressure. 4. a method as claimed in any preceding claim, wherein the internal material comprises reinforcing fibres. 5. a method as claimed in any preceding claim, wherein the internal material is applied as one or more solid sheet having an aperture for the component. 6. a method as claimed in claim 5, wherein the depth of the sheet or sheets is such as to leave a cavity over the component. 7. a method as claimed in claims 5 or 6, wherein the layer includes a dummy aperture to provide a space for excess internal material when it flows. 8. a method as claimed in any preceding claim, wherein application of the internal material and pressing takes place in a vacuum. 9. a method as claimed in any of claims 5 to 8, wherein the internal material is applied as a plurality of solid sheets, one above the other. 10. a method as claimed in claim 9, wherein there are a plurality of components of different heights and the sheets have apertures to accommodate heights of all of the components. 11. a method as claimed in any preceding claim, wherein a conducting layer is applied externally before or after internal material flow. 12. a method as claimed in any of claims 2 to 11, wherein pressure and/or resin depth are dynamically monitored to ensure that the internal material does not become thinner than a target minimum thickness, being greater than the depth of the deepest component. 13. a method as claimed in any preceding claim, wherein the internal material is prepreg. 14. a method as claimed in any preceding claim, wherein an electrical connection is made to a component terminal and a conductor land on a layer by drilling a via through said layer and an insulation layer and plating the via so that the plating inter-connects the conductor land and the component terminal. 15. a method as claimed in claim 14, wherein a component is connected to an internal conducting layer, and the method comprises the further steps of: subsequently applying an outer insulation layer externally of the internal conducting layer, and drilling through the external insulating layer from the outside to the internal conducting layer to make a connection from the outside to the internal conducting layer. 16. a method as claimed in any preceding claim, wherein an electrical connection is made to a component lateral lead. 17. a method as claimed in claim 16, wherein a via is drilled through the lead. 18. a method as claimed in any of claims 14 to 17, wherein the via is laser drilled. 19. a method as claimed in any of claims 14 to 17, wherein the via is mechanically drilled. 20. a method as claimed in any of claims 14 to 17, wherein the via is drilled by acid exposure for selective removal of insulation layer material. 21. a method as claimed in claim 20, wherein an outer conductive laminated layer is selectively etched where vias are required and subsequent acid exposure is performed to remove underlying insulation material, remaining conductive layer acting as etch resist. 22. a method as claimed in claim 21, comprising the further step of back-etching the outer conductive layer. 23. a method as claimed in any of claims 14 to 17, wherein the via is drilled by plasma etching. 24. a method as claimed in any of claims 14 to 17, wherein the via is drilled by high pressure liquid jet machining , with or without abrasives. 25. a method as claimed in any preceding claim, wherein a plurality of components are embedded in the internal material one above the other and are interconnected by a multi-layer vertical bus 26. a method as claimed in claim 25, wherein bus interconnections are made at vias formed through the components. 27. a method as claimed in claim 26, wherein interconnections are made at vias formed through component terminals or bonding pads to stack at least two components with total inter-component interconnection length being only the thickness of the components and intervening layers. 28. a method as claimed in any preceding claim, wherein a via is drilled in a layer and a waveguide is mounted in the via to provide an optical connection to a component. 29. a method as claimed in any preceding claim, wherein a layer comprises a transparent portion for emission or absorption of light or other electromagnetic radiation for signal or power exchange by a component. 30. a method as claimed in claim 29, wherein said layer is formed to provide at least one lens. 31. a method as claimed in any preceding claim, comprising the further step of providing a heat-transfer layer thermally connected to any external or internal part of a component 32. a method as claimed in claim 31, wherein the layer is thermally connected by vias and/or by electrical connections. 33. a method as claimed in claims 31 or 32, wherein the heat-transfer layer is a substrate onto which the component is placed. 34. a method as claimed in claims 32 to 34, wherein said heat transfer layer also acts as a power plane. 35. a method as claimed in any preceding claim, comprising the further step of applying an external electromagnetic shielding layer. 36. a method as claimed in any preceding claim, wherein an external layer comprises a board etched and/ or plated for interconnection of components. 37. a method as claimed in any preceding claim, wherein the internal material is powder-form epoxy, and it is flowed and attached by initially applying heat and subsequently flowed by heat and pressure. 38. a method of manufacturing a circuit substantially as described with reference to the drawings. 39. a circuit whenever produced by a method of any preceding claim.
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"electronics circuit manufacture" introduction field of the invention the invention relates to manufacture of circuits having passive components such as resistors and capacitors and/or active components such as transistors and integrated circuits either packaged or unpackaged (die form). prior art discussion us pat. no. 6,400,573 bl (texas instruments inc.) pertains to packaging of semiconductor components and more particularly to packaging of multiple semiconductor die in a laminated substrate with an interconnect layer formed in a* deposited overlay structure. cavities of specific depths are made in the upper surface of a polymer substrate to accommodate integrated circuit chips such that the to ' surface of the chip and the top surface of the substrate are coplaήar. a layer of laminate film is then disposed on top of the die and substrate surfaces with yia openings. the via openings are disposed such that they expose bonding pads on the die surface. a conductor pattern is disposed on the laminate film so as to extend between at least some of the via openings and provide electrical connections to the bonding pads. subsequent layers of high density interconnect (hdi) are then applied. a disadvantage of this technique is the complexity of forming the cavities to the required dimensions. also, it appears that the die are not completely encapsulated as voids exist in the cavities after the die have been placed because the cavities are slightly larger than the die that are placed in them. us pat. no. 6,403,881 bl (elliot industries ltd) relates to an electronic component package assembly and method of manufacturing the same. an electronic component package assembly is produced in the form of a panel. a planar base substrate, a frame layer made from laminate material with a number of cavities is attached to the planar base substrate. a component is attached to the planar base substrate in each of the cavities and a lid fits over the cavity. the component in the cavity may or may not be enclosed in a protective material. us pat. no. 6,344,688 bl (singapore institute of microelectronics) relates to a multi- chip package for active and/or passive devices. the devices are joined to a flexible tape which is then joined to a substrate having a cavity such that the devices are within the cavity. the flexible tape has a number of interconnect pads and test pads. these are connected to the chips by electrodes or within the flexible tape. us pat. no. 5,564,181 (draper laboratory inc.) relates to a laminated substrate assembly chips-first ultichip module and a method of making it. . electronic components are thinned to a predetermined thickness and are mounted on a flat internal layer in precise positions. a mechanical spacer layer having precisely- located apertures corresponding to the component locations is applied. spaces between the mechanical spacer layer and components may be filled during laminations by adhesive for securing the mechanical spacer layer to the bottom and top layers. a cover layer is bonded over the mechanical layer and the tops of the components. disadvantages of this method are that the chips must be accurately thinned and the apertures made to precisely fit the chips. also, it appears that voids may remain around components if there is insufficient excess adhesive. ep 0611,129 bl (lockheed) also describes a process in which components of differing shapes and thicknesses are placed on a substrate. a mould form is placed around the components and the mould is filled over the components and the moulding material is cured at 300°c. this approach appears to allow versatility in component height difference. however, it also appears that there is little versatility m component or conductor arrangements above the components, where the moulding material has been cured. jp06247726 describes a method for mounting semiconductor chips in which a chip die bonded to a board is coated on the periphery with an insulating material. holes for wiring are then made in the insulation layer by means of a laser beam. the hole is filled with a conductor and a wiring pattern is formed on the surface of the insulation layer. a paper by towle et al. entitled "bumpless build-up layer packaging", asme international mechanical engineering congress and exposition, november 2001, describes a method in which a die or dice is embedded in a substrate which then has one or more build up layers formed on top. embedding the die in the panel can be done with moulding or dispensed encapsulation material. a paper by ostmann et al. entitled "chip in polymer - the next step in miniaturization", advancing microelectronics, vol 29, no. 3, may/june 2002, ρpl3-15, describes the embedding thinned silicon chips in to build up layers of a printed circuit board. an aspect of this work is the thinning of the silicon chips to approximately 50 μm. the invention is therefore directed towards achieving a process for embedding a component or components with: improved versatility in component dimensions, avoiding need to pre-machine components; and/ or utilisation of some conventional circuit board production equipment and techniques to minimise lead time and cost for implementations of the method; and/or improved robustness of the end product; and/ or avoidance of voids around the component. summary of the invention according to the invention, there is provided a method of manufacturing a circuit comprising the steps of embedding a component between external layers and making at least one electrical connection to the component through an external layer, wherein the component is encapsulated by: providing an internal material around the component and between the external layers, causing the internal material to flow, and allowing the internal material to cure. thus, by virtue of the internal material flowing the component is completely encapsulated without voids and without need to provide components of a particular height. another major advantage that because the component is embedded in internal material between external layers, conventional multilayer board production equipment and techniques can be used for some of the operations. in one embodiment, the internal material is caused to flow by application of heat and external pressure on both sides. in one embodiment, the internal material comprises a resin of the type which flows under application of heat and pressure . in one embodiment, the internal material comprises reinforcing fibres. in another embodiment, the internal material is applied as one or more solid sheet having an aperture for the component. in one embodiment, the depth of the sheet or sheets is such as to leave a cavity over the component. in one embodiment, the layer includes a dummy aperture to provide a space for excess internal material when it flows. in one embodiment, application of the internal material and pressing takes place in a vacuum. in one embodiment, the internal material is applied as a plurality of solid sheets, one above the other. in one embodiment, there are a plurality of components of different heights and the sheets have apertures to accommodate heights of all of the components. in a further embodiment, a conducting layer is applied externally before or after internal material flow. in one embodiment, pressure and/ or resin depth are dynamically monitored to ensure that the internal material does not become thinner than a target minimum thickness, being greater than the depth of the deepest component. in one embodiment, the internal material is prepreg. in one embodiment, an electrical connection is made to a component terminal and a conductor land on a layer by drilling a via through said layer and an insulation layer and plating the via so that the plating inter-connects the conductor land and the component terminal. in one embodiment, a component is connected to an internal conducting layer, and the method comprises the further steps of: subsequently applying an outer insulation layer externally of the internal conducting layer, and drilling through the external insulating layer from the outside to the internal conducting layer to make a connection from the outside to the internal conducting layer. in one embodiment, an electrical connection is made to a component lateral lead. in one embodiment, a via is drilled through the lead. in one embodiment, the via is laser drilled. in one embodiment, the via is mechanically drilled. in one embodiment, the via is drilled by acid exposure for selective removal of insulation layer material. in one embodiment, an outer conductive laminated layer is selectively etched where vias are required and subsequent acid exposure is performed to remove underlying insulation material, remaining conductive layer acting as etch resist. in another embodiment, the method comprises the further step of back-etching the outer conductive layer. in one embodiment, the via is drilled by plasma etching. in one embodiment, the via is drilled by high pressure liquid jet machining , with or without abrasives. in one embodiment, a plurality of components are embedded in the internal material one above the other and are interconnected by a multi-layer vertical bus in one embodiment, bus interconnections are made at vias formed through the components. in one embodiment, interconnections are made at vias formed through component terminals or bonding pads to stack at least two components with total inter- component interconnection length being only the thickness of the components and intervening layers. in one embodiment, a via is drilled in a layer and a waveguide is mounted in the via to provide an optical connection to a component. in one embodiment, a layer comprises a transparent portion for emission or absorption of light or other electromagnetic radiation for signal or power exchange by a component. in one embodiment, said layer is formed to provide at least one lens. in one embodiment, the method comprises the further step of providing a heat- transfer layer thermally connected to any external or internal part of a component. in one embodiment, the layer is thermally connected by vias and/or by electrical connections. in one embodiment, the heat-transfer layer is a substrate onto which the component is placed. in one embodiment, said heat transfer layer also acts as a power plane. in one embodiment the method comprises the further step of applying an external electromagnetic shielding layer. in one embodiment, an external layer comprises a board etched and/ or plated for interconnection of components. in one embodiment, the internal material is powder-form epoxy, and it is flowed and attached by initially applying heat and subsequently flowed by heat and pressure. the invention also provides a circuit whenever produced by a method as defined above. detailed description of the invention brief description of the drawings the invention will be more clearly understood from the following description of some embodiments thereof, given by way of example only with reference to the accompanying drawings in which:- fig 1 is a cross-sectional diagram showing part of a circuit of the invention, in which components are embedded within a multi-layer board type structure; fig. 2 is a flow diagram illustrating the production process; and figs. 3 to 6 are cross-sectional diagrams of different circuits produced according to the process; description of the embodiments referring to fig 1, a circuit 1 has an smt component 2 embedded within a multilayer circuit having a top foil 3 and a bottom foil 4. the component 2 is connected to the remainder of the circuit by laser-drilled vias 5 and 6 which extend from the top surface, through the foil 3 and terminate at terminals at the top of the component 2. a through via 7 extends fully through the circuit 1. all of the vias are laser-drilled and electro-plated using a conventional electro-plating technique. the multi-layer board comprises fr4 layers 9, 11, and 12 and circuit conductors 8 and 10 on the fr4 layers 9 and 11. the board is manufactured in the conventional manner for multi-layer circuit boards using fr4 prepreg and fr4 material. however, the manufacturing process also embeds the component 2 into the top layer 12. referring to figs. 2(a) to 2(e) the process for embedding a component (semiconductor die) is described. for clarity, the process steps are described for a simple situation in which the substrate is a single layer, and only one component is illustrated. figs. 2(a) and 2(b). a prepared copper-clad fr4 sheet 14 is provided and a die 13 is placed on it with an underfill of compatible adhesive. the underfill is of the type typically used when dies are bonded to a lead frame before injection moulding to produce packaged ics, to absorb cte differences with low loss of thermal conductivity. since such dies have a body of, usually, silicon, and circuitry on only one side (opposite the underfill side), electrical isolation to copper and die circuitry and hence between multiple dies can be achieved through such die bodies. however, such die bodies have a relatively high thermal conductivity, allowing excellent heat dissipation. thinning of die bodies can also be made to further enhance thermal conductivity. the sheet 14 may be selectively etched and suitably pretreated for lamination. three sheets 15 of prepreg material are placed over the sheet 14. the sheets 15 have apertures through which the component 13 and other components fit freely in the x, y, and z directions. the sheets 15 are in this embodiment liquid crystal polymer (lcp) bondsheets (prepreg) available for multilayer board production. the sheets 15 are pre-machined according to a design so that the components fit through them and the depth of the aperture is greater than the thickness of the component. components of different thicknesses can be accommodated by pre-machining the prepreg sheets according to the design. for example, at another xy location there may be apertures in only the two lowermost or uppermost sheets 15. some prepreg layers include dummy apertures to accommodate excess prepreg resin, as described below. the final thickness of the compressed prepreg with all apertures exclusive of component volumes completely filled with resin is calculated at preparation stage. in calculating the aperture for a component, consideration is made for its height so that a thicker (in z) component usually is provided with a larger aperture to be filled with resin than a thinner component, providing similar overall thinning of the prepreg through resin flow into these cavities. extra apertures in the prepreg sheets are then added at suitable locations at this calculation stage to balance the average pressed thickness across the board . consideration here is given to maximum resin travel distance. press parameters such as pressure and 'temperature increase rate' are modified to adjust optimum resin travel distance. consideration is given to ensure that the total of resin is sufficient to fill all of the cavities without allowing its thickness to reach its minimum possible, i.e. when pressure would be exerted onto the prepreg fibres instead of providing liquid pressure to fill cavities. also, the design is such that the final pressed layer thickness exceeds the thickness of every component embedded in it. thus, an advantage over the prior art is that large component height differences (several mms) can be accommodated. by adjusting prepreg build and aperture sizes and dummy apertures as above with suitable safety margins, there is also no risk that a die is being subjected to direct mechanical pressure in z at any local point, potentially resulting in cracked chips. the z press lamination pressure is hereby converted to a uniform xyz liquid pressure only to discrete components until the resin has set. after resin has set, any further application of z pressure will be equally distributed due to prior encapsulation. fig. 2(c) and 2(d). a sheet comprising a prepreg (a lcp bondsheet is one suitable prepreg material for dies, combining absence of halogens and hermetic properties) layer 16(a) and copper foil 16(b) is placed over the prepreg layers 15. this is done leaving an empty (with negligible air) cavity over each component 13. the top-most sheet may, for example, alternatively be an rcc foil. again this is widely used in the multilayer circuit industry. pressure is then applied to the opposed sides of the board in conditions of applied heat and a vacuum so that the prepreg material 15 and 16(a) flows all around the components 13 to completely encapsulate them. the prepreg is then allowed to cure to provide a homogenous cured body 17. this step is analogous to the conventional lamination step for multilayer board production and can be implemented with such equipment. it is only the resin part of the prepreg which flows and then thermosets, any fibres providing mechanical and sometimes required thermal properties. the words 'complete' and 'homogenous' are herein used in relative terms , i.e. as near absolute as required depending on applied vacuum and pressure. the internal pressure is dynamically maintained so that the resin of the prepreg flows sufficiently to completely encapsulate the components irrespective of spaces around components and differing component heights. the prepreg sheet dimensions and internal "dummy" apertures are such as to avoid excessive flow of excess resin outside of the external side edges and to maintain uniform layer height and component encapsulation. after pressing, the cured depth, d2, is greater than the maximum component thickness, dl, with a margin. this is achieved, as described above, by design of the prepreg sheets and by choice of press pressure, and temperature rise and liquid resin viscosity. in an fr4 - embodiment parameters typically range from 12 to 18 bar and 2 to 4 degree/minute. a lower "kiss pressure" of some 20% of full pressure before resin melt starts is usually employed during air evacuation time(15-60 minutes) as well, especially if a large percentage of area is occupied by dies to avoid mechanical deformation of remaining prepreg and following potential damage to dies. other materials have 'standard' times that usually needs to be adjusted accordingly from a standard multilayer press cycle with only prepreg and inner layers to bond. during the pressing operation the (previously evacuated) spaces above (and also any voids around) the components 13 are filled with flowing resin because of countering of the mechanical pressure by a liquid pressure, preventing further collapse. only a small volume of resin escapes at the board (panel) edges. fig. 2(e) the top foil 16(b) and cured resin 16a is after lamination selectively removed (laser usually) down to points on die for connection, and these openings are electroplated to make connections to the components. a via 18 is shown in fig. 2(e). more complex interconnectivity may be achieved by subsequently applying more prepreg layers and foil, pressing, and making external via connections to the (now internal) foil 16(b), equivalent to standard forming of buried micro vias. the layouts for connecting tracks can be near identical for a buried die inside a pcb and the same die in a 'csp' package attached with solder balls, without consideration for minimum solder ball pad size. instead of using the sheet 16(a)/ 16(b), one or more double-sided selectively etched boards may be used to provide connecting track layers. this is particularly advantageous if the components have many connection points, potentially reducing number of lamination cycles to one. for example, there may be a number of components each having 20 x 20 bond pads, and the tracks on the external sheets connect the pads to a bus. also, a shielding layer, for example of cu followed by ni, may be laminated with prepreg again on the outside(s) through further press lamination above or below all components and interconnections as required. this provides shielding and electromagnetic interference noise protection. the hence reduced noise sensitivity may also allow lower operating voltages and higher clock speeds or reduced power consumption and generated emi noise. in the copper sheet embodiment, instead of using an insulating substrate a thermally conductive substrate such as a sheet of thick copper may be used. this provides good heat dissipation from the components, increasing circuit life and improving reliability for most circuit designs, especially when the whole circuit side then can be directly attached to external cooling if a component is optical a via may be drilled to act as a socket for a waveguide interconnection. also, some layers may be transparent at some or all wavelengths to allow emission or absorption of light or other electromagnetic waves for signal or power exchange of light by components, possibly with focusing. an embedding plane may be curved to provide a focusing lens. during pressing, high vacuum in combination with the liquid pressure during resin flow ensures that there is high volume reduction of any remaining air during the encapsulation stage, providing near homogenous encapsulation. also, while the pressing operation is analogous to multilayer board lamination pressing, in the invention prior to resin set there is no direct pressure applied to the components, only indirect and symmetrical pressure via the liquid flowing around the components with a depth exceeding the maximum component depth. after the resin has set, pressure is mechanical again, but totally distributed across dies through the encapsulation process. the clearance also prevents most small dust particles i.e. under or over a die or uneven die topography to exert any direct mechanical pressure on components during pressing. an alternative to laser drilling is to use acid etching to simultaneously form vias. an outer foil is etched to a via pattern, and upon acid dipping the underlying prepreg is dissolved to the desired depth. the extent of dissolving of the prepreg may be greater than that of the foil etch, and so back-etching of the foil may be required to enlarge the foil via diameter to match that of the internal prepreg. the acid dip technique allows all vias to be simultaneously "drilled", as opposed to the sequential laser drilling method. this leads to significantly higher efficiencies and much less use of - in ¬ expensive laser drilling plant, when a very high number of such via holes are required. it will be appreciated that the components are embedded using only a variation of standard manufacturing techniques used in the multi-layer circuit industry. also, there is no need for soldered connections to the flip chip, this being achieved by use of the platings on the layers and the vias, although the embedding as per the invention of panels with components soldered to circuitry can sometimes be a feasible option. another advantage is that there are no need for exposed components on the outside of the multilayer board, and so the circuit may be used for harsh physical and/or electrical environments and they do not need to be physically protected by a housing. also, the invention avoids the problems arising in standard environments of dust particles reducing electrical isolation between conductors, particularly for high-density and/ or high voltage circuits, and reduces possible terminal spacing in all cases when air is replaced by insulators of much greater strength. furthermore, it is possible to place components on the outside surfaces of the board in the conventional manner, and/ or on additional internal layers thus achieving a desired circuit density in a versatile manner. many different configurations of circuits are possible using this method and some are illustrated in figs. 3 to 6. referring to fig. 3 a circuit 20 has a flip chip 21 embedded in a multi-layer board having top and bottom foil layers 22 and 23 respectively and six additional conductor layers in-between. vias 24 interconnect the top surface to the flip chip 21. vias 25 interconnect the top surface to conductors on an internal foil, so that connections to the flip chip 21 are completed by a second set of vias 26. a via 27 extends between the inner foil layers on both sides. the vias 26 and 27 are "buried" vias formed after a first pressing. the "outer" vias 24 (and also any fully through-vias if there were any) are drilled after a second press cycle, after a first plating state is complete. referring to fig. 4 a circuit 40 has a component 41 embedded in a board having only one substrate fr4 layer 45. six layers of prepreg 46 are used to build up to the height of the component 41, and a seventh layer is placed over the top of the component 41 and the other layers. a through via 44 interconnects foil layers 42 and 43. in this embodiment, the vias 44 are electrically connected to lateral leads 47 of the component 41 instead of the top surfaces of the component. this is achieved by drilling through the lead 47 and subsequently electroplating. the block 41 may alternatively be a number of at least two components. in a variation of this embodiment a through-via may be used to interconnect multiple components in the z dimensions. this may be in a bus arrangement, allowing very high frequency connectivity. the processing for connecting vias to component leads may involve back etching of epoxy to obtain clean connections, just like in standard multilayer pcb fabrication. where there is a high density of vertically stacked components there may be at least one thermally conductive cooling layer providing a thermal path to an exposed surface. referring to fig. 5 a circuit 60 has an embedded component 61 over a set of cooling vias 64 extending through an fr4 layer 63. layers of prepreg 65 are placed over the layer 63 in which all but the topmost prepreg sheet 66 has an aperture for accommodating the components 61. in this arrangement there is a combination of underneath electrical connections made by the vias 64 and lateral electrical connections made by through vias 62 extending through component leads 67. such cooling vias can also be drilled, usually with a drill bit with a flat tip with a drill machine equipped with depth control, into the packaged chip to the copper plate the die is attached to, from the non-die side, to provide cooling path(s) through subsequent copper plating. referring to fig. 6 a circuit 80 is produced in a symmetrical manner about an xy plane through its centre. the circuit is achieved in two placement cycles followed by a pressing cycle and a drilling and plating cycle on both external sides. a second press and drilling and plating cycle is required for a buried micro via 85. the items of fig. 6 are: 81: components, 82: prepreg, 83: fr4 layers on to which 81 were placed with suitable adhesive before pressing, the prepreg layers 82 being placed around and above the components 81, 85: micro vias formed after first pressing cycle encapsulating all components, then plated, then buried in a second press cycle, 84: made from prepreg in second press cycle, burying 85, 86: 'double-layer' micro via connecting outer foil with component terminal, 87:copper foil added together with 83 at first press cycle, 88: external components soldered post board manufacture in normal fashion, 89: through via, added after second lamination at same cycle as 86 and 96, 95: internal component connected at same cycle as 89 formed, and 96: connecting via to component 95. it will be appreciated from the above that a wide variety of circuit configurations is possible using only a variation of standard multi-layer board manufacturing techniques. this versatility is in terms of both the locations and types of components and the xyz dimensions of the components. component basic height variations are accommodated by providing an aperture in, say, six prepreg layers for a high component and in only four layers for a low component. full advantage is then taken of the flow properties of thermosetting resins in prepreg. when the vertical lamination pressure is applied on the stack the resin in the layers is temporarily (for 1-5 mins. typically) a liquid. the prepreg layer number and thickness is chosen so that the thickness does not reach a minimum possible pressed thickness, namely that of the non-flowable fibres impregnated in the resin, and does never reach to the height of any component. dummy apertures may be included in some prepreg layers to control flows and thickness. determination of number, size, and locations of component and dummy apertures is according to average resin flow distance linked to its viscosity in the build-up , press cycle pressure and duration, and mechanical cad data for the components. components the components embedded according to the invention may be of any electronic or opto-electronic type such as: - ball grid arrays (bgas) and csps without solder balls, and dies. there may be via connections to lateral terminals. - resistors. - capacitors. - transistors and integrated circuits. - thermoelectric components. it will be appreciated that this versatility arises from the options of top, bottom, and side electrical connections and of thermal conducting layers or vias, and of any desired component height. internal materials it is not essential that prepreg be used. any material having electrical insulation properties and being capable of reflowing (preferably but not necessarily during lamination pressing) without excessive pressure being applied to components may be used. examples are: - polymers containing resins. - high purity oxides or polymides. - a powder epoxy which melts when the circuit/panel and/ or the epoxy itself is heated and dipped into it. the coating thickness will depend on the circuit/panel temperature. such temperature must not allow resin to more then partly cure to provide good resin flow during final pressure lamination step in which the epoxy is re-flowed under pressure. fibres may be mixed with the epoxy for purposes of thermal conductivity and/ or for strength. thick coatings can be applied as there are no solvents in such powder. - glass, graphite, or aramid fibres impregnated with a reactive thermoset resin formulation or a thermoplastic resin. drilling as set out above, acid exposure may be used for simultaneous formation of a large number of vias. alternatively, plasma etching may be used. where acid exposure or plasma etching are used, the internal material may be pre-processed to remove glass from the via locations, thus avoiding any potential barriers to the acid dipping via formation. advantages of the process the process of the invention uses a variant of a standard process for manufacturing multilayer circuit boards, and so may be easily implemented. it allows a very high component density to be achieved with excellent versatility. it also provides excellent protection for the embedded components. another advantage is that there is no need for soldering, thus avoiding the quality problems associated with solder joints. the process may be used to completely encapsulate a circuit for use in a harsh environment, with for example external condensation. the apparent disadvantage of poor thermal dissipation can be avoided by providing thermal conduction planes and/ or vias as described above. a metal layer may double as both a power plane and a heat dissipater. in pcb fabrication standard size panels, often 18" x 24" are used. these often have as many individual circuits as possible, that after manufacturing are cut up into finished units, that in themselves can be electronic components. the further processing cost of a panel of a certain layer count and complexity type after embedding is essentially the same as that of a standard multilayer panel without the components embedded. to obtain the same functions with this technology as with mounting standard discrete packages onto a panel, many times more units of the same complexity can be fitted on the same production panel, reducing overall processing cost per unit. the invention is not limited to the embodiments described but may be varied in construction and detail. for example, when copper is used in this specification it shall be noted that although copper is the most common conductive material used, other suitable conductive materials are not excluded. when "fr4" is used herein it shall be noted that other resin systems are suitable, as set out above. also the term 'via' should be interpreted to include blind 'micro vias' and blind drilled or etched holes and through holes of any suitable size. the term "plated via" should be interpreted accordingly, although sometimes just "via" has been used for this, although the meaning is clear from the context.
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059-351-258-309-626
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US
|
[
"US"
] |
A23L3/3454,B29B9/12,B32B9/00,C12N11/02
| 2008-01-04T00:00:00 |
2008
|
[
"A23",
"B29",
"B32",
"C12"
] |
encapsulation of oxidatively unstable compounds
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an encapsulated material is formed by congealing droplets of a molten blend of oxidatively unstable material and phytosterol in a chilling gas stream to form prilled cores containing oxidatively unstable material and phytosterol, and encapsulating the prilled cores in one or more protective shell layers to form free-flowing microparticles.
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1 . a method for protecting an oxidatively unstable material, which method comprises congealing droplets of a molten blend of oxidatively unstable material and phytosterol in a chilling gas stream to form prilled cores comprising oxidatively unstable material and phytosterol, and encapsulating the prilled cores in one or more protective shell layers to form free-flowing microparticles. 2 . the method of claim 1 wherein the oxidatively unstable material comprises a polyunsaturated fatty acid. 3 . the method of claim 2 wherein the polyunsaturated fatty acid comprises an omega-3 or omega-6 fatty acid. 4 . the method of claim 1 wherein the oxidatively unstable material comprises an acidulant, animal product, antioxidant, carotenoid, catalyst, drug, dye, enzyme, flavor, fragrance, lutein, lycopene, metal complex, natural color, nutraceutical, pigment, polyphenolic, processed plant material, metabiotic, probiotic, protein, squalene, tocopherol, tocotrienol, triacylglycerol, vitamin, unsaturated organic compound, or mixture thereof. 5 . the method of claim 1 wherein the phytosterol comprises a non-esterified phytosterol. 6 . the method of claim 1 comprising drying or prilling a protective shell layer. 7 . the method of claim 1 comprising forming a protective shell layer from gelatin. 8 . the method of claim 1 comprising forming a protective shell layer from triglyceride wax, stearic acid, insoluble fiber, soluble fiber, a water-dispersible oxygen barrier layer, a hydrocolloid layer or a lipophilic layer. 9 . the method of claim 1 wherein the encapsulated oxidatively unstable material has enhanced protection from oxidation compared to the oxidatively unstable material by itself. 10 . the method of claim 1 further comprising combining the microparticles with a food to provide a food product. 11 . an encapsulated material comprising free-flowing microparticles containing a prilled core comprising a congealed blend of oxidatively unstable material and phytosterol, covered by at least one protective shell layer. 12 . the encapsulated material of claim 11 wherein the core comprises a polyunsaturated fatty acid. 13 . the encapsulated material of claim 12 wherein the polyunsaturated fatty acid comprises an omega-3 or omega-6 fatty acid. 14 . the encapsulated material of claim 13 wherein the antioxidant comprises ubiquinol, ubiquione or mixture thereof. 15 . the encapsulated material of claim 11 wherein the core comprises an acidulant, animal product, antioxidant, carotenoid, catalyst, drug, dye, enzyme, flavor, fragrance, lutein, lycopene, metal complex, natural color, nutraceutical, pigment, polyphenolic, processed plant material, metabiotic, probiotic, protein, squalene, tocopherol, tocotrienol, triacylglycerol, vitamin, unsaturated organic compound, or mixture thereof. 16 . the encapsulated material of claim 11 wherein the phytosterol comprises a non-esterified phytosterol. 17 . the encapsulated material of claim 11 wherein the core is greater than 30 wt. % of the encapsulated material. 18 . the encapsulated material of claim 11 wherein the oxidatively unstable material is a solid, gel or liquid at room temperature. 19 . the encapsulated material of claim 11 wherein a protective shell layer comprises gelatin. 20 . the encapsulated material of claim 11 wherein a protective shell layer comprises triglyceride wax, stearic acid, insoluble fiber, soluble fiber, a water-dispersible oxygen barrier layer, a hydrocolloid layer or a lipophilic layer. 21 . the encapsulated material of claim 11 wherein the oxidatively unstable material has enhanced protection from oxidation compared to the oxidatively unstable material by itself. 22 . a food product comprising the encapsulated material of claim 11 .
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cross-reference to related applications this application claims the benefit of the filing date of u.s. provisional application ser. no. 61/224,018 filed jul. 8, 2009, the disclosure of which is incorporated herein by reference. this application is also a continuation-in-part of copending international application nos. pct/us2009/030052 and pct/us2009/030054 each filed jan. 2, 2009 and respectively published as wo 2009/089115 a1 and wo 2009/089117 a1, both of which claim priority from u.s. provisional application ser. no. 61/010,073 filed jan. 4, 2008, the disclosures of which are all incorporated herein by reference. field this invention relates to encapsulation of materials that are sensitive to oxidation. background in the past thirty years much new information on the benefits of a healthy diet has emerged. in addition to the traditional food pyramid, vitamins and minerals, a healthy diet may include components such as soluble and insoluble fiber for promoting gastrointestinal health, phytosterols for lowering cholesterol levels and promoting heart health, antioxidants for discouraging cancer and other inflammatory diseases, and omega-3 and omega-6 polyunsaturated fatty acids (pufas) for promoting heart and brain health. there has been considerable commercial interest in providing deliverable forms of such components even though in many cases the component may be oxidatively unstable. pufa-containing products or materials have introduced or announced by companies including basf se, blue pacific flavors, gat food essentials gmbh, kerry group plc, martek biosciences corp. and ocean nutrition canada. there is at present an ongoing and unmet need for improved methods and systems for packaging, storing or delivering pufas and other oxidatively unstable materials. summary of the invention the present invention provides, in one aspect, a method for protecting an oxidatively unstable material, which method comprises congealing droplets of a molten blend of oxidatively unstable material and phytosterol in a chilling gas stream to form prilled cores comprising oxidatively unstable material and phytosterol, and encapsulating the prilled cores in one or more protective shell layers to form free-flowing microparticles. the invention provides, in another aspect, an encapsulated material comprising free-flowing microparticles containing a prilled core comprising a congealed blend of oxidatively unstable material and phytosterol, covered by at least one protective shell layer. the disclosed encapsulated materials include at least an oxidation sensitive prilled core containing at least one oxidatively unstable material and at least one phytosterol, and at least one protective shell layer surrounding the core. the encapsulated materials may employ a multi-tiered defensive approach involving oxygen barriers, lipophilic antioxidants and hydrophilic antioxidants. the disclosed methods and materials can provide processed oils and other oxidatively unstable materials with enhanced oxidative stability and a desirable dry powder form. brief description of the drawing fig. 1 through fig. 4 are schematic cross-sectional views of various encapsulated materials. detailed description unless the context indicates otherwise the following terms shall have the following meaning and shall be applicable to the singular and plural: the terms “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. thus a microcapsule that contains “a” shell may include “one or more” shells. the term “congealed” when used with respect to a material means that the material was molten, and has been cooled or frozen without substantial solvent mass transfer or evaporation to a rigid or solid state below its melting temperature. the term “congealing” means changing a molten material by cooling or freezing the material without substantial solvent mass transfer or evaporation, so that the material transitions from a soft or fluid state above its melting temperature to a rigid or solid state below its melting temperature. the term “deliverable” when used with respect to an encapsulated substance means that the substance is at least partially surrounded by an additional substance that imparts one or more altered properties to the encapsulated substance, e.g., altered transport, altered flowability, altered resistance to oxidation or moisture, altered abrasion resistance, or altered performance in a commercial application (e.g., a food application). the terms “dried” and “dryable” when used with respect to a material means that the material was or may be present in a liquid solution or dispersion, and has been or may be changed using substantial solvent mass transfer or evaporation to a rigid or solid state. the term “drying” means changing a liquid material by substantial solvent mass transfer or evaporation to a rigid or solid state. the terms “encapsulated material” and “microcapsule” mean particles (often but not always spherical in shape, and often but not always having a diameter of about 10 nanometers to about 5 mm which contain at least one solid core surrounded by at least one continuous membrane or shell. the terms “fluid” and “liquid” when used in reference to a substance means that the substance has a loss modulus (g″) greater than its storage modulus (g′) and a loss tangent (tan δ) greater than 1. the terms “gel” and “gelled” when used in reference to a substance means that the substance is deformable (viz., is not a solid), g″ is less than g′ and tan δ is less than 1. the term “ingestible” means capable of and safe for oral administration. the term “microsphere” means a microcapsule material whose particles contain two or more cores distributed in and surrounded by at least one continuous membrane or shell. the term “minimally processed” when used in reference to a food means that the food meets applicable u.s. department of agriculture (usda) guidelines or regulations for a minimally processed food, or in the absence of such guidelines or regulations is a food which has been subjected to a traditional process for making such food edible, to preserve it or to make it safe for human consumption, such as smoking, roasting, freezing, drying, fermenting or employing physical processes which do not fundamentally alter the raw food product or which only separate a whole, intact food into component parts, e.g. grinding meat, separating eggs into albumen and yolk, or pressing fruits to produce juices. the term “molten” when used with respect to a blend means above the melting temperature for such blend. the term “particulate” means a finely divided dry powder material. the term “prilled” when used in respect to a particulate material means that the particles were formed by prilling. the term “prilling” means forming droplets of a molten material and congealing them in a cooling gas stream to form gelled or solid microparticles. the terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. however, other embodiments may also be preferred, under the same or other circumstances. furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention. the term “taste profile” means a combination of taste, flavor, consistency, odor or other sensory quality associated with eating. the recitation of a numerical range using endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). the recitation of sets of upper and lower endpoints (e.g., at least 1, at least 2, at least 3, and less than 10, less than 5 and less than 4) includes all ranges that may be formed from such endpoints (e.g., 1 to 10, 1 to 5, 2 to 10, 2 to 5, etc.). fig. 1 shows an exemplary deliverable encapsulated material 100 including an oxidatively unstable prilled core 102 surrounded by an outer dried protective shell layer 104 . layer 104 provides a protective and water vapor transmission-resistant shell over core 102 . core 102 contains a congealed gelled or solid blend of oxidatively unstable material and phytosterol (not individually identified in fig. 1 ). the oxidatively unstable material (which may, for example, be a pufa, a refined or extracted triacylglycerol (tag), an antioxidant, or mixture thereof) may provide a health benefit when ingested, and the phytosterol (which may, for example, be campesterol, β-sitosterol, or mixture thereof) may improve oxidation resistance of the oxidatively-sensitive material and may provide a further health benefit when ingested. the phytosterol may also contribute to one or more other properties such as structural stability (viz., keeping the core inside the shell) or steric stability (viz., increasing the shell strength). protective shell layer 104 (which may, for example, be gelatin, agar-agar, carbohydrate, low melting wax such as stearic acid, or mixture thereof) may improve the level of oxidation resistance over that provided by the uncoated core. fig. 2 shows another exemplary deliverable encapsulated material 200 including oxidatively unstable core 102 surrounded by dried protective shell layer 104 as in fig. 1 . core 102 may optionally contain dispersed solid particles 106 which may alter the properties of core 102 or layer 104 , or may provide other features to encapsulated material 100 . particles 106 may be formed for example from solids including calcium salts, alginic acid and salts thereof including sodium or calcium alginate, chelating agents including citric acid, or antioxidants including ascorbic acid. shell 104 is surrounded by an intermediate hydrocolloid shell 206 made for example from alginate, an intermediate fiber/carbohydrate shell 208 made for example from a mixture of maltodextrin, sucrose, trehalose and starch, and an outer protective layer 210 made for example from a mixture of lipid, fiber and protein. layers or shells 104 , 206 and 208 may optionally contain at least one phytosterol. the various layers shown in fig. 2 are merely exemplary and may be rearranged, combined into fewer layers, augmented with additional layers or made from other ingredients or mixtures of ingredients. doing so may facilitate formation of encapsulated materials which maintain, preserve or protect the prilled core and keep oxygen and if desired one or both of water or light away from the core. fig. 3 shows another exemplary deliverable encapsulated material in the form of a microsphere 300 including a plurality of oxidatively unstable core particles 100 similar to those shown in fig. 1 surrounded by intermediate hydrocolloid shells 306 made for example from gelatin or alginate. the particles 100 and their shells 306 may be dispersed in a protective matrix 312 made for example from a mixture of maltodextrin, sucrose, starch, ascorbic acid and oat fiber. the shells 306 or matrix 312 may optionally contain at least one phytosterol. fig. 4 shows another exemplary deliverable encapsulated material in the form of a microsphere 400 including a plurality of oxidatively unstable core particles 100 and surrounding intermediate hydrocolloid shells 306 dispersed in a protective matrix 312 , and surrounded by a protective wax-containing shell 420 . shell 420 may include a variety of other ingredients, e.g., soluble fibers, lipid soluble materials including tocopherols, and dispersed water-soluble particulates including ascorbic acid and citric acid. shell 420 may optionally contain at least one phytosterol. a variety of oxidatively unstable materials may be used in the core. exemplary oxidatively unstable materials include acidulants, animal products, antioxidants, carotenoids, catalysts, drugs, dyes, enzymes, flavors, fragrances, lutein, lycopene, metal complexes, natural colors, nutraceuticals, pigments, polyphenolics, processed plant materials, metabiotics, probiotics, proteins, pufas, squalenes, sterols other than phytosterols, tocopherol, tocotrienol, tags, vitamins (e.g., fat-soluble vitamins)), unsaturated organic compounds (e.g., unsaturated rubbers and unsaturated oils) and mixtures thereof. pufas, antioxidants, sterols other than phytosterols and tags are of particular interest. the oxidatively unstable material may for example represent about 2 to about 96 wt. %, about 5 to about 96 wt. %, about 20 to about 96 wt. % or about 40 to about 96 wt. % of the encapsulated material. for oxidatively unstable materials that normally are liquids at the desired use temperature (e.g., at room temperature or about 25° c.), it may be desirable to gel the liquid in order to facilitate prilling. for example, core materials based on liquids may be gelled as described in u.s. pat. no. 6,858,666 b2 (hamer et al.) where an oxidatively unstable liquid oil is heated in the presence of a suitable gelation agent to melt and dissolve the gelation agent in the continuous oil phase. the resultant solution may then be atomized and congealed to form prilled cores. the amount of gelation agent(s) may for example range from about 1 to about 90 wt. % of the core weight. additional exemplary gelled core particles based on pufas may be formed by combining a pufa with a phytosterol to form triglyceride-recrystallized phytosterols as in u.s. pat. nos. 6,638,547 b2 (perlman et al.) and 7,144,595 b2 (perlman et al.) and u.s. patent application publication no. 2006/0251790 a1 (perlman et al.). some antioxidants, e.g., vitamin e, may also help convert a liquid core material to a gel. oxidatively unstable materials that normally are liquids at the desired use temperature may also be made by carrying out prilling at a sufficiently low temperature to enable formation of gelled or solid prilled cores, followed by encapsulation at a sufficiently low temperature to enable formation of the protective shell layer. exemplary pufas include those found in fish and various grain products, e.g., fish oil, halibut, herring, mackerel, menhaden, salmon, algae, chia, flaxseed and soybeans. pufas based on deodorized fish oils containing substantial amounts of omega-3 or omega-6 fatty acids are of particular interest. exemplary omega-3 fatty acids include all-cis-7,10,13-hexadecatrienoic acid (16:3ω3), α-linolenic acid (ala, 18:3ω3), stearidonic acid (std, 18:4ω3), eicosatrienoic acid (ete, 20:3ω3), eicosatetraenoic acid (eta, 20:4ω3), eicosapentaenoic acid (epa, 20:5ω3), docosapentaenoic acid (dpa, 22:5ω3), docosahexaenoic acid (dha, 22:6ω3), tetracosapentaenoic acid (24:5ω3), tetracosahexaenoic acid (nisinic acid, 24:6ω3) and mixtures thereof. exemplary omega-6 fatty acids include linoleic acid (18:2ω6), gamma-linolenic acid (18:3ω6), eicosadienoic acid (20:2ω6), dihomo-gamma-linolenic acid (20:3ω6), arachidonic acid (20:4ω6), docosadienoic acid (22:2ω6), adrenic acid (22:4ω6), docosapentaenoic acid (22:5ω6), calendic acid (18:3ω6) and mixtures thereof. exemplary antioxidants include menaquinone (vitamin k 2 ), plastoquinone, retinol (vitamin a), vitamin d, vitamin e, phylloquinone (vitamin k 1 ), tocopherols, tocotrienols (e.g., α, β, γ and δ-tocotrienols), ubiquinol, and ubiquione (coenzyme q10)); and cyclic or polycyclic compounds including acetophenones, anthroquinones, benzoquiones, biflavonoids, catechol melanins, chromones, condensed tannins, coumarins, flavonoids, hydrolyzable tannins, hydroxycinnamic acids, hydroxybenzyl compounds, isoflavonoids, lignans, naphthoquinones, neolignans, phenolic acids, phenols (including bisphenols and other sterically hindered phenols, aminophenols and thiobisphenols), phenylacetic acids, phenylpropenes, stilbenes and xanthones. additional cyclic or polycyclic antioxidant compounds include apigenin, auresin, aureusidin, biochanin a, capsaicin, catechin, coniferyl alcohol, coniferyl aldehyde, cyanidin, daidzein, daphnetin, delphinidin, emodin, epicatechin, eriodicytol, esculetin, ferulic acid, formononetin, gernistein, gingerol, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-hydroxycoumarin, juglone, kaemferol, lunularic acid, luteolin, malvidin, mangiferin, 4-methylumbelliferone, mycertin, naringenin, pelargonidin, peonidin, petunidin, phloretin, p-hydroxyacetophenone, (+)-pinoresinol, procyanidin b-2, quercetin, resorcinol, rosmaric acid, salicylic acid, scopolein, sinapic acid, sinapoyl-(s)-maleate, sinapyl aldehyde, syrginyl alcohol, telligrandin ii, umbelliferone and vanillin. antioxidants may also be obtained from plant extracts, e.g., from blackberries, blueberries, black carrots, chokecherries, cranberries, black currants, elderberries, red grapes and their juice, hibiscus, oregano, purple sweet potato, red wine, rosemary, strawberries, tea (e.g., black, green or white tea), and from various plant ingredients as ellagic acid. additional exemplary antioxidants include carotenoids including hydrocarbons such as hexahydrolycopene, lycopersene, phtyofluene, torulene and α-zeacarotene; alcohols such as alloxanthin, cynthiaxanthin, cryptomonaxanthin, crustaxanthin, gazaniaxanthin, loroxanthin, lycoxanthin, pectenoxanthin, rhodopin, rhodopinol and saproxanthin; glycosides such as oscillaxanthin and phleixanthophyll; ethers such as rhodovibrin and spheroidene; epoxides such as citroxanthin, diadinoxanthin, foliachrome, luteoxanthin, mutatoxanthin, neochrome, trollichrome, vaucheriaxanthin and zeaxanthin; aldehydes such as rhodopinal, torularhodinaldehyde and wamingone; ketones such as canthaxanthin, capsanthin, capsorubin, cryptocapsin, flexixanthin, hydroxyspheriodenone, okenone, pectenolone, phoeniconone, phoenicopterone, phoenicoxanthin, rubixanthone and siphonaxanthin; esters such as astacein, fucoxanthin, isofucoxanthin, physalien, siphonein and zeaxanthin dipalmitate; apo carotenoids such as β-apo-2′-cartoenal, apo-2-lycopenal, apo-6′-lycopenal, azafrinaldehyde, bixin, citranaxanthin, crocetin, crocetinsemialdehyde, crocin, hopkinsiaxanthin, methyl apo-6′-lycopenoate, paracentrone and sintaxanthin; nor and seco carotenoids such as actinioerythrin, β-carotene, peridinin, pyrrhoxanthininol, semi-α-carotenone, semi-β-carotenone and triphasiaxanthin; retro and retro apo carotenoids such as eschscholtzxanthin, eschscholtzxanthone, rhodoxanthin and tangeraxanthin; higher carotenoids such as decaprenoxanthin and nonaprenoxanthin; secondary aromatic amines; alkyl and arylthioethers; phosphates and phosphonites; zinc-thiocarbamates; benzofuranone lactone-based antioxidants; nickel quenchers; metal deactivators or complexing agents; and the like. commercially available antioxidants include butylated hydroxyanisole (bha), 2,6-di-t-butyl cresol (bht), 2,2′-methylene bis(6-t-butyl-4-methyl phenol) (available as vulkanox™ bkf from bayer inc., canada), 2,2′-thio bis(6-t-butyl-4-methyl phenol), tert-butyl hydroquinone, di-tert-butyl hydroquinone, di-tert-amyl hydroquinone, methyl hydroquinone, p-methoxy phenol, tetrakis[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane, n-(2-aminoethyl)-3-[3,5-bis(tert-butyl)-4-hydroxyphenyl]propanamide, 5,7-di-tert-butyl-3-(3,4,-dimethylphenyl)-3h-benzofuran-2-one, dilauryl thiodipropionate, dimyristyl thiodipropionate, tris(nonylphenyl) phosphite, and the like, and mixtures thereof. the antioxidants 2,2′-methylene bis(6-t-butyl-4-methyl phenol) and n-(2-aminoethyl)-3-[3,5-bis(tert-butyl)-4-hydroxyphenyl]propanamide may be preferred for some applications, with the latter antioxidant being especially desirable because it includes a reactive amino group which may enable covalent incorporation into a suitably reactive core or shell. antioxidants may, for example, suppress, reduce, intercept, or eliminate destructive radicals or chemical species that promote the formation of destructive radicals which would otherwise lead to more rapid oxidative degradation of the encapsulated material or components thereof. exemplary sterols other than phytosterols include cholesterol, steroidal hormones such as testosterone, vitamins such as d vitamins, eicosanoids (e.g., hydroxyeicostetraones, prostacyclins, prostaglandins and thromboxanes, leukotrienes, lipoxins, resolvins, isoprostanes and jasmonates. exemplary tags include those found in algae oil, almond oil, beef tallow, butterfat, canola oil, chia oil, cocoa butter, coconut oil, cod liver oil, corn oil, cottonseed oil, flaxseed oil, grape seed oil, lard, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, and walnut oil. a variety of phytosterols may be used in the core. exemplary phytosterols include campesterol, stigasterol, β-sitosterol, δ5-avenosterol, δ7-stigasterol, δ7-avenosterol, brassicasterol or mixtures thereof. non-esterified phytosterols are preferred for use in the disclosed method, although esterified phytosterols may also be employed. the phytosterol may for example represent about 0.5 to about 96 wt. %, about 3.5 to about 96 wt. %, about 5 to about 80 wt. % or about 5 to about 60 wt. % of the encapsulated material. cores containing a combination of phytosterol and omega-3 fatty acids are especially preferred. exemplary such combinations include the formulations shown below in table 1: table 1phytosterol, mgomega-3, mgphytosterol/omega-36503220.3 (325:16)6505013.0400508.06501006.56501504.34001004.04001502.7 (8:3) for example, the table 1 formulations may be added to food products or administered as is (e.g., in one or more capsules) to provide recommended daily servings meeting u.s. food and drug administration (fda) guidelines. the core may comprise, consist of or consist essentially of oxidatively unstable material and phytosterol. the core may include additional ingredients having limited or no susceptibility to oxidation, e.g., caveolins, phospholipids, micelle stabilizers, soluble or insoluble fibers, various oils, various salts, and mixtures thereof. phospholipids and micelle stabilizers may be of particular interest. exemplary phospholipids include natural or chemically modified phospholipids, e.g., alkylphosphocholines (viz., synthesized phospholipid-like molecules), cardiolipin, dipalmitoylphosphatidylcholine, glycerophospholipid, lecithin, phosphatidic acid, phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, phosphatidylinositol, phosphatidylinositol 3-phosphate, phosphatidylinositol (3,4)-bisphosphate, phosphatidylinositol (3,5)-biphosphate, phosphatidylinositol (3,4,5)-triphosphate, phosphatidylmyo-inositol mannosides, phosphatidylserine, sphingomyelin, sphingosyl phosphatide and mixtures thereof. an exemplary commercially available phospholipid is ultralec f™ deoiled lecithin from archer daniels midland co. (decatur, ill.). exemplary micelle stabilizers (some of which are phospholipids) include cardolipin, digalactosyldiacylglycerols, monogalactosyldiacylglycerols, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol and sphingolipids and mixtures thereof. the core may be hollow or solid and desirably is solid. the core may be spherical or other than spherical (e.g., oblong) and desirably is spherical. the core desirably has a low melt viscosity, low specific heat capacity and low heat of melting. the core may for example have a melting temperature below about 50° c., below about 100° c., below about 150° c., below about 200° c. or below about 250° c. exemplary core microparticles may for example have particle diameters from about 10 nanometers to about 5,000 micrometers, about 1 micrometer to about 1,000 micrometers, or about 10 micrometers to about 500 micrometers. the core may for example represent at least about 5 wt. %, at least about 20 wt. % or at least about 30 wt. % of the encapsulated material. desirably the core is greater than 30 wt. % of the encapsulated material, e.g., at least about 40 wt. % or at least about 50 wt. %. the core may be formed using a variety of types of prilling equipment. representative such equipment includes systems from buchi corporation, gea niro and armfield ltd. industrial food technology. prilling may also be performed by modifying equipment used for other purposes. appropriate operating parameters for prilling ordinarily will be established empirically, and may vary depending on factors such as the desired core material, desired throughput, ambient conditions and chosen prilling equipment. a variety of microencapsulating materials may be used in the disclosed encapsulated materials to form protective shell layer(s), sometimes also referred to as coatings or membranes, surrounding the core(s), or as additives in a protective shell layer. exemplary such materials provide a barrier to one or more of oxygen, water, light or other oxidation promoters, and include dryable materials and prillable materials. the microencapsulating materials may comprise, consist of or consist essentially of natural, semisynthetic (viz., chemically modified natural materials) or synthetic materials. exemplary natural materials include gum arabic, agar agar, agarose, maltodextrins, alginic acid and salts thereof including sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides including starch or dextran, polypeptides, protein hydrolyzates, sucrose and waxes. oleosins as described in copending pct application no. pct/us2009/030052 or phospholipids as described in copending pct application no. pct/us09/30054 may be employed in the protective shell layer. exemplary semisynthetic materials include chemically modified celluloses including cellulose esters and ethers (for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose) and chemically modified starches including starch ethers and esters (for example, capsul™ modified starch from national starch). exemplary synthetic materials include polymers (for example, polyacrylates, polyamides, polyvinyl alcohol, polyvinyl pyrrolidone, polyureas and polyurethanes). exemplary commercial microcapsule products (the shell materials for which are shown in parentheses) include hallcrest microcapsules (gelatin, gum arabic), coletica thalaspheres™ (maritime collagen), lipotec millicapseln™ (alginic acid, agar agar), induchem unispheres™ (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), unicerin c30 (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), kobo glycospheres™ (modified starch, fatty acid esters), softspheres™ (modified agar agar) and kuhs probiol nanospheres™. preferred dryable microencapsulating materials include gelatin, agar-agar, alginates, pectin, starch, carbohydrates and mixtures thereof. preferred prillable microencapsulating materials include low melting waxes such as triglyceride waxes and mixtures thereof, e.g., bees wax, canola wax, carnauba wax, candelilla wax, castor wax, stearic acid, and commercially available triglyceride waxes including astor™ and a-c™ waxes from honeywell international inc., be square™ waxes from baker petrolite, dritex™-c and dritex-s waxes from ach food companies, inc. and dynasan™ waxes from dynamit nobel, inc. the protective shell layer may for example represent about 2 to about 90 wt. %, about 3.5 to about 90 wt. %, about 10 to about 80 wt. % or about 30 to about 60 wt. % of the encapsulated material. the protective shell layer may be in direct contact with a surface of the core, or may be in direct contact with an intermediate layer located between a surface of the core and the protective shell layer. the latter configuration may however have a reduced core content or core loading for a given particle size. the protective shell layer may be covered by one or more additional layers. if the encapsulated material is not required to be ingestible, then the outer and if desired inner layers may be ingestible or not as desired, whereas for ingestible encapsulated materials at least the outermost layer is ingestible. exemplary outer layers include a water-dispersible oxygen-barrier layer, hydrocolloid layer, lipophilic layer or any combination thereof. for example, a hydrocolloid or hc layer made using a natural or chemically-modified hydrocolloid material, e.g., an alginate, may facilitate upper gastrointestinal (ugi) tract bypass when the disclosed encapsulated materials are orally administered to mammalian subjects. further details regarding exemplary hc layers may be found in the above-mentioned pct application nos. pct/us2009/030052 and pct/us09/30054. a particularly useful layer, especially over the protective shell layer, is a fiber/carbohydrate/protein or fpc layer made using a fiber-, carbohydrate or protein-containing film-forming material. exemplary fpc layers may be formed from at least one of dietary fiber (e.g., food grade fiber), a simple carbohydrate (e.g., a monosaccharide or disaccharide such as a sugar), or a protein. further details regarding exemplary fpc layers may be found in the above-mentioned pct application nos. pct/us2009/030052 and pct/us09/30054. the various layer ingredients discussed above may arrange themselves into separate layers around the cores (for example due to reasons such as stereochemistry, surface energy, oleophilicity, oleophobicity, hydrophilicity or hydrophobicity). the layer ingredients may in some embodiments form a matrix of ingredients in a single shell layer surrounding the cores. in some embodiments the protective shell layer or other layers may contain one or more antioxidants. exemplary antioxidants include those discussed above in connection with the core. some antioxidants may be used as core stabilizers and as shell stabilizers. the disclosed encapsulated materials may contain a variety of other adjuvants, including chelating agents, surfactants, uv absorbers and other ingredients or additives that will be familiar to persons having ordinary skill in the microencapsulation art. further details regarding exemplary adjuvants may be found in the above-mentioned pct application nos. pct/us2009/030052 and pct/us09/30054. the disclosed encapsulated materials may also include absorbents, dehydrators, flow aids and other agents that may assist in pouring, storing or dispensing the encapsulated materials or in mixing them with other materials. the agent may in some embodiments form a coating over an outer layer, in effect representing an additional shell, and may in other embodiments be an additive included in an outer layer. the agent may change the surface energy of the encapsulated material, absorb excess oil, or serve other functions. further details regarding exemplary agents may be found in the above-mentioned pct application nos. pct/us2009/030052 and pct/us09/30054. the adjuvant or agent may for example represent about 0.1 to about 5 wt. % of the encapsulated material. a variety of exemplary structures and methods may be used to form the disclosed encapsulated materials. if made using a dryable microencapsulating material, the protective shell layer may for example contain less than 8%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2% or less than 1% of available water. the desired dryness level may be reached by removing water (e.g., if the protective shell layer is formed using an aqueous carrier or solvent) or by adding water (e.g., if the protective shell layer is formed using an organic carrier or solvent) after or during formation of the disclosed encapsulated material. in one exemplary embodiment the prilled cores are formed and then dispersed into an emulsion whose continuous phase contains ingredients capable of forming one and optionally several layers surrounding the core microparticles. the emulsion may be processed (e.g., spray dried) to convert the emulsion into microcapsules having at least one dried protective layer surrounding the cores. in another exemplary embodiment the prilled cores are formed and then coated with gelatin using any of a variety of methods including spray drying, incipient wetness, or coating in a wurstlr™ air suspension coater (from glatt gmbh). for example, gelatin could be added to water heated at or near boiling to dissolve the gelatin, then cooled to near ambient temperature. the prilled cores could be suspended in the gelatin/water mixture, and the mixture could be spray dried to form the disclosed free-flowing microparticles. if made using a prillable microencapsulating material, the microencapsulating material may for example be in fluid form at an elevated temperature (e.g., at above 30° c.) and in solid form when cooled to a lower temperature. the microencapsulating material desirably has a lower melting point (e.g., a melting point at least 2° c., at least 5° c., at least 10° c., or at least 20° c. lower) than that of the prilled core. this will facilitate dispersing the cores into a molten sample of the microencapsulating material and reprilling to provide the disclosed microparticles. in one embodiment the prilled cores are suspended in a low melting wax such as stearic acid, and then re-prilled to form the disclosed free-flowing microparticles. in another exemplary embodiment the prilled cores are dry-blended with a micronized low melting wax such as micronized stearic acid and brief heat or high shear forces are applied to melt the wax onto the cores. the various applied layers may be reacted with a variety of materials to alter some or all of the layer characteristics. this may be carried out using a variety of reaction schemes, materials and other measures. for example, a maillard reaction between proteins and reducing sugars may be used to alter a layer containing protein or a layer containing a reducing sugar by exposing such layers to reducing sugar or protein, respectively, in the presence of sufficient heat to promote a browning reaction. hydrocolloid (e.g., alginate layers) may be crosslinked, e.g., by inclusion of a suitable calcium salt source in the hydrocolloid layer, in an adjacent layer or in the core. an exemplary encapsulated material may for example be made using an oxidatively unstable material (e.g., a tag or pufa) to which has been added a phytosterol and optionally an antioxidant (e.g., tocopherol, lycopene or tocotrienols), chelating agents, or dispersed calcium carbonate or calcium sulfate. the core may be formed by heating the core ingredients to an appropriate temperature above their melting point, for example to about 70-80° c., then atomizing the mixture in a grilling apparatus and rapidly congealing the resulting droplets in a chilled gas stream (e.g., chilled air or liquid nitrogen) to form prilled beads. the beads may be coated with a protective shell layer which may be made from a variety of materials and formed using a variety of techniques. the formation of a protective shell layer may be repeated several (e.g., one to four) times. hc shell (hcs) layers may be formed, for example from an aqueous sodium alginate hydrocolloid solution to which a variety of other materials may also be added. fcps layers may be formed, for example by adding fibers such as insoluble fiber or carboxymethyl cellulose (cmc) fibers and optional additives to a solution containing water-soluble antioxidants and reducible sugars. the resulting mixture may be formed into encapsulated materials, e.g., by adding the prilled cores to the solution and spray drying to form fcp-coated microparticles. in a preferred process the resulting spray dried product is added to a melt for prilling or otherwise converted in order to form an outer lipophilic shell or lps over an fcp-coated core. separation of microcapsules by centrifugation or filtration and drying to a dry state may also or instead be used to form various layers. using these various general processes for manufacture, a variety of different materials, layers and constructions can be used to provide a variety of encapsulated materials. set out below in table 2 are several non-limiting exemplary structural components, ingredients and functions for use in such processes. the terms “ai” and “ao” in table 2 respectively refer to an “active ingredient” and an “antioxidant”, functions which in some cases may be performed by the same material. typically an ai or ao will be carried and protected by the core, protective shell, hcs, fcps or other layer until such time as the ai or ao may be delivered to an intended host or site for a subsequent designed use. other abbreviations are identified in the footnotes to table 2. to simplify the table appearance, the first row for each new structural component (e.g., core, protective shell, etc.) includes the structural component label, and subsequent rows showing other materials for use in or as such structural component do not explicitly show the structural component label but are deemed to have been so labeled. table 2structuralcomponentingredientfunctioncorepufa 1ai 2vegetable oilai or ao 3lycopeneai or aoluteinai or aotocopherolai or aophytosterolai, organogellation agent or aobht 4ai or aocalcium compoundcrosslinking agent for hcs 5citric acidmetal chelating agent forprooxidants or aiedta 6 saltmetal chelating agent forprooxidantsphytosterolai, oxygen barrier or aophospholipidphospholipidliposome shell, core stabilizershelland aophytosterolliposome shell stabilizer or aooleosinliposome shell stabilizerhydrocolloidalginateshell matrix, ugi 7 bypass andshelloxygen barriercmc 8shell, oxygen barrierinsoluble fibershell, oxygen barrierhpmc 9shell, oxygen barrieranthocyaninaobhtaoluteinaolycopeneaotocopherolaocarbohydrateaidextrosereducible sugar for maillardreaction and carbohydratefructosereducible sugar for maillardreaction and carbohydratelactosereducible sugar for maillardreaction and carbohydratesucrosenonreducible sugar andcarbohydratetrehalosenonreducible sugar andcarbohydratecaseinprotein for maillard reactionwpc 10protein for maillard reactionphytosterolai, oxygen barrier or aofiber/pectinsoluble fiber for ugi bypasscarbohydrate/protein shellinsoluble fiberoxygen barrieralginatematrix, soluble fiber, oxygenbarrierstarchmatrix, soluble fiber, oxygenbarrierdextrosereducible sugar for maillardreaction and carbohydratefructosereducible sugar for maillardreaction and carbohydratelactosereducible sugar for maillardreaction and carbohydratesucrosenonreducible sugar andcarbohydratetrehalosenonreducible sugar andcarbohydratecaseinprotein for maillard reactiongelatinmatrix protein for maillardreaction, oxygen barrierwpcprotein for maillard reactionwheyreducible sugar and proteinfor maillard reactionlycopeneaoluteinaotocopherolaobhtaophytosterolai, oxygen barrier or aolipophilichydrogenated oiloxygen barrier, aoshellphytosterolai, oxygen barrier or ao1 pufa is polyunsaturated fatty acid.2 ai is active ingredient.3 ao is antioxidant.4 bht is 2,6-di-t-butyl cresol.5 hcs is hydrocolloid shell.6 edta is ethylenediaminetetraacetic acid.7 ugi is upper gastrointestinal tract.8 cmc is carboxymethylcellulose.9 hpmc is hydroxypropylmethylcellulose.10 wpc is whey protein concentrate. for encapsulated materials having a core surrounded by a single protective shell layer, the core:shell weight ratio may for example range from about 20:1 to about 1:20, about 10:1 to about 1:10, about 8:1 to about 1:1, or about 2:1 to about 2:3. for encapsulated materials having a core surrounded by four shell layers (e.g., a core having protective shell, hcs, fcps and lps layers), the core may for example represent about 5 to about 70, about 5 to about 60 or about 10 to about 40 wt. % of the total encapsulated material weight. set out below in table 3 are exemplary constructions showing core and layer amounts (expressed in parts by weight) for a variety of encapsulated materials containing protective shell-coated cores, and additional layers each of which may also serve as a protective layer, together with the approximate core weight percent. table 3layer\exampleabcdefcore808080808080protective shell202020201520alginate shell202020202020fiber/carbohydrate/120804012020120protein shelllipophilic shell240240240001400percent core16%18%20%33%60%5% the data in table 3 show encapsulated materials with four shell layers containing about 5-60 wt. % core content. by varying the presence or absence of the various layers and their ingredients and relative amounts, encapsulated materials having a variety of properties can be formed. for example, if the lipophilic shell is eliminated and a fiber/carbohydrate/protein shell containing mainly a soluble fiber such as pectin or alginate is employed, a taste-masked encapsulated material with ugi bypass characteristics may be prepared. if a phytosterol-containing lipophilic shell is employed, a high temperature encapsulated material with an ao shell may be prepared for use in baked products and baking applications. encapsulated materials whose cores or lipophilic shells contain organogels, and encapsulated materials with lipophilic shells containing hydrogenated oils crystallized in the beta form, may provide oxygen barrier or zero order (viz., concentration-independent) release characteristics. oxidative stability may be evaluated using a variety of tests. simple but sensitive subjective tests such as olfactory tests or taste tests will suffice for many applications. for example, a subjective taste profile measurement may be performed using a panel of at least five people and the following six point scale: 0=no difference1=very slight difference2=slight difference3=moderate difference4=large difference5=extreme difference the panel members may be asked to sample unaged or aged (e.g., for one, three, six or twelve months) food products containing the disclosed encapsulated materials, and to compare their tastes using the six point scale. an aged food product having a 0 or 1 rating may be regarded as having a minimal off taste profile. a variety of objective tests may also be employed, including accelerated oxidative stress tests such as solid phase micro extraction (spme) at an elevated temperature, e.g., 50° c. in an oxidizing atmosphere such as pure oxygen. aging at 50° c. in pure oxygen represents a fairly severe test regime, and materials which provide low spme values (or little change in the spme value compared to the initial spme value) when so aged may provide very good protection under less stringent (e.g., room temperature) storage conditions. an spme measurement is shown for example in the above-mentioned pct application nos. pct/us2009/030052 and pct/us09/30054. the spme value after 48 hours at 50° c. in pure oxygen may for example be less than 8,000, less than 5,000 or less than 4,000. the ratio of spme after 48 hours at 50° c. to initial spme may also be evaluated, and may for example be less than 8, less than 4, less than 2, less than 1.7 or less than 1.3. the disclosed encapsulated materials may be used in a variety of products and applications including foods for human or animal consumption, e.g., beverages (for example dairy products including milk and yoghurt, and juice drinks including dry juice mixes), mixes (for example, baking mixes), prepared foods (for example, baked, frozen or precooked foods), food additives, food supplements, condiments (for example, barbecue sauce, mayonnaise, mustard or salad dressing), dietary supplements (for example, for use in weight maintenance or in nursing home care), nutritional snacks, nutritional supplements, neutraceuticals, medicines (for example, for maintaining heart health in humans and animals), and for non-food uses including catalysts, inks and coatings. the invention is further described in the following examples, in which all parts and percentages are by weight unless otherwise indicated. examples example 1 solubility evaluations the solubility of arboris™ as-2 phytosterol (from arboris, llc) in soybean cooking oil was evaluated by heating the oil to 150° c., fully dissolving a graded series of phytosterol concentrations (from 1 to 5 wt. %, in steps of 0.5 wt. %) in the heated oil, cooling the samples to room temperature and waiting 24 hours for any supersaturating phytosterol to crystallize. the phytosterol appeared soluble in room temperature cooking oil up to at least a concentration of 1.5 wt. %, and exhibited precipitates at concentrations at or above 2.0 wt. %. the results are set out below in table 4: table 4runas-2as-2oilno.(wt. %)(g)(g)observations after coolingctrl.0.00.0005.00control-no apparent change10.50.0254.98no apparent change21.00.0504.95no apparent change32.00.1004.90no apparent change43.00.1504.85long needle-like crystals, slight increase in viscosity54.00.2004.80cloudy-flocculent, increased viscosity65.00.2504.75same as above with slight increase in viscosity710.00.5004.50two phases: crust at surface, viscous oil below820.01.0004.00same as above with slight increase in oil viscosity940.02.0003.00solid wax-like but easily defotmed1060.03.0002.00solid, harder than above1180.04.0001.00solid, very hard1290.04.5000.50solid, very hard similar results were obtained when the phytosterol was added to eterna™ omega-3 fish oil (from hormel) containing 2000 ppm tocopherol. the phytosterol appeared soluble in room temperature fish oil up to at least a concentration of 1.5 wt. %, and exhibited precipitates at concentrations at or above 2.0 wt. %. above 10 wt. % phytosterols, the mixture was relatively solid in appearance. in a further set of runs, cardioaid™ phytosterols (from archer daniels midland) were added at eight different concentrations to heated omega-3 oil. for each run, a 5.0 g sample of the omega-3 oil was placed in a small aluminum weighing dish and heated at the lowest setting on a hot plate. the phytosterols were added to the hot oil and allowed to dissolve fully until there was no evidence of clouding or other insolubility. the samples were removed from the hot plate, allowed to cool to room temperature and observed about 18 hours later. the results are shown below in table 5: table 5runcardioaidcardioaidobservations ~18 hoursno.(g)(wt. %)after coolingctrl.0.000.00no apparent change in oil10.203.85cloudy20.509.09very soft gel, easily drips30.7513.04gel41.0016.67flowable paste51.2520.00soft paste, slight flow61.5023.08paste, moderately stiff70.050.99solid granules apparent,little effect on viscosity80.101.96grainy, increase in viscosity the phytosterol appeared soluble in room temperature fish oil up to at least a concentration of 1.5 wt. %, and exhibited precipitates at concentrations at or above 2.0 wt. %. above 9 wt. % phytosterols, the mixture was relatively solid in appearance, and above 23 wt. % phytosterols a paste was formed. example 2 prill formation three different core formulations were prepared using the ingredients shown below in table 6: table 6arboriseternaas-2formulationomega-3 oilphytosterolno.(wt. %)(wt. %)17723245.554.5329.570.5 stainless steel vessels on hotplates were used to melt 1 kg of each formulation. the oil was added to each vessel and the vessels were flushed with nitrogen and covered, then heated to about 150° c. the phytosterol was added slowly with stirring by hand, and each addition was allowed to melt fully before proceeding. the vessels were again flushed with nitrogen and covered before storing in a 150° c. oven. prilling was completed within three hours of melting, by atomizing the formulations in a niro™ mobil minor™ spray drier (from gea niro) modified to supply liquid nitrogen to the drying chamber at a rate sufficient to maintain the exhaust temperature below about −20° c. the molten core formulations were passed through a spray nozzle into the focal point of the cool nitrogen causing rapid congealing and solidification of the spray into prilled core particles. after collection, each sample was immediately placed in a −20° c. freezer. the respective prill yields for formulations 1 through 3 were 449 g (44.9%), 728 g (72.8%) and 778 g (77.8%). the samples were analyzed using differential scanning calorimetry (dsc) to determine their melting point. the formulation 1 through 3 prills had respective melting point values of 119.91, 122.76 and 127.11° c. the formulation 2 and 3 prills were analyzed using a horiba™ la-930 particle size analyzer (from horiba instruments, inc.) to determine particle size distribution (psd) data, and found to have respective average particle diameters of 77.18 μm and 68 μm. the formulation 1 prill formed an agglomerated mass that was not subjected to psd analysis. example 3 gelatin-coated omega-3/phytosterol prill using 1 kg of the formulation 3 prilled cores, a gelatin protective layer could be applied as follows. a 20 g portion of 75 bloom gelatin may be added to 600 g of 80° c. deionized (di) water and allowed to hydrate fully. a water bath may be used to cool the gelatin solution to 40° c. using a wurster suspension coater equipped with a gaseous nitrogen drying feed, the prilled cores may be added to the solids fluidizer using a 340 l/min flow rate and the gelatin solution may be added to the liquids fluidizer using a 0.24 mpa atomization pressure and 65° c. coating temperature. free-flowing microparticles may be formed by removal of water from the gelatin-coated omega-3/phytosterol microparticles. after collection, the microparticles may be placed in a −20° c. freezer for storage. the microparticles should contain about 69.1 wt. % phytosterol, 28.9 wt. % omega-3 oil and 2 wt. % gelatin. example 4 carnauba wax-coated omega-3/phytosterol prill using 1 kg of the formulation 2 prilled cores, a carnauba wax protective layer could be applied as follows. a 200 g portion of carnauba wax (melting point 82-86° c.) may be melted in a stainless steel vessel on a hotplate. the vessel may be flushed with nitrogen and covered prior to an initial heating to about 90° c. the formulation 2 prilled cores may be stirred into the melted carnauba wax. re-prilling may be carried out using a modified niro mobil minor™ spray drier like that employed in example 2 to form carnauba wax-coated omega-3/phytosterol microparticles. after collection, the microparticles may be placed in a −20° c. freezer for storage. the microparticles should contain about 45.4 wt. % phytosterol, 37.9 wt. % omega-3 oil and 16.7 wt. % carnauba wax. example 5 stearic acid-coated omega-3/phytosterol prill using 1 kg of the formulation 2 prilled cores, a stearic acid protective layer could be applied as follows. a 50 g portion of stearic acid (melting point 70° c.) could be dry-blended with the formulation 2 prilled cores for 5 minutes under high shear conditions in a waring™ blender (from waring products, inc.). the dry blending process should impart sufficient heat to the stearic acid and prilled cores to form stearic acid-coated omega-3/phytosterol microparticles. after collection, the microparticles may be placed in a −20° c. freezer for storage. the microparticles should contain about 51.9 wt. % phytosterol, 43.3 wt. % omega-3 oil and 4.8 wt. % stearic acid. example 6 stearic acid-coated omega-3/phytosterol prill using 1 kg of the formulation 1 prilled cores and a procedure similar to that shown in example 5, a stearic acid protective layer could be applied as follows. a 100 g portion of stearic acid (melting point 70° c.) could be dry-blended with the formulation 1 prilled cores in a waring™ blender for 5 minutes as in example 5. the resulting stearic acid-coated omega-3/phytosterol microparticles may then be passed quickly through a hot air zone of at least 90° c. to ensure that the stearic acid surface forms an even coating on the omega-3/phytosterol prilled cores. after collection, the microparticles may be placed in a −20° c. freezer for storage. the microparticles should contain about 20.9 wt. % phytosterol, 70 wt. % omega-3 oil and 9.1 wt. % stearic acid. the encapsulated materials in examples 3 through 6 would contain the ingredient amounts shown below in table 7: table 7oxidizable oil,phytosterol,protective shell,examplewt. %wt. %wt. %328.9%69.1%2.0% gelatin437.9%45.4%16.7% carnauba wax543.3%51.9%4.8% stearic acid670.0%20.9%9.1% stearic acid the disclosed invention involves a number of embodiments, including: 1. a method for protecting an oxidatively unstable material, which method comprises congealing droplets of a molten blend of oxidatively unstable material and phytosterol in a chilling gas stream to prilled cores comprising oxidatively unstable material and phytosterol, and encapsulating the prilled cores in one or more protective shell layers to form free-flowing microparticles. 2. the method of embodiment 1 wherein the oxidatively unstable material comprises a polyunsaturated fatty acid. 3. the method of embodiment 2 wherein the polyunsaturated fatty acid comprises an omega-3 or omega-6 fatty acid. 4. the method of embodiment 1 wherein the oxidatively unstable material comprises a triacylglycerol. 5. the method of embodiment 1 wherein the oxidatively unstable material comprises an antioxidant. 6. the method of embodiment 1 wherein the oxidatively unstable material comprises an acidulant, animal product, carotenoid, catalyst, drug, dye, enzyme, flavor, fragrance, lutein, lycopene, metal complex, natural color, nutraceutical, pigment, polyphenolic, processed plant material, metabiotic, probiotic, protein, squalene, tocopherol, tocotrienol, vitamin, unsaturated organic compound, or mixture thereof. 7. the method of embodiment 1 wherein the oxidatively unstable material is a solid at room temperature. 8. the method of embodiment 1 wherein the oxidatively unstable material is a gel at room temperature. 9. the method of embodiment 1 wherein the oxidatively unstable material is a liquid at room temperature. 10. the method of embodiment 1 comprising drying a protective shell layer. 11. the method of embodiment 1 comprising prilling a protective shell layer. 12. the method of embodiment 1 comprising forming a protective shell layer from gelatin. 13. the method of embodiment 1 comprising forming a protective shell layer from a triglyceride wax. 14. the method of embodiment 1 comprising forming a protective shell layer from stearic acid. 15. the method of embodiment 1 comprising forming a protective shell layer comprising insoluble or soluble fiber. 16. the method of embodiment 1 comprising forming a protective shell layer from a water-dispersible oxygen barrier layer, a hydrocolloid layer or a lipophilic layer. 17. the method of embodiment 1 wherein the encapsulated oxidatively unstable material has enhanced protection from oxidation compared to the oxidatively unstable material by itself. 18. the method of embodiment 1 further comprising combining the microparticles with a food to provide a food product. 19. the method of embodiment 18 wherein the food product when aged for three months has a minimal off taste profile. 20. the method of embodiment 18 wherein the food product is minimally processed. 21. an encapsulated material comprising free-flowing microparticles containing a prilled core comprising a congealed blend of oxidatively unstable material and phytosterol, covered by at least one protective shell layer. 22. the encapsulated material of embodiment 21 wherein the core comprises a polyunsaturated fatty acid. 23. the encapsulated material of embodiment 22 wherein the polyunsaturated fatty acid comprises an omega-3 or omega-6 fatty acid. 24. the encapsulated material of embodiment 23 wherein the core contains omega-3 fatty acid and phytosterol in a weight ratio of about 325:16 to about 8:3. 25. the encapsulated material of embodiment 21 wherein the core comprises a triacylglycerol. 26. the encapsulated material of embodiment 21 wherein the core comprises an antioxidant. 27. the encapsulated material of embodiment 26 wherein the antioxidant comprises vitamin a, d, e, k or mixture thereof. 28. the encapsulated material of embodiment 26 wherein the antioxidant comprises ubiquinol, ubiquione or mixture thereof. 29. the encapsulated material of embodiment 21 wherein the core comprises an acidulant, animal product, carotenoid, catalyst, drug, dye, enzyme, flavor, fragrance, lutein, lycopene, metal complex, natural color, nutraceutical, pigment, polyphenolic, processed plant material, metabiotic, probiotic, protein, squalene, tocopherol, tocotrienol, vitamin, unsaturated organic compound, or mixture thereof. 30. the encapsulated material of embodiment 21 wherein the core is greater than 30 wt. % of the encapsulated material. 31. the encapsulated material of embodiment 21 wherein the oxidatively unstable material is a solid at room temperature. 32. the encapsulated material of embodiment 21 wherein the oxidatively unstable material is a gel at room temperature. 33. the encapsulated material of embodiment 21 wherein the oxidatively unstable material is a liquid at room temperature. 34. the encapsulated material of embodiment 21 wherein a protective shell layer comprises gelatin. 35. the encapsulated material of embodiment 21 wherein a protective shell layer comprises triglyceride wax. 36. the encapsulated material of embodiment 21 wherein a protective shell layer comprises stearic acid. 37. the encapsulated material of embodiment 11 wherein a protective shell layer comprises insoluble or soluble fiber. 38. the encapsulated material of embodiment 21 wherein a protective shell layer comprises a water-dispersible oxygen barrier layer, a hydrocolloid layer or a lipophilic layer. 39. the encapsulated material of embodiment 21 wherein the oxidatively unstable material has enhanced protection from oxidation compared to the oxidatively unstable material by itself. 40. a food product comprising the encapsulated material of embodiment 21. 41. the food product of embodiment 40 wherein the food product when aged for three months has a minimal off taste profile. 42. the food product of embodiment 40 wherein the food product is minimally processed. 43. the food product of embodiment 40 wherein the food is a baked food product. 44. the food product of embodiment 40 wherein the food is a nutritional snack. 45. the food product of embodiment 40 wherein the food is a dietary supplement. although specific examples, compositions, ingredients, temperatures and proportions have been disclosed in various aspects of the present invention, those disclosures are intended to be exemplary of species within a generic invention.
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059-412-443-385-598
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US
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[
"US"
] |
E01C11/00,E01C23/06,E01C23/088
| 1977-02-04T00:00:00 |
1977
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[
"E01"
] |
method for resurfacing a paved roadway
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a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope, particularly wherein the existing paved roadway has at least one irregular depression therein extending below the predetermined grade and wherein the portion of the roadway above the predetermined grade is removed in particulate form for use as a recyclable aggregate in resurfacing the roadway.
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1. a method for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope, wherein the existing paved roadway has at least one irregular depression therein extending below the predetermined grade, the method comprising the stpes of: removing the material of the paved roadway within a predetermined distance of the depression to a predetermined depth below the bottom of the depression; applying a substantially uniform layer of new pavement material within the depression, the layer having an upper surface above the predetermined grade and a density substantially the same as the density of the existing pavement material surrounding the depression; and, passing a rotating planing cutter over the paved roadway at the predetermined grade and cross slope to remove the material of the paved roadway above the predetermined grade and cross slope. 2. a method for resurfacing an existing paved roadway of the asphalt type to produce a new roadway surface, the method comprising the steps of: passing a rotating planing cutter over the paved roadway to cut the top portion of the paved roadway to a predetermined grade and cross slope in a full offset pattern having laterally adjacent cutting paths longitudinally offset on the order of one full length of each path; and, passing a fixed moldboard over the paved roadway at the predetermined cross slope and at a second predetermined grade slightly above the predetermined grade to remove the material of the paved roadway above the second predetermindd grade and the predetermined cross slope.
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background of the invention 1. field of the invention the present invention relates generally to roadway construction apparatus, and more particularly, but not by way of limitation, to a method and apparatus for resurfacing an existing paved roadway, particularly wherein the existing paved roadway has at least one irregular depression therein extending below a predetermined grade. 2. description of the prior art a very detailed examination of the state of the art of planers used to resurface existing paved roadways has been made of record in the related u.s. patent application ser. no. 672,326, filed mar. 31, 1976 and entitled "a method and apparatus for planing a paved roadway", and is therefore incorporated herein by reference to preclude reiteration of this lengthy discussion. in addition, however, it has been proposed in u.s. pat. no. 3,843,274, issued to gutman et al., to provide a vehicle having means for heating the upper layer of asphalt of an existing paved roadway, a rotating cutter for lifting the heated asphalt, a pugmill for pulverizing the lifted asphalt, a spreader for spreading the pulverized asphalt, and a leveler for leveling the distributed asphalt. however, such a vehicle is totally inapplicable to existing concrete roadways. further, the method and apparatus is ineffecient at best, and often totally ineffective, in a wide variety of commonly occuring environments due to inherent humidity and temperature limitations. since it is certainly not uncommon to find irregular depressions or "pot holes" in existing paved roadways, it would not be unreasonable to assume that an existing paved roadway to be resurfaced to provide a new roadway surface having a predetermined grade and cross slope would have at least one irregular depression therein extending below the predetermined grade. prior to the present invention, the most common mode of "repairing" such a depression would be to fill the depression with a quantity of hot mix asphalt and compact the asphalt either by hand or using compacting rolling machines or the like. however, it has been demonstrated that these "repaired" depressions deteriorate far more rapidly than the surrounding existing paved roadway primarily due to the inability of the current technique to compact the new asphalt material to substantially the same density as the surrounding pavement and also a general inability to induce satisfactory bonding between the new asphalt material and the existing pavement. summary of the invention the present invention provides a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope, particularly wherein the existing paved roadway has at least one irregular depression therein extending below the predetermined grade, and wherein the portion of the roadway above the predetermined grade is removed in particulate form for use as a recyclable aggregate in the production of new paving material for reapplication to the roadway. it is a primary object of the present invention to provide a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope. another object of the present invention is to provide a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope, particularly wherein the existing paved roadway has at least one irregular depression therein extending below the predetermined grade. yet another object of the present invention is to provide a method for repairing irregular depressions in existing paved roadways, particularly wherein the irregular depression extends below a predetermined grade to be provided during the course of resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope. stil another object of the present invention is to provide a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope in a manner that permits year-round operation, independent of most weather considerations. another object of the present invention is to provide a method and apparatus for resurfacing an existing paved roadway wherein a portion of the roadway lying above a predetermined grade and cross slope is removed in particulate form suitable for reuse as a recyclable aggregate in the production of new paving material. it is a further object of the present invention to provide a method and apparatus for resurfacing an existing paved roadway to produce a new roadway surface having a predetermined grade and cross slope in a manner which is highly efficient and very effective in operation. other objects and advantages of the invention will be evident from the following detailed description when read in conjunction with the accompanying drawings which illustrate various embodiments of the invention. brief description of the drawings fig. 1 is a diagrammatical representation of a cross section of a typical paved roadway that has been resurfaced. fig. 2 is a side elevational view of a planar type road construction apparatus. fig. 3 is a top plan view of the planar apparatus shown in fig. 2. fig. 4 is a block diagram depiction of the steering, elevation and cross slope control mechanisms of the planar apparatus of fig. 2. fig. 5 is a front elevational view in partial detail of the planing cutter of the planer apparatus of fig. 2. fig. 6 is a view of the planer cutter taken at 6--6 in fig. 5. fig. 7 is a view of one of the cutting heads used on the planing cutter shown in fig. 5. fig. 8 is a side elevational view showing the hood and one of the end shield members. fig. 9 is a side elevational view in partial cutaway depiction of the floating moldboard of the planer apparatus shown in fig. 2. fig. 10 is a partial plan view showing the attachment of the base elevator to the floating moldboard in the planer apparatus of fig. 2. fig. 11 is a side elevational view of a planer apparatus of the type shown in fig. 2 and having a sweeper assembly attached thereto. fig. 12 is a diagrammatical representation of a cross section of a typical paved roadway illustrating the method of the present invention for repairing irregular depressions. fig. 13 is a top plan view of paved roadway sections illustrating typical patterns formed therein in the resurfacing thereof according to the present invention. fig. 14 is a longitudinal cross sectional view of the paved roadway sections shown in fig. 13 taken along the line 14--14. fig. 15 is a partial, transverse cross sectional view of one of the paved roadway sections shown in fig. 13 taken along the line 15--15. fig. 16 is a side view of a cutting head particularly suitable for use with the present invention for resurfacing asphalt roadways. fig. 17 is a transverse cross sectional view of the cutting head shown in fig. 16 taken along the line 17--17. fig. 18 is a side elevational view of a planer apparatus constructed in accordance with the preferred embodiment of the present invention. description of figs. 1 through 11 since a detailed description of figs. 1 through 11 is contained in the copending u.s. patent application no. 672,326, filed mar. 31, 1976, now u.s. pat. no. 4,139,318 entitled "a method and apparatus for planing a paved roadway", only such discussion as is necessary to support the present invention will be included herein. referring to fig. 1, shown therein is a diagrammatical representation of a cross section of a typical paved roadway 10 that has been resurfaced. the paved roadway 10 has an original base layer of bituminous asphalt 12 that developed through traffic usage, a very rough top surface 14 that has highs and lows therein, a peak 16 and a valley 18 being typical. a typical repair of the paved roadway 10 depicted in fig. 1 would be to overlay the base layer 12 with a bituminous layer 20, a technique that is well known and practiced widely throughout the road construction industry. the layer 20 (also referred to herein as the old technique layer) would normally be compacted with a bituminous paving roller to obtain a smooth upper surface 22. of course, it will be appreciated that the layer 20 must have sufficient thickness 24 over the peak 16 to give a strong resurfacing job, and further, that the layer 20 must have a thickness at the valley 18 to give the smooth upper surface 22. it is well known that the wear of a bituminous layer will be greatly influenced by the uniformity of its substrate. that is, a bituminous layer that is laid over a uniformly even substrate surface will hold up very well in traffic usage. one of the reasons for this is that the layer is capable of receiving uniform compaction in the final rolling operation commonly practiced in the roadbuilding art. on the other hand, when a bituminous layer is laid over a surface like the one depicted by the top surface 14 in fig. 1, experience has shown that the amount of compaction achieved is not uniform, and that less compaction will occur over the valley 18 than over the peak 16. as the new layer 20 is subjected to traffic, it wll be further compacted by the traffic and the smooth upper surface 22 will be shifted and redistributed. as wear forces continue, the roadway once again will come into a state of disrepair. the present invention contemplates the use of precision planing wherein a portion of the base layer 12 will be removed prior to the resurfacing of a paved roadway. thus, the present invention teaches a method and apparatus for selectively removing material from the roadway down to a new roadway surface 28 as indicated by the dashed line. it should be noted that the new roadway surface 28 is shown in a location just below the valley 18, which is a plane of recession selected so as to have some material removed at all points of the old top surface 14. while this is not essential, it is desirable as a more uniformly even new roadway surface is thereby obtained. once the new roadway surface 28 has been created by planing the old top surface 14, a uniform layer 29 of bituminous material can be laid to a level indicated by a broken line 30 having a thickness 32 that may be the same as, or less than, the thickness 24 that was needed over the peak 16 by the old paving technique. it is obvious that far less bituminous material will be necessary for the layer 29 (also referred to as the new technique layer) as compared to the amount of material for the old technique layer 20 for the reason that it is no longer necessary to fill the valley 18 in order to cover the peak 16. in fact, the new technique layer 29 can be made significantly thinner than the minimum thickness required of the old technique layer 20. the reason for this is that the thickness 24 of the old technique layer 20 must be adequate to withstand lateral tearing forces incurred with the shifting of the material in the layer 20 during traffic wearing as mentioned above. since lateral movement is less of a consideration in the new technique layer 29 laid over the uniform new roadway surface 28, the thickness 32 can be reduced to between approximately 1/3 to approximately 1/2 of previously used resurfacing layer, with the actual thickness used being dependent upon the traffic requirements of a particular location. an added benefit of a precision planing operation prior to resurfacing is the lack of buildup of the paved roadway that occurs in the old method of adding successive resurfacing layers. this buildup has become so great in many areas that the pavement has overrun the original curbing, gutters and manhold skirts, leading to the necessity in many such cases of having to extend these items to reach the increased pavement elevation. in the practice of the present invention, this buildup is avoided as the surface of the new layer can be maintained with a grade and cross slope approximately equal to that of the original pavement, and this can be achieved for each subsequent resurfacing layer laid on a paved roadway throughout the life of the roadway. further, the resultant planed surface 28 that is created by the method and apparatus taught herein is a very clear surface, being free of oil and other road films. the planed surface 28 is a generally smooth, yet textured, surface which provides a very good bonding surface for overlay with concrete, latex concrete or asphalt. in fact, there are many applications in which the planed surface 28 can be used without an overlay, as for example when removing the top portion of a roadway that has received several bituminous layers. such roads can possibly be planed several times in a repair program designed to lessen the overall thickness of paved material while using the new roadway surface 28 as an intermediate roadway. while a bituminous roadway has been shown in fig. 1 to illustrate the present invention, it is not limited to the planing of bituminous material. the invention teaches precision planing, and it relates as well to other types of pavement, such as concrete or the like, as will become clear in the following discussion. when bituminous material is removed by the invention, the removed pavement material can be recycled by heating the removed pavement material and adding it in controlled measure to new bituminous pavement material. removed concrete, or other such pavement materials, may also find recycle use as aggregate fill material. shown in figs. 2 and 3 are a planer type road construction apparatus 40 constructed to have many of the features of the present invention. the planer apparatus 40 includes a main frame 42 having a forward end 44, a rearward end 46, a left side 48 and a right side 50. the main frame 42 is supported via a rear drive assembly 52 and a front track assembly 54, the rear drive assembly 52 being drivingly connected to a power drive unit 56 for drivingly moving the main frame 42 during the operation of the planer type road construction apparatus 40. the power drive unit 56 may be of a conventional design such as, for example, a diesel powered engine, and the construction and operation of such a power unit, and the various interconnecting components and operation thereof to drivingly connect the power drive unit 56 to the endless track members, are well known in the art and a detailed description thereof will not be required herein. the major portion of the various manually operated and control actuating elements, which are utilized by an operator to control and operate the planer type road construction apparatus 40, is, in a preferred form, supported in a control console 58. the control console 58 is supported on the main frame 42, generally near the forward end 44 thereof, and a guard-rail type of structure 60 is connected to the main frame 42, as shown in figs. 2 and 3. a steering assembly 62 is connected to the main frame 42 and to a portion of the front track assembly 54 for steering the planer type road construction apparatus 40. more particularly, the steering assembly 62 is constructed to automatically steer the front track assembly 54 in a steering direction 64 and a steering direction 66, as shown in fig. 3, to steeringly maintain the alignment of the planer type road construction apparatus 40 relative to a control reference, commonly a "string-line", in one aspect of the operation of the planer type road construction apparatus 40. a planer assembly 68 is supported on the main frame 42, generally near the forward end 44 thereof, and a floating moldboard 70 is also connected to the main frame 42, generally near the planer assembly 68. a reclaimer assembly 80, which generally includes a base conveyor 82 and an elevated conveyor 84, is supported on the main frame 42 for receiving the removed pavement material removed by the planer assembly 68 for depositing same in a predetermined, controlled, remote location or selected depository. the reclaimer assembly 80 is of the type taught in u.s. pat. no. 3,946,506, entitled "trim-type road construction apparatus with pivotally connected conveyor", assigned to the assignee of the present invention. therefore, a detailed description of the various components, and the cooperation of those components, of the reclaimer assembly 80 will not be required herein. rather, it will be sufficient to state that the base conveyor 82 is supported generally between the left side 48 and the right side 50, and extends angularly downwardly from near the rearward end 46 of the main frame 42 to the floating moldboard 70. as will become clear below, the base conveyor 82 receives removed pavement material at a material receiving end 90 and moves the material toward a material delivery end 92 which is disposed near the rearward end 46 of the planer type road construction apparatus 40. the elevated conveyor 84 has a material receiving end 96 disposed in material receiving relationship to the material delivery end 92 of the base conveyor 82, and the material received therefrom is moved via an endless belt to a material delivery end 98 for depositing the material in a selected position behind the planer type road construction apparatus 40. the general construction details of the base conveyor 82 and the elevated conveyor 84 are provided in u.s. pat. no. 3,946,506, mentioned above, and the further details are not necessary herein, with the exception that the material receiving end 90 of the base conveyor 82 is supported by the floating moldboard 70 as described below. the front track assembly 54 and the rear drive assembly 52 are of the type described in u.s. pat. no. 3,802,525, entitled "trimmer type road construction apparatus or the like", and assigned to the assignee of the present invention. therefore, it will not be necessary to fully describe the construction details of the front track assembly 54 in the present disclosure. the rear drive assembly 52 comprises a left track assembly 110 connected to the left side 48 of the main frame 42 and a right track assembly 112 connected to the right side 50 of the main frame 42. the planer apparatus 40 as illustrated herein comprises a planer assembly 68 mounted on a frame that is supported and driven by a three track drive assembly. this illustration is exemplary only, as the present invention is not limited to the drive assemblies 52, 54 described herein for purposes of this disclosure, an important consideration being that when the planer assembly 68 is rigidly fixed to the frame of the propelling machine, which is the preferred embodiment, the frame must be supported in such a manner that the frame may be precisely controlled as to grade and cross slope while the planer assembly 68 is operating. preferably, the planer apparatus 40 is automatically actuated in an actuated position thereof in response to an output signal of a track steering sensor that senses the location of an external reference line such as a string-line. also, the elevation of the main frame 42 relative to the front track assembly 54 and the rear drive 52 is automatically actuated and controlled in an actuated position thereof in response to an elevation sensor that senses the location of an external reference line such as a string-line. a track steering sensor 100 and an elevation sensor 102 are each supportedly connected to the left side 48 of the main frame 42 generally near the forward end 44 thereof. the construction of such sensors and the utilization of sensors such as the track steering sensor 100 and the elevation sensor 102 to provide an output signal responsive to a control reference as well known in the art, such sensors for example being described in u.s. pat. no. 3,423,859, entitled "road construction methods and apparatus", assigned to the assignee of the present invention. furthermore, the application of such sensors and the supporting hydraulic and electrical circuitry to steeringly control the main frame 42 and to raise and lower the main frame 42 relative to the drive assembly (the track assemblies 54, 110 and 112) in an actuated position thereof is described in u.s. pat. no. 3,802,525, entitled "trimmer type road construction apparatus or the like", assigned to the assignee of the present invention. therefore, further details of the construction and operation of such sensors are not necessary for purposes of the present disclosure. further, in the manner of that described in u.s. pat. no. 3,802,525, the elevation of one side of the main frame 42 is set in a predetermined elevation setting and the elevation of the other side thereof is automatically controlled via an automatic slope sensor and control apparatus to position the main frame 42 in a predetermined grade and slope position during the operation thereof. automatic control equipment to establish a predetermined grade and slope of the main frame 42 is also taught in u.s. pat. no. 3,423,859, cited above. therefore, a detailed description of such equipment and the cooperation of the components necessary to provide such control is not required herein. as stated above, construction details of the control of the steering, elevation and cross slope of the main frame 42 are not required herein as this may be readily obtained from the cited patents. however, it is believed useful to include a discussion of the operation of such equipment by reference to a block diagram as shown in fig. 4. as shown therein, a double acting front elevation cylinder 120 is shown connected to a front elevation control apparatus 122. also, a double acting, left rear elevation cylinder 124 is also connected to a rear elevation control apparatus 125. as described in the patents cited above, the front elevation cylinder 120 is connected to the forward end 44 of the main frame 42 and to the front track assembly 54 for the purpose of raising or lowering the forward end 44 when the front elevation cylinder 120 is actuated. in like manner, the left rear elevation cylinder 124 is connected to the left side 48 of the main frame 42 and to the left rear track assembly 110 for the purpose of raising or lowering the left side 48 when the left rear elevation cylinder 124 is actuated. in operation, an external reference line 126 (which may be a string-line or the like) is followed by the elevation sensor 102 and an appropriate control signal is sent thereby to the front elevation control apparatus 122 that in turn sends pressure fluid to extend or retract the cylinder 120 to establish the elevation of the main frame 42 at the forward end 44 at a predetermined elevation. the left rear elevation cylinder 124 can be extended and established in a setting corresponding to a predetemined grade (known as locked to grade), or the left rear elevation cylinder 124 can be controlled via a rear elevation control apparatus 125. the operation of the rear elevation control apparatus 125 is identical to that which is described above for the front elevation control apparatus 122. that is, an elevation sensor 127 (not shown in figs. 2 and 3) follows the external reference line 126 and an appropriate control signal is sent thereby to the rear elevation control apparatus 125 that in turn sends pressure fluid to extend or retract the cylinder 124 to establish the elevation of the left side 48 of the main frame 42 at a predetermined elevation. the right side 50 of the main frame 42 is controlled by a double acting, right rear elevation cylinder 128 that is connected to the right side 50 of the main frame 42 and to the right track assembly 112 for the purpose of raising or lowering the right side 50 when the right rear elevation cylinder 128 is actuated. a cross slope sensor and control apparatus 130 senses the cross slope of the main frame 42, compares the cross slope of the main frame 42 to a predetermined cross slope value, and actuates the right rear elevation cylinder 128 to maintain the cross slope of the main frame 42 at the predetermined cross slope value. also shown in fig. 4 is a double acting steering cylinder 132 that is connected to the forward end 44 of the main frame 42 and to the front track assembly 54 for the purpose of pivoting the front track assembly 54 relative to the main frame 42. the steering cylinder 132 is actuated by a steering control apparatus 134. the track steering sensor 100 senses the reference line 126 and signals the steering control apparatus 134 that sends pressurized hydraulic fluid to actuate the steering cylinder 132 as required to maintain the desired path of the planer apparatus 40. the above comments relative to fig. 4 are illustrative only, as it will be understood that the planar apparatus 40 may be equipped for other modes of operation as well. that is, the track steering sensor 100 and the elevation sensors 102 and 127 may be supported at the right side 50 of the main frame 42, and the reference line 126 disposed along the right side of the planer apparatus 40. the elevation of the main frame 42 would then be achieved by control of the cylinders 120 and 128, while the cross slope would be controlled via the left rear elevation cylinder 124. also, it is common to equip road construction apparatus such as the planer apparatus 40 with other types of automatic steering equipment and elevation and cross slope actuating equipment that are of known construction, and the details of such equipment are unnecessary herein. in summation then, the above described steering, elevation and cross slope controls are exemplary only, and it is within the contemplation of the present invention to provide automatic steering controlled from either side of the planar apparatus 40; to provide automatic elevation capability on all suspension points controlled from either side of the planer apparatus 40; and to provide cross slope capability, controlling as necessary, either side of the planer apparatus 40. and although a string reference line 126 is shown, it is contemplated that a conventional ski or grade averaging apparatus can be used to provide a reference line on either side of the planer apparatus 40, with such apparatus being supported on one side of the planer apparatus 40 to give an elevation of a roadway lane or the like that exists alongside of the selected travel of the planer apparatus 40. in this way, the planer apparatus 40 can be controlled to provide precision planing with reference to the grade of an existing surface. the planer assembly 68 performs the function of planing the top surface of a paved roadway (such as the top surface 14 of the roadway 10 before being resurfaced) by cutting away a selected portion of the roadway, as discussed above. the planer assembly 68 in the preferred form comprises a planing cutter 138 that comprises a rotary drum 140 as shown in fig. 5. the drum 140 is rotatably supported under the main frame 42 by way of the trunions 142 and 144 that are journaled in the support members 146 that extend downwardly from the main frame 42. the drum 140 is rotatable about its longitudinal axis 148 by a conventional hydraulic driving assembly (not shown) powered by the power drive unit 56. extending about the drum 140 is a spirally winding first flight 152 that begins near the end 154 and terminates near the center portion 156 of the drum 140. another spirally winding second flight 158 begings near the end 160 and terminates near the center portion 156. the winding pitches of the flights 152 and 158 are opposite to each other and are designed so that the first flight 152 has apparent motion in the first end-to-center direction 162, and the second flight 158 has apparent motion in the second end-to-center direction 164 when the drum is rotated in the rotary direction 166 as viewed in fig. 6. the planing cutter 138 is preferably rotated in the rotary direction 166 so as to cause the removed portion of the paved roadway 10 to be directed forwardly of the planing cutter 138 and generally moved from the ends 154, 160 in the apparent directions 162, 164 as the main frame 42 is driven in a forward direction 168. attached along each of the flights 152 and 158 at approximately equal intervals are a plurality of cutting heads 170, a side view of one such cutting head being shown in fig. 7. the cutting head 170 shown in fig. 7 comprises a support block 172 which is attached to the outer edge 174 of the first flight 152. the support block 172 has an angled support surface 176 to which is attached a cutter 178, the cutter 178 having a cutting point 180 that is preferably made as an insert of tungsten carbide or the like. in the preferred form the planing cutter 138 is dimensioned such that the cutting points 180 of all of the cutting heads 170 are disposed equidistantly from the longitudinal axis 148 of the drum 140 so that the cutting points 180 form a uniform plane of cutting that is defined as being the location of the lowest point reached by the cutting points 180 as the planing cutter 138 is rotated. in other words, this cutting plane contains a line 182 that is defined as touching each of the cutting points 180 at their lowest point in the rotation of the planing cutter 138. the line 182 extends transversely to the paved roadway over which the planer apparatus 40 is driven for the reason that the planing cutter 138 is rigidly held by the main frame 42 across the roadway in transverse disposition thereto. in fig. 6, the planing cutter 138 is shown in cutting engagement with the top surface 14 of the paved roadway 10. (the numbered references relative to the roadway in fig. 6 are used to relate to the depiction shown in fig. 1.) as the planing cutter 138 is rotated in the rotary direction 166 and moved in the forward direction 168, the new roadway surface 28 is produced. this new roadway surface 28 will be very uniform if the cutting plane of the cutting heads 170 is uniform and coincident with the new roadway surface 28. referring to fig. 5, it should be noted that a number of laterally extending paddle bars 184 are attached to the flights 152 and 158 at spaced intervals about the drum 140 near the center portion 156. the paddle bars 184 are recessed from the cutting heads 170 and serve in the fashion of scoops to throw the removed paving material cuttings upwardly to generally follow the drum 140 in the rotary direction 166. the purpose of this will become clear below. continuing with a description of the planer assembly 68, it will be noted by reference to fig. 2 that a hood 190, supported by conventional means on the main frame 42, is provided to partially surround the planing cutter 138 in the manner more clearly depicted by fig. 8. the hood 190 comprises an arcuately shaped member 193 that is supported by the main frame 42 via conventional bolting means to form a cover substantially forwardly, rearwardly and over the planing cutter 138, excepting the lower portion of the planing cutter 138 for exposure of the planing cutter 138 to cuttingly engage a paved roadway surface. an end panel 194 is attached to the member 193 at each end thereof for partially enclosing the planing cutter 138. also, each end of the hood 190 is equipped with a sliding shield member 195, one of which is viewed in fig. 8. the shield member 195 comprises a plate member 196 having a pair of slots 197 and an arbor clearing cutout 198. the shield member 195 is slidably supported on the end panel 194 via bolts 199 that extend through the slots 197. a pair of spring members 200 are compressingly supported between the lugs 201, extensive from the end panel 194, and the lugs 202, extensive from the plate member 196. an arcuately shaped runner member 203 is attached to the plate member 196 and serves as the pavement contacting edge of the shield member 195. as the planer assembly 68 is passed in cutting engagement with a pavement surface, the shield members 195 are biased downwardly via the springs 200 to yieldingly close the lower ends of the hood 190 to retain the removed pavement material generally within the confines of the hood 190 for removal thereof via the floating moldboard 70 and the reclaimer assembly 80 as described more fully below. in the manner described above, the hood 190 forms a material directing compartment 204 generally over the planing cutter 138. as the planing cutter 138 is rotated, the cutting heads 170 remove a selected top portion of the paved roadway 10, and the removed pavement material is directed upwardly into the material directing compartment 204. the lifting action imparted to the removed pavement material by the velocity of the cutting heads 170 is assisted by the movement of the flights 152 and 158 that tend to move the removed pavement material from the ends 154, 160 of the drum 140 toward the center portion 156 thereof. further, the paddle bars 184 rotating about the drum 140 tend to scoop and impart lifting action to the removed pavement material near the center portion 156. in order to minimize the effects of airborne dust and debris, a spray assembly 205 is provided that comprises a supply header 206 that is supported on the hood 190. a plurality of spray nozzles 207 are connected at intervals along the header 206 and are extensive through appropriately located ports into the material directing compartment 204. a supply tank and pump (not shown) are supported by the main frame 42, and a liquid such as water is carried in the supply tank. as this liquid is pumped to the supply header 206, a vapor mist is formed by the spray nozzles 207 in the material directing compartment 204. the effect of the vapor mist is to coalesce the airborne dust and debris, and serves to keep the mass of removed pavement material together as a body. the net result of this spraying is that the cutting action of the planer assembly 68 is practically dustless. the floating moldboard 70 is disposed just rearwardly of the planing cutter 138, and a semi-detailed view of the moldboard 70 is shown in fig. 9. the moldboard 70 is a longitudinal member that is approximately the same length as the drum 140, and comprises a body portion 210 that has a pair of generally upwardly protruding guide members 211 and a pair of rearwardly extending members 212, one of each of the guide members 211 and the extending members 212 being disposed near the opposite ends of the floating moldboard 70. the side view shown in fig. 9 shows one each of the guide members 211 and the extending members 212. for each of the extending members 212 there is provided a hollow member 213 extensive downwardly from the underside of the main frame 42. the cross sectional shape of the extending member 212 is approximately rectangular and is dimensioned to be freely slidable in the hollow core of its respective member 213. a lip portion 214 extends upwardly from the body portion 210 along an outer surface 215 of the member 213 to assist in maintaining the free-sliding action of the floating moldboard 70 in the upward direction 216 and in the downward direction 217. a pair of hydraulic cylinders 218 are provided, one each connected to each of the rearwardly extending members 212 as shown in fig. 9. the hydraulic cylinder 218 shown therein has a retractable rod member 219 that is connected via conventional bolting means to the member 212, and a cylinder portion 220 that is bolted via the connector 222 to the main frame 42. the hydraulic cylinder 218 is connected to a conventional source of pressurized fluid via conduits (not shown) and the rod member 219 is yieldingly forced in the downward direction 217. the moldboard 70 further comprises a heel portion 226 that is pressed by the biasing action of the hydraulic cylinders 218 into sliding contact with the new roadway surface 28 formed by the cutting action of the planer assembly 68. a molding panel 228 is attached to and forms the leading surface of the heel portion 226. the floating moldboard 70 is carried by the main frame 42 behind the planer assembly 68, and together with the reclaimer assembly 80 described above, serves to clear the roadway of the removed pavement material. as was mentioned above, it is desirable to have the material receiving end 90 of the base conveyor 82 in close proximity to the floating moldboard 70. this is achieved as shown in fig. 10 by pivotally and supportingly connecting the material receiving end 90 of the base conveyor 82 to the back side 230 of the floating moldboard 70. this may be achieved by attaching the side frame members 232 and 233 of the base conveyor 82 via conventional bolting means 234. the base conveyor 82 is also supported via pivoting hangers (not shown) to the main frame 42, permitting the material receiving end 90 to follow the upward and downward movement of the floating moldboard 70. a passageway 240 is disposed in the body portion 210 of the floating moldboard 70 to facilitate the passage of removed pavement material from the material directing compartment 204 to the base conveyor 82. appropriately shaped directing shields (not shown) may be provided to assist the flow of the removed pavement material onto the base conveyor 82, and the use of conventional flexible sealing flaps (not shown) is suggested to prevent spillage of the removed pavement material onto the new pavement surface 28 in back of the floating moldboard 70. operation of the embodiment shown in figs. 1 through 11 in operation, the planer apparatus 40 is placed over the roadway so as to transverse the pavement with the planing cutter 138 at a predetermined grade as established via a string-line or the like. the planer apparatus 40 would then be driven down the paved roadway alongside the string-line, utilizing the steering control 134 in conjunction with the track steering sensor 100 engaging the string-line. the elevation of the main frame 42 would be maintained utilizing the elevation control 122 in conjunction with the elevation sensor 102 engaging the string-line. also, the main frame 42 would be maintained at a predetermined cross slope via the cross slope sensor and cotrol apparatus 130. since the planer assembly 68 is rigidly secured under the main frame 42, the planing cutter 138 will cut along a cutting plane extending transversely to the paved roadway 10 as the plural cutting heads 170 cut along the line 182 that extends transversely to the paved roadway 10. as the plane of cutting is established via the means described above for establishing the grade and cross slope of the main frame 42 at predetermined values thereof, the result will be a uniform cutting action of the top surface of the roadway, exposing a uniform new roadway surface 28 as depicted in fig. 1. the rotation of the planing cutter 138 is preferably in the rotating direction 166 as shown in fig. 6 since cutting up against the grain of the paved roadway causes faults such as undetected cracks and weak portions to be most evident. while the planing cutter 138 could be established to rotate in a counter direction to the rotary direction 166, the cutting action as illustrated in fig. 6 reduces the impact force on the pavement since the cutters cut through and clear of the removed material, while in reverse cutting the cutters enter the roadway and continue through the pavement under the weight of the planing cutter 138. another benefit of rotating the planing cutter 138 in the rotating direction 166 is that a pile of the removed pavement material is continuously caused to form in the forward path of the travel of the planing cutter 138 along the roadway. this removed pavement material is dampened by the vapor mist that is sprayed by the spray assembly 205, and the removed pavement material that continuously piles immediately in front of the planing cutter 138 serves to contain the dust created by the cutting action of the cutting heads 170, and to partially muffle the sound of the cutting. and although the removed pavement material is continuously removed via the lifting action described above, there is usually sufficient piling of the removed pavement material to give this beneficial dust containing and sound muffling function. as the top portion of the roadway is removed in the manner described above, it has been determined that the removed portion of a bituminous roadway will be removed in relatively small pieces which are readily moved toward the center portion 156 of the drum 140 by the action of the flights 152 and 158, and that the rotating action of the paddle bars 184 will generally lift the cuttings of the removed pavement material up and over the planing cutter 138 to be received through the passageway 240 onto the material receiving end 90 of the base conveyor 82, and of course removed in a manner described above for the reclaiming assembly 80. the floating moldboard 70 serves to push any remaining cuttings in front thereof to the point that these overflow the moldboard via the passageway 240 or are slung around in front of the planing cutter 138 by the action of the flights 152 and 158. in practice, the combined action of the planing cutter 138 and the floating moldboard 70 has provided a very satisfactory clearing of the new pavement surface 28 and the placement of the cuttings of the new portion onto the reclaimer assembly 80 thereby. in most applications of the planer apparatus 40, the newly created surface will be sufficiently cleared of the cuttings of the removed roadway material in the manner described above. however, it is contemplated that there will be some applications in which it is desirable to sweep the new roadway surface following the path of the planer apparatus 40 to remove fine dust and debris not collected by the planer apparatus 40. this can be achieved by a following sweeper apparatus of the type shown in fig. 11, wherein a sweeper assembly 250 is pulled behind the planer apparatus 40 via an extension bar 252 connected to the rearward end 46 of the main frame 42. the sweeper assembly 250 is conventional in design, and there are a large number of such sweepers available commercially, each having a sweeper 254 and a depository 256 cooperatively sweeping and retaining the dust and debris left on the new pavement surface 28 following the passage of the planer apparatus 40. of course, a sweeper assembly performing the function of the sweeper assembly 250 could be mounted under the main frame 42, but the preferred embodiment is that as shown in fig. 11 wherein the sweeper assembly 250 may be disengaged when not required. description of figs. 12 through 14 referring to fig. 12, shown therein is a diagrammatical representation of a cross section of a typical paved roadway 10a having at least one irregular depression 258 therein, and illustrating the method of the present invention for repairing such depressions 258. more particularly, the depression 258 extends not only through the old roadway surface 14a but also below a desired new roadway surface 28a having a predetermined grade and cross slope established as described generally above. according to the present invention, the first step in repairing the depression 258 is to remove the portion of the existing paving material 12a of the paved roadway 10a within a predetermined distance of the outer periphery 260 of the depression 258, down to a predetermined depth below the bottom 262 of the depression 258. in other words, the existing paving material 12a of the paved roadway 10a should be removed from around the periphery 260 and below the bottom 262 of the irregular depression 258 so as to form a generally regular depression 264 having substantially vertical sidewalls 266 and a relatively flat bottom 268. in accomplishing the removal of the portion of the existing paving material 12a surrounding and underlaying the irregular depression 258, various well known apparatus may be employed such as that shown and described in u.s. pat. no. 3,333,646, entitled "mobile hammer unit and position control apparatus therefor", assigned to the assignee of the present application. following the removal of the desired portion of the material 12a to form the regular depression 268, a substantially uniform layer 270 of new pavement material 272, such as hot mix asphalt, should be applied with the regular depression 264, the layer 270 having an upper surface 274 above the predetermined grade and a density substantially the same as the density of the existing pavement materials 12a surrounding the regular depression 264. although other apparatus may be as satisfactory in compressing the new pavement material 272 to the desired density, it has been determined that the apparatus described in u.s. pat. no. 3,333,646, is particularly well adapted to accomplish this step in view of the ability of this apparatus to precisely control the compression force and stroke length of the compression tool mounted thereon. in this regard, the substantially vertical sidewalls 266 and relatively flat bottom 268 of the regular depression 264 contributes substantially to the success of the present method in obtaining a density within the layer 270 approximating the density of the surrounding existing pavement material 12a, in addition to facilitating the bonding of the layer 270 to the existing pavement material 12a. after the layer 270 has been afforded sufficient opportunity to reach an equilibrium condition relative to the surrounding existing pavement material 12a, all of the material of the paved roadway 10a lying above the predetermined grade and cross slope may be removed by passing a rotating planing cutter, such as that referred to above as the planing cutter 138, over the paved roadway 10a at the predetermined grade and cross slope via a planer type road construction apparatus, such as that referred to above as the planer type road construction apparatus 40. during the course of resurfacing the paved roadway 10a to produce the new roadway surface 28a, it will be readily recognized that the passage of the cutting heads 170 through the pavement material 12a will impart an identifiable pattern on the new roadway surface 28a. as will be clear to those skilled in the art, the particular pattern impressed upon a given roadway surface 28a will be highly dependent upon the spacing and positioning of the cutting heads 170 on the surface of the rotating planing cutter 138, in conjunction with the rotational speed of the planing cutter 138 and the forward velocity of the planer apparatus 40. for example, four distinctive patterns are shown by way of example in figs. 13 and 14. in a first pattern, which may conveniently be designated as a full spaced pattern 276, passage of the cutting heads 170 are coordinated so that the paths 278 created thereby are laterally aligned, with longitudinally successive rows of paths 278 being longitudinally spaced on the order of one full length of the paths 278. this full spaced pattern 276 provides generally adequate surface adhesion qualities but induces particularly annoying vibrations in vehicles passing at significant velocities thereover. in a second pattern, which may conveniently be referred to as a staggered pattern 280, the passage of each transversely successive cutting head 170 is coordinated so that the paths 282 created thereby are longitudinally offset from the laterally adjacent cutting paths 282 on the order of 1/2 the length of the path. such a staggered pattern 280 produces a significantly higher rate of wear of the cutting heads 170, while satisfactorily eliminating the irritating vibrational patterns inherent in the full spaced pattern 276. it has been determined that the staggered pattern 280 is particularly advantageous in the resurfacing of concrete roadways due to the excellent surface adhesion qualities inherent therein. in a third pattern, which may conveniently be referred to as a full offset pattern 284, the passage of each transversely successive cutting head 170 is coordinated so that the cutting paths 286 created thereby are longitudinally offset from the laterally adjacent paths 286 on the order of one full length of each path 286. the production of the full offset pattern 284 induces a rate of wear of the cutting heads 170 substantially the same as the rate of wear induced in the production of the full spaced pattern 276, but satisfactorily elimates substantially all of the undesirable vibrational tendencies of the full spaced pattern 276. it has been determined that the full offset pattern 284 is particularly desirable in the resurfacing of asphalt roadways, especially where the cutting heads 170 are constructed similar to that shown in fig. 16 and described in detail below. in a fourth pattern, which may conveniently be referred to as a continuous pattern 288, the passage of the cutting heads 170 are coordinated so that the paths 290 created thereby are laterally aligned, with longitudinally successive rows of paths 290 being at most only slightly longitudinally offset from the adjacent rows of paths 290. the production of the continuous pattern 288 produces a particularly high rate of wear of the cutting heads 170 with the resulting surface exhibiting little if any advantage over the previously described patterns 276, 280 and 284. however, the continuous pattern 288 respresents a particularly smooth traveling surface and may be desired in certain situations. description of figs. 15 through 17 it has been determined through extensive operational utilization of machines constructed similar to the planer type road construction apparatus 40, that cutting heads 170 of the type shown in fig. 7 are particularly advantageous when resurfacing paved roadways 10 of the concrete type. however, when the cutting heads 170 are utilized to resurface a paved roadway 10 of the asphalt type, there is normally a significantly higher rate of wear of the metal comprising the cutter 178 relative to the rate of wear of the metal forming the cutting point 180, with the effect of "washing" away the cutter 178 leaving the cutting point 180 relatively unsupported. it is therefore proposed to provide an improved cutter 178a for use in resurfacing asphalt roadways, wherein the cutter 178a is provided with a chisellike cutting point 180a defining the leading face of the cutter 178a. preferably, the cutter 178a is provided with scallops 292 on either side thereof relatively rearwardly of the cutting point 180a so as to maximize the support being provided the cutting point 180a while minimizing the amount of surface area being subjected to the "washing" action experienced during utilization of the cutter 178a. in operation, the improved cutter 178a will impart a substantially rectangular groove to the pavement being resurfaced. for example, shown in fig. 15, is a partial, transverse cross sectional view of the full offset pattern 284 as it would appear if produced via the improved cutter 178a. thus, the laterally alternate, substantially rectangular grooves 294 and 296 are separated by a ridge 298 formed by the cooperation of intermediate cutters 178a, the associated flights 152 or 158, and the molding panel 228 forming the leading surface of the moldboard 70. it has been determined that the "floating" characteristic of the floating moldboard 70 may be undesirable when the improved cutter 178a is being used to produce the full offset pattern 284 due to the tendency of the floating moldboard 70 to "ride up" on the ridges 298 rather than "cutting through" them. to remedy this situation, it is proposed to operate the moldboard 70 in a fixed mode by connecting each of the hydraulic cylinders 218 (see fig. 6) into the hydraulic control circuitry of the planer assembly 40 via hydraulic conduits 299. in this mode of operation, the hydraulic cylinders 218 may be actuated in a double acting manner to fix the position of the moldboard 70, and particularly the lower edge of the molding panel 228, at a second predetermined grade slightly above the predetermined grade selected for the planer assembly 68, to facilitate removal of the material of the paved roadway 10 above the second predetermined grade and the predetermined cross slope. since the "fixed" moldboard 70 is still being maintained at the same selected cross slope, the tops of the ridges 298 formed by the passage of the moldboard 70 are all at substantially the same elevation relative to the bottoms of the grooves 294 and 296. of course, if desired, the "fixed" moldboard 70 may be positioned at the same predetermined grade as the planer assembly 68 so as to remove all of the material of the paved roadway 10 above the predetermined grade and cross slope and leave no identifiable ridges 298. description of the preferred embodiment shown in fig. 18 is a planer type road construction apparatus 40a constructed in accordance with the preferred embodiment of the present invention for resurfacing an existing paved roadway 10 as the planer apparatus 40a is driven forwardly over the roadway 10. more particularly, the planer apparatus 40a is constructed substantially the same as the planer apparatus 40 described above, except that the planer apparatus 40a is provided with an asphalt paving assembly 300 in place of the reclaimer assembly 80. the planer apparatus 40a includes a planer assembly 68a which is substantially the same as the planer assembly 68 described above, i.e. the planer assembly 68a is connected to and supported by the planer apparatus 40a transversely to the paved roadway 10 at a predetermined grade and cross slope. thus, the planer assembly 68a cuts the paved roadway 10 along a cutting plane having the predetermined grade and cross slope to remove the portion of the roadway 10 above the cutting plane in particulate form suitable for use as a recyclable aggregate. in addition, the planer apparatus 40a is provided with a floating moldboard 70a which is substantially the same as the floating moldboard 70, with the floating moldboard 70a acting to channel and lift the recyclable aggregate produced by the planer assembly 68a for introduction to the asphalt paving assembly 300. the asphalt paving assembly 300 is comprised primarily of an asphalt supply assembly 302, a mixer 304, a spreader 306, and a screed 308. the asphalt supply assembly 302 consists of a reservoir 310 disposed adjacent the rearward end 46a of the planar apparatus 40, and a supply conduit 312 connected between the reservoir 310 and the mixer 304. while the reservoir 310 may in some embodiments be constructed to supply conventional heated asphaltic composition, in the preferred embodiment the reservoir 310 provides an asphaltic emulsion prepared in a conventional manner to effectively react with the recyclable aggregate. the mixer 304, which is preferably of the pug mill type, has a forward end 314 disposed adjacent the floating moldboard 70a for receiving the recyclable aggregate from the floating moldboard 70a. the mixer 304 has at least one rotating paddle assembly (not shown) for mixing the recyclable aggregate with a predetermined quantity of the asphaltic composition injected thereinto from the reservoir 310 via the supply conduit 312 to produce new paving material for discharge through a rearward end 316 thereof. the spreader 306 is connected to the planer apparatus 40a immediately rearwardly of the mixer 304 for spreading the new paving material discharged from the mixer 304 across the paved roadway 10 above the cutting plane. the spreader 306 is preferably of the screw conveyor type taught in u.s. pat. no. 3,997,277, entitled "material transfer mechanism" assigned to the assignee of the present invention. therefore, a detailed description of the various components of the spreader 306 will not be included herein. the screed 308 is connected to the planer apparatus 40a immediately rearwardly of the spreader 306 with the lower surface 318 of the screed 308 being maintained at a second predetermined grade and cross slope, the second predetermined grade being substantially parallel to but spaced above the predetermined grade described above as defining the cutting plane. the screed 308 is constructed in a conventional manner to compact the new paving material on the paved roadway 10 to produce a new roadway surface 28 having the second predetermined grade and cross slope. the screed 308 is preferably of the type taught in u.s. pat. no. 3,997,277, referred to above, and thus will not be described in detail herein. although the spreader 306 and the screed 308 may be connected as an integral part of the planer apparatus 40a, it has been determined that a more satisfactory construction is to connect at least the screed 308 and preferably the spreader 306 to the planer apparatus 40a via a pair of conventional tow bars 320 (only one of which is shown for convenience). in particular, each of the tow bars 320 is pivotally connected at a medial portion thereof to a rearward portion of the main frame 48 of the planer apparatus 40a via fixed pivots 322, while the forward ends 324 of the tow bars 320 are each vertically adjustable via a conventional hydraulic cylinder 326 connected between the planer apparatus 40a adjacent the floating moldboards 70a and the forward ends 324 of the tow bars 320. the screed 308 may then be pivotally connected to the tow bars 320 adjacent the rearward ends 328 thereof via riser members 330, with crank assemblies 332 extending between the screed 308 and the rearward ends 328 of the tow bars 320 to adjust the angle of inclination of the screed 308. thus, the grade and cross slope of the screed 308 may be adjusted substantially independently of the grade and cross slope of the main frame 48 via the cylinders 326. the construction of the tow bars 320 and the connection thereof between the planer apparatus 40a and the screed 308 is taught in u.s. pat. no. 3,997,277, referred to above. operation of the preferred embodiment the planer type road construction apparatus 40a will operate substantially the same as the planer type road construction apparatus 40 described in detail above. however, instead of removing the material cut from the old roadway surface 14 the planer apparatus 40a utilizes the material as recyclable aggregate in the preparation of new paving material which may be reapplied to produce a new roadway surface 28. in particular, as the planer apparatus 40a is driven forwardly over the roadway 10, the planer assembly 68a will cut the paved roadway 10 along the predetermined cutting plane to remove the portion of the roadway 10 above the cutting plane in particulate form suitable for use as a recyclable aggregate. the recyclable aggregate will then be introduced into the mixer 304 via the floating moldboard 70a, the mixer 304 mixing the recyclable aggregate with a predetermined quantity of asphaltic composition provided by the asphalt supply assembly 302 to produce new paving material. upon the discharge of the new paving material onto the roadway 10 by the mixer 304, the spreader 306 will spread the new paving material across the paved roadway 10 generally above the cutting plane. thereafter, the screed 308 will compact the new paving material on the paved roadway 10 to produce a new roadway surface 28 having a predetermined grade and cross slope related in a known way to the cutting plane. description of an alternate embodiment as an alternative to providing the asphalt paving assembly 300 in place of the reclaimer assembly 80, it may be desirable in some circumstances to utilize the spray assembly 205, which is supported by the main frame 42 adjacent to and forwardly of the planer assembly 68, as a means for applying the asphaltic composition directly to the recyclable aggregate as it is produced via the planing cutter 138. thus, the natural agitation of the recyclable aggregate through the action of the planing cutter 138 acts to mix the asphaltic composition with the recyclable aggregate thereby eliminating the need for a separate mixing assembly. in such a configuration, the reclaimer assembly 80 may be conveniently utilized for collecting the recyclable aggregate and asphalt composition mixture and depositing the mixture at a predetermined position relative to the planer apparatus 40. thereafter, the mixture may either be transported to a paving site or left in place for spreading and compacting by auxiliary machines. in view of the large quantities of asphaltic composition consumed during the application thereof to the recyclable aggregate via the spray assembly 205, it may be desirable to augment the existing storage capacity of the planer apparatus 40 by providing a self-propelled storage vehicle 334 (see figs. 2 and 3) for supplying the asphaltic composition via a connecting conduit 336. similarly, if desired, the storage vehicle 334 may be utilized as the exclusive source of the asphaltic composition to the exclusion of any supply tanks (not shown) normally provided on the planer apparatus 40. although the method and apparatus of the present invention have been described herein as utilizing only the material cut by the planer assembly 68a above the cutting plane in the production of new paving material, it will be readily recognized that additional new paving material may be easily furrowed in a conventional manner forwardly of the planer apparatus 40a with such additional material being automatically combined with the recyclable aggregate for processing by the asphalt paving assembly 300. in addition, other changes may be made in the construction and the arrangement of the various parts or elements of the apparatus, or of the steps of the method of the invention disclosed herein, without departing from the spirit and scope of the invention as defined in the following claims.
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059-933-732-946-439
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US
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[
"US"
] |
G06F3/06,G06F12/08,G06F21/78,G06F21/79,G11C7/10,G11C29/00,G11C29/42,G11C29/44,G11C29/52
| 2016-09-27T00:00:00 |
2016
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[
"G06",
"G11"
] |
method of processing incomplete memory operations in a memory device during a power up sequence and a power down sequence using a dynamic redundancy register
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a method of writing data into a memory device is disclosed. the method comprises utilizing a pipeline to process write operations of a first plurality of data words addressed to a memory bank. further, the method comprises writing a second plurality of data words and associated memory addresses into a cache memory, wherein the cache memory is associated with the memory bank and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the memory bank or is to be re-written into the memory bank. the method also comprises detecting a power down signal and responsive to the power down signal, transferring the second plurality of data words and associated memory addresses from the cache memory into a secure memory storage area reserved in the memory bank. finally, the method comprises powering down the memory device.
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1. a method of writing data into a memory device, the method comprising: utilizing a pipeline to process write operations of a first plurality of data words addressed to a memory bank; writing a second plurality of data words and associated memory addresses into a cache memory, wherein said cache memory is associated with said memory bank and wherein further each data word of said second plurality of data words is either awaiting write verification associated with said memory bank or is to be re-written into said memory bank; detecting a power down signal; responsive to the power down signal, transferring the second plurality of data words and associated memory addresses from said cache memory into a secure memory storage area reserved in the memory bank; and powering down the memory device. 2. a method as described in claim 1 wherein said memory bank comprises a plurality of spin-transfer torque magnetic random access memory (stt-mram) cells. 3. a method as described in claim 1 further comprising: responsive to said power down signal, transferring any partially completed write operations of said pipeline to said secure memory storage area. 4. a method as described in claim 1 further comprising: responsive to said power down signal, and before said transferring, copying any partially completed write operations of said pipeline to said cache memory. 5. a method as described in claim 1 wherein said transferring comprises utilizing a secure communication process substantially compliant with one of: voting; ecc encoding; use of multiple copies; comparing multiple copies; and voting from multiple copies. 6. a method as described in claim 1 wherein said power down signal originates from a system level software stack and represents a system wide orderly power down event. 7. a method as described in claim 1 further comprising removing a data word and its associated address from said cache memory responsive to an indication that said data word has been verified as properly written to said memory bank. 8. a method as described in claim 1 , further comprising: receiving a power up signal; responsive to the power up signal, transferring the second plurality of data words and associated memory addresses from the secure memory storage area to the cache memory; and processing said second plurality of data words, from said cache memory, through said pipeline for writing into said memory bank. 9. a memory device for storing data, the memory device comprising: a memory bank comprising a plurality of addressable memory cells; a pipeline configured to process write operations of a first plurality of data words addressed to said memory bank; a cache memory operable for storing a second plurality of data words and associated memory addresses, wherein said cache memory is associated with said memory bank and wherein further each data word of said second plurality of data words is either awaiting write verification associated with said memory bank or is to be re-written into said memory bank; and a logic module operable to: detect a power down signal; responsive to the power down signal, transfer the second plurality of data words and associated memory addresses from said cache memory into a secure memory storage area reserved in the memory bank; and power down the memory device. 10. a memory device as described in claim 9 wherein said plurality of addressable memory cells of said memory bank comprises spin-transfer torque magnetic random access memory (stt-mram) cells. 11. a memory device as described in claim 9 wherein said logic module is further operable to, responsive to said power down signal, transfer any partially completed write operations of said pipeline to said secure memory storage area. 12. a memory device as described in claim 9 wherein said logic module is further operable to, responsive to said power down signal, and before said transfer, copy any partially completed write operations of said pipeline to said cache memory. 13. a memory device as described in claim 9 wherein said logic module utilizes a secure communication process substantially compliant with one of: voting; ecc encoding; use of multiple copies; comparing multiple copies; and voting from multiple copies. 14. a memory device as described in claim 9 wherein said power down signal originates from a system level software stack and represents a system wide orderly power down event. 15. a memory device as described in claim 9 wherein a data word and its associated address are removed from said cache memory responsive to an indication that said data word has been verified as properly written to said memory bank. 16. a memory device as described in claim 9 wherein said logic module is further operable to: detect a power up signal; responsive to the power up signal, transfer the second plurality of data words and associated memory addresses from the secure memory storage area to the cache memory; and cause said pipeline to process said second plurality of data words, from said cache memory, for writing into said memory bank. 17. a memory device for storing data, the memory device comprising: a memory bank comprising a plurality of addressable memory cells; a pipeline configured to process write operations of a first plurality of data words addressed to said memory bank; a cache memory operable for storing a second plurality of data words and associated memory addresses, wherein said cache memory is associated with said memory bank and wherein further each data word of said second plurality of data words is either awaiting write verification associated with said memory bank or is to be re-written into said memory bank; and a logic module operable to: detect a power up signal; responsive to the power up signal, transfer the second plurality of data words and associated memory addresses from said a secure memory storage area to said cache memory; and cause said pipeline to process said second plurality of data words, from said cache memory, for writing into said memory bank. 18. a memory device as described in claim 17 wherein said plurality of addressable memory cells of said memory bank comprises spin-transfer torque magnetic random access memory (stt-mram) cells. 19. a memory device as described in claim 17 wherein said power signal is generated in response to an initiation of a power up process and wherein further said pipeline is operable to process said second plurality of data words, during said power up process. 20. a memory device as described in claim 17 wherein said memory bank comprises said secure memory storage area.
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cross-reference to related application the present application is a continuation-in-part of, claims the benefit of and priority to u.s. application ser. no. 15/277,799, filed sep. 27, 2016, entitled “device with dynamic redundancy registers” and hereby incorporated by reference in its entirety. field the present patent document relates to registers that are added to devices, and more particularly registers added to random access memory (ram). the methods and devices described herein are particularly useful in spin-transfer torque magnetic memory (stt-mram) devices. background magnetoresistive random-access memory (“mram”) is a non-volatile memory technology that stores data through magnetic storage elements. these magnetic storage elements are two ferromagnetic plates or electrodes that can hold a magnetic field and are separated by a non-magnetic material, such as a non-magnetic metal or insulator. in general, one of the plates has its magnetization pinned (i.e., a “reference layer”), meaning that this layer has a higher coercivity than the other layer and requires a larger magnetic field or spin-polarized current to change the orientation of its magnetization. the second plate is typically referred to as the free layer and its magnetization direction can be changed by a smaller magnetic field or spin-polarized current relative to the reference layer. mram devices store information by changing the orientation of the magnetization of the free layer. in particular, based on whether the free layer is in a parallel or anti-parallel alignment relative to the reference layer, either a “1” or a “0” can be stored in each mram cell. due to the spin-polarized electron tunneling effect, the electrical resistance of the cell changes due to the orientation of the magnetization of the two layers. the cell's resistance will be different for the parallel and anti-parallel states and thus the cell's resistance can be used to distinguish between a “1” and a “0.” mram devices are generally considered as non-volatile memory devices since they maintain the information even when the power is off. the two plates can be sub-micron in lateral size and the magnetization direction can still be stable with respect to thermal fluctuations. mram devices are considered as the next generation structures for a wide range of memory applications. mram products based on spin torque transfer switching are already making its way into large data storage devices. spin transfer torque magnetic random access memory (“stt-mram”) has an inherently stochastic write mechanism, wherein bits have certain probability of write failure on any given write cycle. the write failures are most generally random, and have a characteristic failure rate. a high write error rate (wer) may make the memory unreliable. in memory devices, and especially stt-mram, methods and systems for verifying and re-writing data words are beneficial. summary and claimable subject matter in an embodiment, a device with dynamic redundancy registers is disclosed. in one aspect, a memory device comprising random access memory (ram) device, and specifically an stt-mram device, is provided. the present disclosure provides backup dynamic redundancy registers that allow the device to operate with high write error rate (wer). the dynamic redundancy registers allow verifies, re-writes, and relocation of data words that fail to write correctly to a memory bank, generally, without loss of throughput, speed, or restriction on random access addressing. in one aspect, the present disclosure teaches a memory bank that is coupled to an e 1 register. the e 1 register is coupled to the e 2 register. the e 1 register stores data words that are to be verified or re-written to the memory bank. the e 1 register also stores an associated address for data words within the memory bank. data words in the e 1 register may be verified against data words in the memory bank at the associated address within the memory bank. if a system write operation fails on the memory bank, a re-write operation may be tried by writing a data word from the e 1 register to the memory bank. the fact that the system write operation failed may be determined through a verify operation. re-write operation from e 1 register to memory bank may be tried as many times as necessary to successfully complete write operation or may not be tried at all. in one example, the number of re-write operations may be configurable based on control bit(s) associated with re-write attempts. in one aspect, the number of re-write operations may be configurable on a per-bank basis or per-segment of bank basis. these control bits may be stored in the e 1 register and associated with a particular data word and communicated and updated as appropriate. in one aspect, the re-write operation may be tried only when memory bank is idle (that is there are no write or read operations for that memory bank). in this way, re-write operations may be transparent to and with no delay of incoming system read and system write operations. after the desired number of re-write attempts (0 to n) from the e 1 register, the memory device moves (relocates) data word from the e 1 register to the e 2 register. the memory device may also move associated address within memory bank for data word from the e 1 register to the e 2 register. in one aspect, the memory device does not comprise an e 2 register. instead, after a desired number of re-write attempts, the memory device relocates the data word and associated address from the e 1 register to a secure area in memory reserved for storing data words associated with pending re-write and verify operations in the e 1 register. in one embodiment, a re-write operation may occur only once from the e 1 register to the memory bank. the memory device then relocates the data word and associated address from the e 1 register to the e 2 register if the re-write operation failed. alternatively, if there is no e 2 register, the memory device then relocates the data word and associated address from the e 1 register to the secure storage area in memory. although explained with reference to one memory bank and two dynamic redundancy registers, one or more memory banks and two or more dynamic redundancy registers may also be used. alternatively, in certain embodiments only one dynamic redundancy register may be used, e.g., embodiments without an e 2 register. typically, the first level dynamic redundancy register (e 1 register) may operate at clock cycle speed of memory bank (some operations may operate at clock cycle speed of memory bank while other operations may occur independent or multiples of memory bank clock cycle speed). the e 1 register may be either non-volatile or volatile, and may typically comprise sram. the e 1 register may also comprise a content addressable memory (cam) array which allows reduced size of e 1 register. in one embodiment, e 1 register may be high-speed, smaller register than a last level register. typically, the last level dynamic redundancy register (e 2 register) may operate at clock cycle speed of main memory bank (some operations may operate at clock cycle speed of memory bank while other operations may occur independent or multiples of memory bank clock cycle speed). the last level may be either non-volatile or volatile, and may typically comprise mram. the e 2 register may also comprise a cam. the last level dynamic register may beneficially comprise non-volatile memory which allows data to be backed up on power down. the e 2 register typically prioritizes reliability over size as compared to memory bank. in one embodiment, the last level register may comprise more entries than the e 1 register. in one embodiment, e 2 register entries may be invalidated when a write operation occurs for a data word having associated address common with data word in e 2 register. alternatively, in an embodiment without an e 2 register, entries in the secure memory storage area may be invalidated when a write operation occurs for a data word having an associated address common with data word in the secure memory storage. in one aspect, the e 1 register stores a data word and an associated address for data words in a pipeline structure that have not had an opportunity to verify. for example, a data word may not have an opportunity to verify because of row address change. that is, a write operation may occur on a different row address than a verify operation. thus, the data word for a verify operation would be stored within e 1 register and verify would be performed, if possible, on another data word from e 1 register having common row address with the data word for write operation. this feature is especially beneficial in pseudo-dual port memory banks. a dual port memory bank allows read and write operations to be performed simultaneously. a pseudo-dual port allows read and write operations to be simultaneously (e.g., substantially within the same memory device clock cycle) performed on less than all ports. in one example, a pseudo-dual port mram may allow verify and write operations to be simultaneously performed as long as the operations share a common row address and different column addresses. in one aspect, a data word may be read from the e 1 register rather than main memory bank if the data word failed to write or verify to memory bank. in another aspect, the e 1 or e 2 register data word, associated address, and control bits can be deleted, overwritten, invalidated such that the data is not used, or otherwise considered garbage when another write operation for the same associated address occurs on the memory bank. in one aspect, a data word may be read from the e 2 register rather than the main memory bank if such read operation is beneficial. for example, if e 1 register relocated a data word to e 2 register. in another aspect, data stored in the e 2 sram and cam is backed up onto the e 2 non-volatile ram for storage during power down. in another embodiment, data stored in e 2 non-volatile ram may be transferred to e 2 volatile ram during power up. in another aspect, the memory device may move data from the e 1 register to the e 2 register in order to free room in the e 1 register. in another aspect, e 2 register may not store data words and associated addresses but instead remap data words and associated addresses received from e 1 register into a different area of memory bank. in another aspect e 2 register may move data words to memory bank upon power down. typically, e 2 register should be more reliable than memory bank because data may not be recoverable in case of e 2 register failure. thus, schemes can be implemented to increase reliability of e 2 register. for example, e 2 register may comprise status bits that allow data manipulation of a particular data word or other entry within e 2 only if all or a predetermined number of status bits are set to one. in another scheme, multiple copies of data word may be maintained in e 2 register and selected based on a voting scheme. in another scheme, a more stringent error correction code (ecc) scheme may be performed within e 2 register than in memory bank. in another scheme, e 2 register points to particular addresses within main memory for storing data words rather than storing the data word within e 2 itself. in one embodiment of the present invention, only one dynamic redundancy register, e.g., the e 1 register may be used in a memory device. in other words, the memory device will have no e 2 register. in one embodiment, upon receiving the power down signal, the e 1 register may attempt to perform all the pending operations, e.g., verify and re-write operations associated with the data words stored in the e 1 register prior to shutting down. in other words, upon receiving the power down signal, the e 1 register may attempt to perform all the pending verify operations and move all the data words associated with pending re-write operations (e.g. operations that have failed verification) stored within it to the appropriate corresponding locations in the memory bank. in one embodiment, if the verify operations and re-write operations succeed, the corresponding entries for the data words in the e 1 register may be deleted prior to shutting down (if the e 1 register comprises non-volatile memory). any data words in the e 1 register that could not be successfully re-written or verified prior to shutting down will be stored in a secure memory storage area. in one embodiment, the memory device ensures that data is written securely to the secure memory storage area by using one or multiple schemes including voting, error-correcting code (ecc), or storing multiple copies. in one embodiment where only the e 1 register is used, upon power up of the memory device and receipt of power up signal, another attempt can be made to perform all the pending re-write or verify operations using the associated addresses for the data words. as stated above, subsequent to powering down, the secure memory storage area will comprise data words (with their associated addresses) that have not yet been verified or that have failed verification. the verify and re-write operations can be directly attempted from the secure memory storage area or they can be recalled to the e 1 register prior to processing the pending operations to the pipeline. in one embodiment, if the attempt to verify or write the data words back to memory on power up succeeds, the corresponding entries for the data words in the secure memory storage area or the e 1 register may be deleted. any data words that could not be successfully re-written or verified subsequent to powering up will be stored in the e 1 register. in one aspect, the present disclosure teaches an access method and system into memory banks. pseudo-dual ports allow using the disclosed y-mux structure to simultaneously perform verify and write operations on two data words sharing a common row address (e.g., sharing a common word line). in other embodiments, dual port memory bank could allow simultaneous read and write operations. the y-mux structure of the present disclosure operates using two column decoders for the column address. one column decoder allows decoding for write column addresses. the other column decoder allows decoding for read and verify column addresses. the disclosed pseudo-dual port memory bank with y-mux structure requires only a single-port memory cell. as explained, a dual port memory bank may allow read and write operations to be simultaneously performed, but requires a dual port memory cell. a single port memory cells, for example an stt mram memory cell, may be more area efficient than a dual port memory cell, for example a dual port stt mram memory cell. thus, the present disclosure teaches, in one embodiment, a y-mux structure to create a pseudo dual port memory bank with single port memory cells. thus, e 1 register operates with the disclosed pseudo dual port memory bank to permit write and verify operations sharing common row address to occur simultaneously. in another aspect, the memory device includes control bits and signals that are used for the control logic of this disclosure. the memory device may thus know whether data is located in a memory bank, memory pipeline, e 1 register, or e 2 register for read operations. in another aspect, data for operations may invalidated based on control bits and signals to maintain consistency of operations. such control bits and signals may include valid bit, active bank signal, fail count bits, e 2 entry inactive bit. a valid bit indicates that particular data within a register is valid for data manipulation operations. an active bank signal indicates whether the memory bank for operation is active (i.e., that a system write or system read is being performed in that bank). fail count bits indicate the number of re-write operations have occurred for the data word. the e 2 entry inactive bit indicates that the associated entry in e 2 should not be used for data manipulation operations. in another aspect, the present disclosure teaches a memory device having pipeline structure for write and verify, among other data manipulation operations. this pipeline structure may be used to control system write, verify, and re-write operations, among other data manipulation operations. using the pipeline structure of the present disclosure, data integrity is maintained and data flow is structured. in one embodiment, a delay register implements a delay cycle allowing memory to reach stable state before performing a verify operation on a data word. this delay cycle allows a write operation to be performed for a data word, followed by a delay cycle, followed by a verify operation for the data word. in one embodiment, a method of writing data into a memory device is disclosed. the method comprises utilizing a pipeline to process write operations of a first plurality of data words addressed to a memory bank. the method further comprises writing a second plurality of data words and associated memory addresses into a cache memory, e.g., an e 1 register, wherein the cache memory is associated with the memory bank and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the memory bank or is to be re-written into the memory bank. further, the method comprises detecting a power down signal and responsive to the power down signal, transferring the second plurality of data words and associated memory addresses from the cache memory, e.g., the e 1 register, into a secure memory storage area reserved in the memory bank. finally, the method comprises powering down the memory device. it should be noted that in this embodiment only one dynamic redundancy register, e.g., the e 1 register may be used in the memory device. in other words, the memory device will have no e 2 register. in one aspect of this embodiment, the memory bank comprises a plurality of spin-transfer torque magnetic random access memory (stt-mram) cells. in another aspect, the method further comprises responsive to the power down signal, transferring any partially completed write operations of the pipeline to the secure memory storage area. in a different aspect, the method further comprises responsive to the power down signal, and before the transferring, copying any partially completed write operations of the pipeline to the cache memory. in one aspect of the embodiment, the transferring comprises utilizing a secure communication process that is substantially compliant with one of: voting; ecc encoding; use of multiple copies; comparing multiple copies; and voting from multiple copies. in another aspect, the power down signal originates from a system level software stack and represents a system wide orderly power down event. in a different aspect, the power down sequence is initiated when an analog detector detects that the operating power of the chip has decreased by a predetermined threshold level. in one aspect, the method further comprises removing a data word and its associated address from the cache memory responsive to an indication that the data word has been verified as properly written to the memory bank. in another, the method further comprises receiving a power up signal and responsive to the power up signal, transferring the second plurality of data words and associated memory addresses from the secure memory storage area to the cache memory and processing the second plurality of data words from the cache memory, through the pipeline for writing into the memory bank. in one embodiment, a method of writing data into a memory device is disclosed. the method comprises utilizing a pipeline to process write operations of a first plurality of data words addressed to a memory bank. the method further comprises writing a second plurality of data words and associated memory addresses into a cache memory, wherein the cache memory is associated with the memory bank and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the memory bank or is to be re-written into the memory bank. the method also comprises detecting a power down signal and responsive to the power down signal, and before the memory device is powered down, processing data words of the second plurality of data words and associated memory addresses through the pipeline to write data into the memory bank. the method finally comprises powering down the memory device. in one aspect, the memory bank comprises a plurality of spin-transfer torque magnetic random access memory (stt-mram) cells. in another aspect, the power down signal originates from a system level software stack and represents a system wide orderly power down event. in a different aspect, the power down sequence is initiated when an analog detector detects that the operating power of the chip has decreased by a threshold level. in one aspect, the method further comprises removing a data word and its associated address from the cache memory responsive to an indication that the data word has been verified as properly written to the memory bank. in yet another aspect, the method further comprises subsequent to the processing the data words and before the power down, transferring any unprocessed data words of the second plurality of data words from the cache memory to a secure memory storage area of the memory bank. in one aspect, the transferring comprises utilizing a secure communication process substantially compliant with one of: voting; ecc encoding; use of multiple copies; comparing multiple copies; and voting from multiple copies. in one aspect, the method also comprises receiving a power up signal and responsive to the power up signal, transferring any data words and associated memory addresses from the secure memory storage area to the cache memory and processing the data words, from the cache memory, through the pipeline for writing into the memory bank. in one embodiment, a method of writing data into a memory device is disclosed. the method comprises utilizing a pipeline to process write operations of a first plurality of data words addressed to a memory bank. the method further comprises writing a second plurality of data words and associated memory addresses into a cache memory, wherein the cache memory is associated with the memory bank and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the memory bank or is to be re-written into the memory bank. the method also comprises detecting a power down signal and responsive to the power down signal, transferring the second plurality of data words and associated memory addresses from the cache memory into a secure memory storage area in the memory bank. additionally, the method comprises detecting a power up signal and responsive to the power up signal, and before the memory device is powered up, transferring the second plurality of data words and associated memory addresses from the secure memory storage area to the cache memory. further, the method comprises responsive to the transferring, and before the memory device is powered up, processing the second plurality of data words and associated memory addresses from the cache memory to the pipeline for writing data to the memory bank during power up. in one aspect, the memory bank comprises a plurality of spin-transfer torque magnetic random access memory (stt-mram) cells. further, in one aspect, the method further comprises responsive to the power down signal, transferring any partially completed write operations of the pipeline to the secure memory storage area. in another aspect, the method further comprises responsive to the power down signal, copying any partially completed write operations of the pipeline to the cache memory. in one aspect, the transferring comprises utilizing a secure communication process substantially compliant with one of: voting; ecc encoding; use of multiple copies; comparing multiple copies; and voting from multiple copies. in one embodiment, the power down signal originates from a system level software stack and represents a system wide orderly power down event. in a different aspect, the power down sequence is initiated when an analog detector detects that the operating power of the chip has decreased by a threshold level. in another aspect, the method further comprises removing a data word and its associated address from the cache memory responsive to an indication that the data word has been verified as properly written to the memory bank. in one embodiment, a memory pipeline for performing a write operation in a memory device is disclosed. the memory pipeline comprises an initial pipe-stage comprising an input register operable to receive a first data word and an associated address to be written into a memory bank. the memory pipeline also comprises a pre-read register of the first pipe-stage coupled to the input register and operable to receive the first data word and the associated address from the input register and further operable to pre-read a second data word stored in the memory bank at the associated address, and wherein the pre-read register is further operable to store mask bits associated with pre-reading the second data word, wherein the mask bits comprise information regarding a bit-wise comparison between the first data word and the second data word. further, the memory pipeline comprises a write register of the second pipe-stage operable to receive the first data word, the associated address and the mask bits from the pre-read register, wherein the write register is further operable to use information from the mask bits to write the first data word into the memory bank by changing those bits in the first data word that differ from the second data word, and wherein the second pipe-stage follows the first pipe-stage. in one aspect the memory bank comprises memory cells that are spin-transfer torque magnetic random access memory (stt-mram) cells. in another aspect, the pre-read register further comprises ecc bits for correcting bit errors in data words read from the memory bank. in one aspect, the pre-read is performed as part of a bit redundancy remapping operation. in another aspect the pre-read register stores the mask bits in a first level dynamic redundancy register. in a further aspect, the memory pipeline further comprises a delay register of the third pipe-stage operable to provide delay cycles between the write register and a verify register, wherein the delay cycles are used to find a verify operation in a first level dynamic redundancy register with a row address in common with the first data word wherein the third pipe-stage follows the second pipe-stage. in one aspect the delay register is further operable to receive the first data word and associated address from the write register. in another aspect, the delay register is further operable to transmit the first data word and associated address to the first level dynamic redundancy register responsive to receipt of a row address change signal. in one aspect, the memory pipeline further comprises a verify register of the fourth pipe-stage operable to receive the first data word and associated address from the delay register, and further operable to read a third data word at the associated address from the memory bank, wherein the fourth pipe-stage follows the third pipe-stage. further, the memory pipeline comprises compare logic operable to compare contents of the first data word and the third data word to determine if the first data word wrote correctly to the memory bank. in one embodiment, a memory pipeline for performing a write operation in a memory device is disclosed. the memory pipeline comprises an initial pipe-stage comprising an input register operable to receive a first data word and an associated address to be written into a memory bank. further, the pipeline comprises a first write register of a first pipe-stage coupled to the input register and operable to receive the first data word and the associated address from the input register in a first clock cycle, wherein the first write register is further operable to perform a first attempt at writing the data word into the memory bank at a location corresponding to the associated address. the pipeline also comprises a second write register of the second pipe-stage coupled to the first write register and operable to receive the first data word and the associated address from the first write register in a second clock cycle, wherein the second write register is further operable to perform a second attempt at writing the first data word into the memory bank at the location corresponding to the associated address, and further wherein a second data word is input into the first write register in the second clock cycle subsequent to writing the first data word into the second write register from the first write register, wherein the second pipe-stage follows the first pipe-stage. in one aspect, the pipeline further comprises a delay register of the third pipe-stage operable to receive the first data word and the associated address from the second write register on a third cycle, wherein a third data word is input into the first write register and the second data word is transferred from the first write register into the second write register for a second attempt at writing the second data word on the third cycle into the memory bank, wherein the third pipe-stage follows the second pipe-stage. in one aspect, the delay register is further operable to provide a delay cycle between the write register and a verify register, wherein the delay cycle is used to find a verify operation in a first level dynamic redundancy register with a row address in common with the first data word. in one aspect, the delay register is further operable to transmit the first data word and the associated address to the first level dynamic redundancy register responsive to receipt of a row address change signal. in another aspect, the memory pipeline further comprises a verify register of the fourth pipe-stage coupled to the delay register wherein the verify register is operable to receive the first data word from the delay register on a fourth clock cycle, and wherein the verify register performs a read operation on the memory bank at the associated address to determine whether the first data word wrote correctly to the memory bank, wherein the fourth pipe-stage follows the third pipe-stage. in yet another aspect, the memory pipeline also comprises compare logic operable to perform a compare operation between the first data word in the verify register and a data word read from the memory bank at the associated address in the verify register. in one aspect, the memory pipeline additionally comprises a verify results register of the fifth pipe-stage operable to receive the first data word and the associated address from the verify register, wherein responsive to a determination that a verify operation associated with the compare operation failed, the verify results register is further operable to transfer the first data word and the associated address to a first level dynamic redundancy register, wherein the fifth pipe-stage follows the fourth pipe-stage. in one aspect, the memory cells of the memory bank comprise spin-transfer torque magnetic random access memory (stt-mram) cells. in another aspect responsive to receiving a read operation, write operations associated with the memory pipeline are stalled until the read operation is completed. in one embodiment of the present invention, a memory device for storing data is disclosed. the memory device comprises a memory bank comprising a plurality of addressable memory cells configured in a plurality of segments wherein each segment contains n rows per segment, wherein the memory bank comprises a total of b entries, and wherein the memory cells are characterized by having a prescribed write error rate, e. the memory device also comprises a pipeline comprising m pipestages and configured to process write operations of a first plurality of data words addressed to a given segment of the memory bank. further, the memory comprises a cache memory, e.g., the e 1 register comprising y number of entries, the cache memory associated with the given segment of the memory bank wherein the cache memory is operable for storing a second plurality of data words and associated memory addresses, and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the given segment of the memory bank or is to be re-written into the given segment of the memory bank, and wherein the y number of entries is based on the m, the n and the prescribed word error rate, e, to prevent overflow of the cache memory. in one aspect, the y number of entries is at least (n*m)+(b*e) entries. in one aspect, the memory cells of the memory bank comprise spin-transfer torque magnetic random access memory (stt-mram) cells. in one aspect, the memory device further comprises a plurality of pipelines and a plurality of cache memories, and wherein further each segment of the plurality of segments has associated therewith a respective pipeline of the plurality of pipelines and a respective cache memory of the plurality of cache memories. in one aspect, the cache memory comprises one or more status indicators for indicating a partial occupancy level of the cache memory. in one aspect, the pipeline supports multiple write attempts for a given write operation. in another aspect, the pipeline supports a pre-read operation for a given write operation. in one aspect, the pipeline is operable to flush a currently processing first memory operation to the cache memory if a second memory operation enters the pipeline has a different row address as the first memory operation. in one embodiment, a memory device for storing data is disclosed. the memory device comprises a plurality of memory banks, wherein each memory bank comprises a plurality of addressable memory cells and a plurality of pipelines each comprising a plurality of pipe-stages, wherein each pipeline is associated with a respective one of the plurality of memory banks, and wherein each pipeline is configured to process write operations of a first plurality of data words addressed to its associated memory bank. the memory device further comprises a plurality of cache memories, wherein each cache memory is associated with a respective one of the plurality of memory banks and a respective one of the plurality of pipelines, and wherein each cache memory is operable for storing a second plurality of data words and associated memory addresses, and wherein further each data word of the second plurality of data words is either awaiting write verification associated with the given segment of an associated memory bank or is to be re-written into the given segment of the associated memory bank. in one aspect, the addressable memory cells of the associated memory bank comprise spin-transfer torque magnetic random access memory (stt-mram) cells. in one aspect, each pipeline is operable to flush a currently processing first memory operation to an associated cache memory if a second memory operation that enters the pipeline has a different row address as the first memory operation. in another aspect, each cache memory comprises one or more status indicators for indicating a partial occupancy level of the cache memory. in one aspect, each pipeline supports multiple write attempts for a given write operation. in another aspect, each pipeline supports a pre-read operation for a given write operation. in one embodiment, a memory device for storing data is disclosed. the memory device comprises a memory bank comprising a memory array of addressable memory cells and a pipeline configured to process read and write operations addressed to the memory bank. further, the memory comprises an x decoder circuit coupled to the memory array for decoding an x portion of a memory address for the memory array and a y multiplexer circuit coupled to the memory array and operable to simultaneously multiplex across the memory array based on two y portions of memory addresses and, based thereon with the x portion, for simultaneously writing a value and reading a value associated with two separate memory cells of the memory array, wherein the x decoder and the y multiplexer comprise a read port and a write port which are operable to simultaneously operate with respect to the memory array. in one aspect, the x decoder is operable to assert a row line of the memory array and wherein the two separate memory cells share the row line in common. in another aspect, the read port and the write port allow a write operation and a read-verify operation, that share a common row, to simultaneously access the memory array. in one aspect, the read port and the write port allow a write operation and a read-verify operation, that share a common row and that have different y portions, to simultaneously access the memory array. in another aspect, the addressable memory cells comprise spin-transfer torque magnetic random access memory (stt-mram) cells. in one aspect of the invention, the x portion of the memory address decodes to a common row line shared by the two separate memory cells of the memory array and wherein further the two y portions of memory addresses respectively select first and second sets of bit lines associated with the two separate memory cells of the memory array. in one aspect, the memory device further comprises a plurality of input/output channels, the plurality of input/output channels coupled to the y multiplexer circuit. these and other objects, features, aspects, and advantages of the embodiments will become better understood with reference to the following description and accompanying drawings. moreover, the object, features, aspect, and advantages of the embodiments can be modified and combined without departing from the teachings of the present disclosure. brief description of the drawings the accompanying drawings, which are included as part of the present specification, illustrate the presently preferred embodiments and, together with the general description given above and the detailed description given below, serve to explain and teach the principles of the mtj devices described herein. fig. 1 is a block diagram of exemplary memory device of the present disclosure having redundancy registers. fig. 2 is an exemplary embodiment for a process flow showing a write operation using exemplary memory device of the present disclosure and illustrates the high-level write operation performed on a memory device. fig. 3 is a block diagram of exemplary embodiment of a memory device of the present disclosure having dynamic redundancy registers. fig. 4 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing y-mux structure. fig. 5 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows verification and re-write operations. fig. 6 is an exemplary process flow showing an embodiment of a system read operation using an embodiment of memory device of the present disclosure. fig. 7 is a block diagram of an embodiment of a memory device showing a first level dynamic redundancy register. fig. 8 is a block diagram of an embodiment of a memory device of the present disclosure showing a last level dynamic redundancy register. fig. 9 is a block diagram of exemplary memory device of the present disclosure having a single redundancy register. fig. 10 depicts an exemplary embodiment for a process flow showing the processing of pending memory related operations in a dynamic redundancy register on power down in an exemplary memory device of the present disclosure. fig. 11 depicts an exemplary embodiment for a process flow showing the processing of pending memory related operations in a secure memory storage area on power up using a dynamic redundancy register in an exemplary memory device of the present disclosure. fig. 12 depicts an exemplary embodiment for a process flow showing the processing of performing a blind save of the contents of a dynamic redundancy register on power down in an exemplary memory device of the present disclosure. fig. 13 depicts an exemplary embodiment for a process flow showing the processing of performing a blind recall of the contents of the memory bank into a dynamic redundancy register on power up in an exemplary memory device of the present disclosure. fig. 14 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows pipestages for performing a pre-read operation for a write operation. fig. 15 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows an additional cycle for write operation for storing a data word. fig. 16 is a block diagram of an exemplary pipeline structure for a memory device that comprises an additional write stage in accordance with an embodiment of the present invention. fig. 17 illustrates the manner in which a memory bank can be segmented in accordance with an embodiment of the present invention. fig. 18 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing the operation of a row and column decoder in conjunction with a y-mux structure in accordance with an embodiment of the present invention. fig. 19 depicts an exemplary embodiment for a process flow showing the manner in which a pre-read register is used to perform a write operation in an exemplary memory device of the present disclosure. fig. 20 is a block diagram of an exemplary pipeline structure for a memory device that comprises a pre-read pipe-stage for a write operation in accordance with an embodiment of the present invention. fig. 21 illustrates a smart design for a dynamic redundancy register in accordance with an embodiment of the present invention. the figures are not necessarily drawn to scale and the elements of similar structures or functions are generally represented by like reference numerals for illustrative purposes throughout the figures. the figures are only intended to facilitate the description of the various embodiments described herein; the figures do not describe every aspect of the teachings disclosed herein and do not limit the scope of the claims. detailed description the following description is presented to enable any person skilled in the art to create and use dynamic redundancy registers that allow devices, and especially magnetic semiconductor device such as an mram, to operate with high write error rate (wer). each of the features and teachings disclosed herein can be utilized separately or in conjunction with other features to implement the disclosed system and method. representative examples utilizing many of these additional features and teachings, both separately and in combination, are described in further detail with reference to the attached drawings. this detailed description is merely intended to teach a person of skill in the art further details for practicing preferred aspects of the present teachings and is not intended to limit the scope of the claims. therefore, combinations of features disclosed in the following detailed description may not be necessary to practice the teachings in the broadest sense, and are instead taught merely to describe particularly representative examples of the present teachings. in the following description, for purposes of explanation only, specific nomenclature is set forth to provide a thorough understanding of the present teachings. however, it will be apparent to one skilled in the art that these specific details are not required to practice the present teachings. fig. 1 is a block diagram of exemplary memory device of the present disclosure having dynamic redundancy registers (e 1 register 104 and e 2 register 106 , in this case). fig. 1 shows memory devices 100 described herein that includes memory bank 102 , e 1 register 104 , and e 2 register 106 . moreover, memory device 100 communicates with data signals, for example, address signal 108 , data word signal 110 , clock signal 112 , write and chip select signals 114 , power down signal 116 , power up signal 118 . note that fig. 1 illustrates certain teachings of the present disclosure. however, it should be understood that the specific signals 108 - 118 illustrated may be modified by those with ordinary skill in the art without departing from the teachings of the present disclosure. moreover, other communication interfaces, for example a double data rate (ddr) interface, to the memory device may be used. although shown with only two dynamic redundancy registers here (e 1 register 104 and e 2 register 106 ) and one memory bank (memory bank 102 ), memory device 100 may comprise two or more dynamic redundancy registers and one or more memory banks. the two or more dynamic redundancy registers could be implemented using some combination e 1 register 104 and e 2 register 106 . the two or more dynamic redundancy registers may also operate hierarchically or in parallel. memory bank 102 comprises an array of data storage elements comprising data bits and may be implemented by volatile or non-volatile ram technologies such as static random-access memory (sram), dynamic random-access memory (dram), resistive random-access memory (rram), phase-change memory (pcm), mram, stt-mram, or other ram technologies. in an exemplary embodiment, memory bank 102 may include an error correcting code block (not pictured). the teachings of the present disclosure are especially beneficial when memory bank 102 comprises stt-mram which suffers from an inherently stochastic write mechanism, wherein bits have certain probability of write failure on any given write cycle. the teachings of the present disclosure allow memory bank 102 to be operated with high wer. however, many such errors can be corrected using the teachings of the present disclosure. operating with high wer may allow memory bank 102 to operate under other beneficial conditions. for example, memory bank 102 could operate under high write speed, low write voltage (which may enable higher bitcell endurance), reducing ecc bits, or increased ecc decode speed, among other beneficial conditions. in one embodiment, memory bank 102 may comprise 65,536×50 addressable bits. further, the 50 bits comprise a 32-bit data word and 18 parity bits for error correction. operations may be performed on memory bank 102 including system read, system write, re-write and verify operations, among other data manipulations. a particular operation, for example a write operation, may occur at a particular address within memory bank 102 . the operation may have a row address, indicating a word line, and a column address. the address for write operations may be communicated through a write port of memory bank 102 . the address for read or verify operations may be communicated through a read port of memory bank 102 . in one embodiment, memory bank 102 comprises a pseudo-dual port memory bank allowing memory device 100 to simultaneously (e.g., substantially within a memory device clock cycle) perform a write operation and a verify operation sharing a common row (word line) address. system read operations to memory bank 102 generally supersede write and verify operations. thus, system read operation would be performed before the scheduled write and verify operations. write and verify operation could then happen on a subsequent clock cycle. it should be noted that if a dual-port memory bank 102 is used, read and write operations may be simultaneously performed. in other words, a dual-port memory bank would also permit two write operations (or two read operations) to be performed simultaneously. by contrast, a pseudo-dual port memory bank can comprise two ports, however, both ports may not be designed to service the same operations. for example, typically a write operation requires a write driver with corresponding sense amplifiers that can support the higher current requirements of a write operation. in other words, a write driver tends to occupy more surface area on the chip as compared to a read driver because of the high current requirements for a write operation. a dual port memory bank optimizes both ports to support write operations, which, in turn, means that both ports can also support read operations because the requirements for read drivers are less stringent than for write drivers. a pseudo dual port memory bank, on the other hand, optimizes one of the ports to support a write operation and one of the ports to support a read operation. in the current case, because memory device 100 will be receiving a write and a verify operation sharing a common row (word line) address in the same clock cycle, a pseudo-dual port memory bank can be used to process the write and verify operation simultaneously. the e 1 register 104 is coupled to memory bank 102 and e 2 register 106 . the e 1 register 104 comprises an array of data storage elements comprising data bits and may be implemented by volatile and non-volatile ram technologies. the e 1 register 104 may also comprise control bits and communicate using control signals that maintain consistency of operations within memory device 100 . typically, data is more reliably written to e 1 register 104 than within memory bank 102 . thus, if memory bank 102 comprises stt-mram, then e 1 register 104 might comprise sram. in other embodiments, e 1 register may comprise non-volatile ram such as stt-ram. the e 1 register may also comprise a dual-port stt-ram to allow simultaneous read and write operations. in this case, e 1 register 104 can run at the same cycle throughput speed as a memory bank. the e 1 register 104 may also comprise content addressable memory (cam). in one embodiment, the e 1 register may be located off the memory chip and on a system card or even on the cpu. in other words, the e 1 register can be located on a different chip besides the memory chip. generally, e 1 register 104 stores data words and associated addresses for data in memory bank 102 that has not been verified or has failed verification. in one embodiment, e 1 register 104 may store data words that have not been verified. for example, e 1 register 104 receives a rowchg signal that indicates row address change within a pipeline structure of the present disclosure. the rowchg signal indicates that the data word and the associated address from the pipeline structure should be stored within e 1 register 104 . the rowchg signal may also indicate that that another data word and associated address should be transmitted from e 1 register 104 to the pipeline structure for a verify operation. if a pseudo-dual port memory bank is used, e 1 register 104 may choose a data word and an associated address such that they share a common row address with a data word in the write register of the pipeline structure. in this way, a write operation and a verify operation can be simultaneously performed since the data words share a common row address. in another embodiment, e 1 register 104 may store data words that have failed verification. for example, the pipeline structure may transmit a signal to e 1 register 104 indicating that a data word has failed to write (i.e., failed verification) to memory bank 102 . the pipeline structure may also transmit data word and associated address (in the case that e 1 register 104 does not already contain the data word and associated address) to e 1 register 104 in order to later try to re-write the data word to memory bank 102 . in another example, a read operation may occur and pipeline structure may determine that the read operation did not occur within a predetermined error budget. the pipeline structure may then transmit a signal indicating that the read operation failed and transmit the data word and associated address to e 1 register 104 for storage. from the preceding, one of ordinary skill in the art will understand that e 1 register 104 may store data words and associated addresses for future verification. for example, a data word may not have had an opportunity to verify due to a row address change. thus, e 1 register 104 may transmit the data word and associated address to the pipeline structure of the present disclosure during some subsequent clock cycle to verify the data word. typically, a control signal may indicate to e 1 register 104 that a row address change will occur or that memory bank 102 will become inactive during subsequent clock cycles. the e 1 register 104 may then determine the appropriate data word sharing a common row address with the data word to be written (in case of row address change) during the subsequent clock cycle. the e 1 register 104 then transmits the data word and associated address to verify register of the pipeline structure. in one embodiment, e 1 register 104 may also transmit the physical address within e 1 register 104 if the data word is already stored within e 1 register 104 . in this way, control bits associated with the data word may be updated. from the preceding, a person skilled in the art will understand that e 1 register 104 may also store data words for future re-write attempts. the e 1 register 104 may receive data words that have failed verification from the pipeline structure of the present disclosure. memory device 100 may have attempted a write operation and the data word failed a verify operation. memory device 100 may also have attempted a read operation and the data word may have failed to read within a specified error budget. in both cases, the pipeline structure of the present disclosure may transmit the data word to e 1 register 104 . memory bank 102 may become inactive during a subsequent cycle. the e 1 register 104 may then determine an appropriate data word to attempt to re-write to memory bank 102 . in this case, e 1 register 104 may transmit a data word and associated address to the pipeline structure. the e 1 register 104 transmits the data word such that a write register could re-write the data word during the clock cycle that memory bank 102 would otherwise be inactive. generally, e 1 register 102 may also relocate data words, associated addresses, and control bits to e 2 register 106 . if no more re-write attempts are desired, e 1 register 104 may relocate data word and associated address to e 2 register 106 . the e 1 register may also relocate data to memory bank 102 or e 2 register 106 on power down so that data is stored in non-volatile memory in the case that e 1 register 104 comprises volatile memory. the e 1 register 104 may also relocate data to e 2 register 106 in the case that e 1 register 104 lacks space for data words. the e 1 register comprises control bits and communicates using control signals. in one embodiment, e 1 register comprises valid bits indicating whether the associated data word is a valid entry within e 1 register. in another embodiment, e 1 register comprises fail count bits indicating the number of re-write attempts associated with a data word. in this way, memory device 100 may try only a specified number of re-write attempts. in another embodiment, e 1 register comprises bits indicating that the associated data word has not been verified due to row address change and should be verified. the e 2 register 106 is coupled to e 1 register 104 and may also be coupled to memory bank 102 . the e 2 register 106 comprises an array of data storage elements comprising data bits and may be implemented by volatile and non-volatile ram technologies. the e 2 register 106 may also comprise an ecc block and cam. the e 2 register 106 may comprise data words, associated addresses, and control bits. typically, e 2 register 106 will comprise a non-volatile memory technology, for example stt-mram. in one embodiment, the e 2 register may be located off the memory chip and on a system card or even on the cpu. in other words, the e 2 register can be located on a different chip besides the memory chip. the e 2 register 106 stores data words and associated addresses relocated from e 1 register 104 . in another embodiment, rather than storing data words and associated data words from e 1 register 104 , e 2 register 106 remaps those data words to addresses within memory bank 102 . for example, e 2 register 106 may store remap addresses in memory bank 102 . the e 2 register 106 then temporarily stores a data word from e 1 register and then writes it to an appropriate remap address in memory bank 102 . when a data word should be read, e 2 register contains the appropriate remap address for reading the data word from memory bank 102 . data words and associated addresses may be relocated to e 2 register 106 or remapped based on different conditions. in one embodiment, e 1 register 104 relocates data words and associated addresses to e 2 register 106 because the data words failed to write to memory bank 102 after the specified number of re-write attempts. in another embodiment, e 1 register 104 relocates data words and associated addresses to e 2 register 106 because power down signal 116 indicates that data word and associated address should be moved to non-volatile memory, such as e 2 register 106 comprising stt-mram. in one embodiment, e 1 register 104 may attempt to process any pending verifies or re-write attempts associated with data words stored in e 1 prior to relocating the contents of the e 1 register to the e 2 register upon receipt of the power down signal. in other words, when a power down signal is received, but before the chip powers down, the e 1 register can, in one embodiment, attempt to process all the entries within the e 1 register prior to storing the entries in the e 2 register. for example, the e 1 register may attempt sending data words associated with any pending re-write operations or verify operations to the pipeline structure to process them prior to moving them to the e 2 register. any operations that are successfully processed may then be deleted, overwritten or invalidated from the e 1 register and would not need to be stored in the e 2 register. any operations that are not successfully processed on power down, will be stored in the e 2 register. in another embodiment, e 1 register 104 relocates data words and associated addresses to e 2 register 106 because e 1 register 104 lacks space. one of ordinary skill in the art will understand that desired control bits may also be relocated with associated data word. in another embodiment, if data word fails to write to a physical address within e 2 register 106 after a predetermined number of write attempts a different physical address may be chosen for data word. the e 2 register 106 may also be coupled to an input register of a pipeline structure. in this way, e 2 register 106 may receive control signals indicating that a write operation for a data word sharing a common associated address with a data word within e 2 register 106 may be occurring. thus, control bits within e 2 register 106 may indicate that a data word within e 2 register 106 is invalid because of a system write operation. memory device 100 also communicates using exemplary signals 108 - 118 . address signal 108 comprises address within memory bank 102 of data to be written to or read from (or otherwise manipulated). data word signal 110 comprises a data word to be written to (or otherwise manipulated) memory bank 102 . clock signal 112 comprises a memory device 100 clock signal or other clock signal (such as for specific components within memory device 100 ). write and chip select signals 114 comprise signals used to determine the operation to be performed within memory bank 102 . for example, if write signal is high and chip select signal is low a read operation might be performed on memory bank 102 . power down signal 116 indicates whether power will be removed from memory device 100 or specific components within memory device 100 . thus, power down signal 116 may be used to determine that contents of e 1 register 104 should be written to memory or e 2 register 106 . as mentioned above, the e 1 register 104 may attempt to process any pending verifies or re-write attempts associated with data words stored in e 1 prior to relocating the contents of the e 1 register to the e 2 register upon receipt of the power down signal but before the device powers down. power up signal 118 indicates that power is provided to memory device 100 . power up signal may indicate that e 2 non-volatile memory contents should be loaded to e 2 volatile memory. one of ordinary skill in the art will recognize that the specific signals 108 - 118 may be modified without departing from the present disclosure. in one embodiment, upon receipt of the power up signal and before loading the memory contents to e 2 volatile memory, another attempt is made to process any pending verifies or re-write attempts associated with data words stored in the e 2 register. if the e 2 register is connected to the pipeline structure, the attempts to process the data words in the e 2 register may occur directly from the e 2 register. in a different embodiment, the e 2 register may need to move its contents to the e 1 register prior to attempting the verify and re-write operations through the pipeline. power down signal 116 may indicate that e 2 register 106 volatile memory contents should be moved to e 2 register 106 non-volatile memory. for example, e 2 register 106 volatile memory contents not already stored in e 2 non-volatile memory may be moved to e 2 register 106 non-volatile memory. again, in one embodiment, if the e 2 register is connected to the pipeline structure, upon receipt of the power down signal, the e 2 register may attempt to process any pending verify or re-write operations prior to moving the contents into non-volatile memory. in another embodiment, power down signal 116 may indicate that e 2 register 106 contents should be moved to non-volatile memory bank 102 . in another embodiment, power down signal 116 may indicate that certain data words within e 1 register 104 should be verified to memory bank 102 . in another embodiment, power down signal 116 indicates that certain data words within e 1 register 104 should be re-written to memory bank 102 . if the verify or re-write operations are unsuccessful, as mentioned above, the data words associated with those operations would then be moved to the e 2 register upon power down. fig. 9 is a block diagram of exemplary memory device of the present disclosure having a single dynamic redundancy register (e 1 register 904 in this case). fig. 9 shows memory devices 900 described herein that includes memory bank 902 and e 1 register 904 . as compared to the embodiment shown in fig. 1 , the embodiment of fig. 9 does not comprise an e 2 register. instead memory bank 902 comprises a secure memory storage area 932 that may be reserved for the e 1 register to relocate data words, associated addresses, and control bits. in one embodiment, the reserved secured memory storage area 932 performs substantially the same function as the e 2 register described in fig. 1 . however, instead of dedicating a separate dedicated register, the e 1 register is able to relocate its contents to a secured location in memory as will be further described below. additionally, memory device 900 communicates with data signals, for example, address signal 908 , data word signal 910 , clock signal 912 , write and chip select signals 914 , power down signal 916 , and power up signal 918 . note that fig. 9 illustrates certain teachings of the present disclosure. however, it should be understood that the specific signals 908 - 918 illustrated may be modified by those with ordinary skill in the art without departing from the teachings of the present disclosure. moreover, other communication interfaces, for example a double data rate (ddr) interface, to the memory device may be used. although shown with only one memory bank (memory bank 102 ), memory device 900 may comprise one or more memory banks. note further that while write and chip select signals have been lumped into one signal 914 in fig. 9 , write, chip select and read may all comprise separate signals to memory device 900 . memory bank 902 comprises an array of data storage elements comprising data bits and may be implemented by volatile or non-volatile ram technologies such as static random-access memory (sram), dynamic random-access memory (dram), resistive random-access memory (rram), phase-change memory (pcm), mram, stt-mram, or other ram technologies. in an exemplary embodiment, memory bank 902 may include an error correcting code block (not pictured). as noted above, the teachings of the present disclosure are especially beneficial when memory bank 902 comprises stt-mram which suffers from an inherently stochastic write mechanism, wherein bits have certain probability of write failure on any given write cycle. the teachings of the present disclosure allow memory bank 902 to be operated with high wer. however, many such errors can be corrected using the teachings of the present disclosure. operating with high wer may allow memory bank 902 to operate under other beneficial conditions. for example, memory bank 902 could operate under high write speed, low write voltage (which may enable higher bitcell endurance), reducing ecc bits, or increased ecc decode speed, among other beneficial conditions. in one embodiment, memory bank 902 may comprise 65,536×50 addressable bits for instance. further, the 50 bits comprise a 32-bit data word and 18 parity bits for error correction. operations may be performed on memory bank 902 including system read, system write, re-write and verify operations, among other data manipulations. a particular operation, for example a write operation, may occur at a particular address within memory bank 902 . the operation may have a row address, indicating a word line, and a column address. the address for write operations may be communicated through a write port of memory bank 902 . the address for read or verify operations may be communicated through a read port of memory bank 902 . in one embodiment, memory bank 902 comprises a pseudo-dual port memory bank allowing memory device 900 to simultaneously (e.g., substantially within a memory device clock cycle) perform a write operation and a verify operation sharing a common row (word line) address. system read operations to memory bank 902 generally supersede write and verify operations. thus, system read operation would be performed before the scheduled write and verify operations. write and verify operation could then happen on a subsequent clock cycle. as explained above, a pseudo-dual port memory bank can used to implement the write and verify operation on the same clock cycle. the e 1 register 904 is coupled to memory bank 902 . the e 1 register 904 comprises an array of data storage elements comprising data bits and may be implemented by volatile and non-volatile ram technologies. the e 1 register 904 may also comprise control bits and communicate using control signals that maintain consistency of operations within memory device 900 . typically, data is more reliably written to e 1 register 904 than within memory bank 902 . thus, if memory bank 902 comprises stt-mram, then e 1 register 904 might comprise sram. in other embodiments, e 1 register may comprise non-volatile ram such as stt-ram. the e 1 register may also comprise a dual-port stt-ram to allow simultaneous read and write operations. in this case, e 1 register 904 can run at the same cycle throughput speed as a memory bank. the e 1 register 904 may also comprise content addressable memory (cam). generally, e 1 register 904 stores data words and associated addresses for data in memory bank 902 that have not been verified or have failed verification. in one embodiment, e 1 register 904 may store data words that have not been verified. for example, e 1 register 904 receives a rowchg signal that indicates row address change within a pipeline structure of the present disclosure. the rowchg signal indicates that the data word and the associated address from the pipeline structure should be stored within e 1 register 904 . the rowchg signal may also indicate that that another data word and associated address should be transmitted from e 1 register 904 to the pipeline structure for a verify operation. if a pseudo-dual port memory bank is used, e 1 register 904 may choose a data word and an associated address such that they share a common row address with a data word in the write register of the pipeline structure. in this way, a write operation and a verify operation can be simultaneously performed since the data words share a common row address. in another embodiment, e 1 register 904 may store data words that have failed verification. for example, the pipeline structure may transmit a signal to e 1 register 904 indicating that a data word has failed to write (e.g., failed verification) to memory bank 902 . the pipeline structure may also transmit data word and associated address (in the case that e 1 register 904 does not already contain the data word and associated address) to e 1 register 904 in order to later try to re-write the data word to memory bank 902 . in another example, a read operation may occur and pipeline structure may determine that the read operation did not occur within a predetermined error budget. the pipeline structure may then transmit a signal indicating that the read operation failed to occur within the error budget and transmit the data word and associated address to e 1 register 904 for storage. from the preceding, one of ordinary skill in the art will understand that e 1 register 904 may store data words and associated addresses for future verification. for example, a data word may not have had an opportunity to verify due to a row address change. thus, e 1 register 904 may transmit the data word and associated address to the pipeline structure of the present disclosure during some subsequent clock cycle to verify the data word. typically, a control signal may indicate to e 1 register 904 that a row address change will occur or that memory bank 902 will become inactive during subsequent clock cycles. the e 1 register 904 may then determine the appropriate data word sharing a common row address with the data word to be written (in case of row address change) during the subsequent clock cycle. the e 1 register 904 then transmits the data word and associated address to verify register of the pipeline structure. in one embodiment, e 1 register 904 may also transmit the physical address within e 1 register 904 if the data word is already stored within e 1 register 904 . in this way, control bits associated with the data word may be updated. from the preceding, a person skilled in the art will understand that e 1 register 904 may also store data words for future re-write attempts. the e 1 register 904 may receive data words that have failed verification from the pipeline structure of the present disclosure. memory device 900 may have attempted a write operation and the data word failed a verify operation. memory device 900 may also have attempted a read operation and the data word may have failed to read within a specified error budget. in both cases, the pipeline structure of the present disclosure may transmit the data word to e 1 register 904 . memory bank 902 may become inactive during a subsequent cycle. the e 1 register 904 may then determine an appropriate data word to attempt to re-write to memory bank 902 . in this case, e 1 register 904 may transmit a data word and associated address to the pipeline structure. the e 1 register 904 transmits the data word such that a write register could re-write the data word during the clock cycle that memory bank 902 would otherwise be inactive. in the embodiment of fig. 9 , the e 1 register 902 may relocate data words, associated addresses, and control bits to secure memory storage 932 in memory bank 902 . if no more re-write attempts are desired, e 1 register 904 may relocate data word and associated address to secure memory storage 332 . the e 1 register may also relocate data to secure memory storage 932 on power down so that data is stored in non-volatile memory in the case that e 1 register 104 comprises volatile memory. as mentioned above, generally, e 1 register 904 stores data words and associated addresses for data in memory bank 902 that have not been verified or have failed verification. processing operations pending in a dynamic redundancy register prior to powering down in one embodiment, upon receiving the power down signal, the e 1 register 904 may attempt to perform all the pending operations associated with the data words stored in the e 1 register prior to the device shutting down. for example, the e 1 register may attempt to store all the data words to be re-written back into memory to the targeted locations in the memory bank 102 using the associated addresses for the data words (also stored within e 1 ). it should be noted, however, that prior to attempting pending operations stored in the e 1 register, the memory device will first flush out the pipeline and finish up any pending operations in the pipeline from before the power down signal was received. note that, in one embodiment, the power down signal originates from a system level software stack and represents a system wide orderly power down event. however, in a different embodiment, the power down signal may not be part of a system wide orderly power down event. in other words, an analog detector may be configured to monitor the power level of the chip (e.g., a vcc power supply pin) and initiate a power down sequence if the power level of the chip falls below a certain threshold level, e.g., falls 10% or more. further, one or more capacitors may be configured to hold charge in order to sustain the power level above a threshold level, which allows the entire power down sequence to finish to completion. in one embodiment, a status pin(s) or register may be configured that allows the system to determine whether a power down sequence is complete. this status pin(s) or register may be used whether the shut down sequence is a result of an orderly shut down process or not. the status pin(s) or register may, for example, be associated with a timer that is set to allow the system enough time to run the entire power down sequence to completion. as mentioned above, the e 1 register may comprise data words that have not yet been verified or that have failed verification. upon receiving the power down signal, but before powering down, the e 1 register may attempt to perform all the pending verify operations and move all the data words associated with pending re-write operations (e.g. operations that have failed verification) stored within it to the appropriate corresponding locations in the memory bank. in this embodiment, the power down sequence will typically take longer because it may take a few cycles for the e 1 register to attempt to perform all the pending verify or re-write operations. in one embodiment, the power down signal 916 from the user or system warns the e 1 register 904 to expect a shut down sequence. upon notification of the power down signal, the e 1 register can then attempt to perform the pending verify and re-write operations. in one embodiment, an option bit (or bits) or pin(s) (not shown) is provided to the user to disable the processing of the contents of the e 1 register prior to shutting down. for example, if a user wants to avoid a long power down sequence, an option may be provided to disable this scheme. by way of further example, the option bit(s) may be used to disable the scheme during a test mode. in one embodiment, the e 1 register may simply transmit the data words to the appropriate registers in the pipeline structure. for example, a data word to be re-written into the memory bank may be transmitted to the write register in the pipeline from the e 1 register. from the pipeline, the data can be directed to the targeted locations within the memory bank 902 . another data word to be verified may be transferred to the verify register in the pipeline. further details regarding the pipeline are provided in connection with fig. 5 . in one embodiment, if the verify operations or the attempt to re-write the data words back to memory succeed, the corresponding entries for the data words in the e 1 register may be deleted prior to shutting down. in other words, any data words that were successfully re-written or verified can be deleted from the e 1 register prior to shutting down. any data words in the e 1 register that could not be successfully re-written or verified prior to shutting down will be stored in secure memory storage area 932 . in one embodiment, where e 1 comprises volatile memory, the data words that were successfully re-written or verified do not need to be pro-actively deleted, instead they will be deleted automatically once the power down sequence completes. memory bank 902 can comprise a secure area reserved for e 1 register to transfer its contents into upon shutting down. in one embodiment, the memory device 900 ensures that data is written securely to the secure memory storage area 932 by using one or multiple schemes including voting, error-correcting code (ecc), or storing multiple copies. for example, in one embodiment, multiple copies of each of the data words can be written into secure memory storage area 932 . when one of the data words needs to be read, each of the copies of the data word are read from the secure memory storage area and compared to determine if the data between all the copies is consistent. in case of inconsistency, a voting scheme is used to determine the correct data word. in other words, the most frequently occurring version of the data word between the various copies is selected as the data word. in another embodiment, ecc is used to ensure that the data words are error corrected to ensure that they are written accurately into the secure memory storage area 932 . processing operations pending in secured memory location upon powering up using a dynamic redundancy register in one embodiment, upon power up of the memory device and receipt of power up signal 918 , but before the device enters mission mode (or starts accepting commands), another attempt can be made to perform all the pending re-write or verify using the associated addresses for the data words. as mentioned previously, subsequent to powering down, the secure memory storage area will comprise data words (with their associated addresses) that have not yet been verified or that have failed verification. the pending re-write or verify operations will now be stored in non-volatile memory in secure memory storage area 932 where they were re-located to following power down. the verify and re-write operations can be directly attempted from the secure memory storage area 932 or they can be recalled to the e 1 register prior to processing the pending operations. if the contents of secure storage area 932 are moved to the e 1 register prior to re-attempting the pending operations, subsequent to the receipt of the power up signal 918 , the e 1 register may attempt to perform all the pending verify operations and move all the data words associated with pending re-write operations (e.g. operations that have failed verification) to the appropriate corresponding locations in the memory bank. alternatively, secure memory storage area 932 may be connected to the pipeline structure and the data words for the pending operations can be directed directly from secure memory storage area 932 to the pipeline structure. for example, a re-write operation can be sent directly from the secure memory storage area to a write register in the pipeline structure. similarly, a pending verify operation may be sent to a verify register in the pipeline structure directly from the secure memory storage area. the verify and re-write operations that do not complete successfully can be transferred to the e 1 register. in other words, the verify and re-write operations that cannot complete in the specified amount of time are transferred to the e 1 register. it should be noted that power up sequence in this scheme will typically take longer because it may take a few cycles to attempt to perform all the pending verify or re-write operations. in one embodiment, an option bit(s) or pin(s) (not shown) can be set to determine whether to enable or disable this feature. some users, for example, may not want a long power up sequence. in such cases, an option bit may be provided to users to disable this feature. in one embodiment, the data words associated with pending operations may be simply transmitted to the appropriate registers in the pipeline structure (from either the e 1 register or the secured memory storage). from the pipeline, the data can be directed to their targeted locations within the memory bank 902 . in one embodiment, if the attempt to verify or write the data words back to memory on power up succeeds, the corresponding entries for the data words in the secure memory storage area 932 or the e 1 register may be deleted prior to shutting down. in other words, any data words that were successfully re-written or verified can be deleted from both the secure memory storage area 932 and the e 1 register 904 . any data words that could not be successfully re-written or verified subsequent to powering up will be stored in the e 1 register. performing a blind save into a dynamic redundancy register on power down and a blind recall into a dynamic redundancy register on power up in one embodiment, instead of attempting to process entries in the e 1 register on power down, the memory device blindly transfers all the contents of the e 1 register into secure memory storage area 932 on power down. as mentioned previously, the power down signal 916 can be used to indicate that a power down sequence is expected. in response to the power down signal, e 1 register 904 can dump the entirely of its contents into secure memory storage area 932 . the blind save on power down will typically require more time than a regular power down sequence, but will not consume as many cycles as trying to execute pending operations in the e 1 register prior to shut down. in one embodiment, the memory device 900 ensures that data is written securely to the secure memory storage area 932 by using one or multiple schemes including voting, error-correcting code (ecc), or storing multiple copies. for example, in one embodiment, multiple copies of each of the data words can be written into secure memory storage area 932 . when one of the data words needs to be read, each of the copies of the data word are read from the secure memory storage area and compared to determine if the data between all the copies is consistent. in case of inconsistency, a voting scheme can be used to determine the correct data word. in other words, the most frequently occurring version of the data word between the various copies is selected as the data word. in another embodiment, ecc is used to ensure that the data words are error corrected to ensure that they are written accurately into the secure memory storage area 932 . in one embodiment, instead of attempting to process pending verify and re-write entries from the secure memory storage area 932 on power up, the memory device blindly transfers all the contents from the secure area of the memory array into the e 1 register. in other words, no attempt is made to process the operations associated with the data words stored in the secure memory storage area 932 on power up. the data words are simply saved to the e 1 register. it should be noted that the design for memory device 900 does not necessitate attempting pending verify and re-write operations on both shut down and power up. in other words, memory device may attempt to process pending re-write and verify operations only on power up, but not on power down. alternatively, in one embodiment, memory device may attempt pending operations only on power down, but not during the power up sequence (e.g., not before the device enters mission mode). in a different embodiment, memory device may attempt pending operations both on power down and power up. in cases where the pending verify and re-write operations are not processed, the corresponding data words are either transferred directly from the e 1 register to the secure memory storage area 932 (on power down) or from the secure memory storage area to the e 1 register (on power up). the e 1 register 904 may also relocate data to secure memory storage 932 in the case that e 1 register 904 lacks space for data words. the e 1 register comprises control bits and communicates using control signals. in one embodiment, e 1 register comprises valid bits indicating whether the associated data word is a valid entry within e 1 register. in another embodiment, e 1 register comprises fail count bits indicating the number of re-write attempts associated with a data word. in this way, memory device 900 may try only a specified number of re-write attempts. in another embodiment, e 1 register comprises bits indicating that the associated data word has not been verified due to row address change and should be verified. memory device 900 also communicates using exemplary signals 908 - 918 . address signal 908 comprises address within memory bank 902 of data to be written to or read from (or otherwise manipulated). data word signal 910 comprises a data word to be written to (or otherwise manipulated) memory bank 902 . clock signal 912 comprises a memory device 900 clock signal or other clock signal (such as for specific components within memory device 900 ). write and chip select signals 914 comprise signals used to determine the operation to be performed within memory bank 902 . for example, if write signal is high and chip select signal is low a read operation might be performed on memory bank 902 . note that in such case write and chip select signals can be separate signals. power down signal 916 indicates whether power will be removed from memory device 900 or specific components within memory device 900 in accordance with an orderly shut down. thus, power down signal 916 may be used to determine that contents of e 1 register 904 should be written to secure memory storage area 932 as detailed above. further, as detailed above, in one embodiment, power down signal 916 may indicate that certain data words within e 1 register 904 should be verified to memory bank 902 . in another embodiment, power down signal 916 indicates that certain data words within e 1 register 904 should be re-written to memory bank 902 . power up signal 918 indicates that power is provided to memory device 900 . power up signal may indicate that contents of the non-volatile secure memory storage area 932 should be loaded to the e 1 volatile memory. further, as detailed above, in one embodiment, power up signal 918 may indicate that certain data words within secure memory storage 932 should be verified to memory bank 902 . in another embodiment, power up signal 918 indicates that certain data words within secure memory storage 932 should be re-written to memory bank 902 . one of ordinary skill in the art will recognize that the specific signals 908 - 918 may be modified without departing from the present disclosure. fig. 10 depicts an exemplary embodiment for a process flow 1000 showing the processing of pending memory related operations in a dynamic redundancy register on power down in an exemplary memory device of the present disclosure. at step 1002 , a power down signal 916 is received. as stated above, the power down signal originates from a system level software stack and represents a system wide orderly power down event. in a different embodiment, the power down sequence is initiated when an analog detector detects that the operating power of the chip has fallen below a threshold level as noted above. at step 1004 , the memory device 900 determines if an option bit or pin is set for enabling the processing of pending operations in a dynamic redundancy register prior to shutting down. if the option bit or pin is set, then at step 1006 the memory device processes data words associated with pending verify operations in the e 1 register 904 . in other words, any verifies for which corresponding data words and addresses are stored in the e 1 register 904 are attempted prior to powering down. similarly, at step 1008 , the memory device processes any pending re-write operations in the e 1 register. data words corresponding to any verifies or re-writes that are successful are deleted from the dynamic redundancy register at step 1010 . as noted above, if the dynamic redundancy register comprises volatile memory then a pro-active deletion step is not necessary. at step 1012 , the remaining data words, if any, corresponding to operations that did not complete successfully are transferred to non-volatile secure memory storage area 932 . as noted previously, operations may not complete successfully because of certain specification mandated time limits on the power down sequence. at step 1018 , the memory device is ready for power down and/or powers down. alternatively, if at step 1004 , the option bit is not set, then at step 1014 all the contents of the e 1 register are re-located directly to the non-volatile secure memory storage area 932 without attempting any of the verify and re-write operations associated with data words stored in the e 1 register. at step 1016 , the memory device powers down. fig. 11 depicts an exemplary embodiment for a process flow 1100 showing the processing of pending memory related operations in a secure memory storage area on power up using a dynamic redundancy register in an exemplary memory device of the present disclosure. at step 1102 , a power up signal 918 is received from system level resources. at step 1104 , the memory device 900 determines if an option bit is set for enabling the processing of pending operations in a secure memory storage area using a dynamic redundancy register prior to powering up. if the option bit is set, then at step 1106 the memory device processes data words associated with pending verify operations in the secure memory storage area 932 . in other words, any verifies for which corresponding data words and addresses are stored in the secure memory are attempted prior to powering up. similarly, at step 1008 , the memory device processes any pending re-write operations in the secure memory area 932 . as noted above, the data words and addresses associated with the pending verify and re-write operations can be injected directly into the pipeline structure from the secure memory storage area. alternatively, in a different embodiment, the verify and re-write operations can be attempted by first transferring the corresponding data words and addresses to a dynamic redundancy register, e.g. the e 1 register, then to the pipeline. data words corresponding to any verifies or re-writes that are successful are deleted from the secure memory storage area 932 (or the e 1 register if transferred there prior to attempting the operations) at step 1110 . if the verifies and re-writes are attempted directly from the secure memory storage, then at step 1112 , the remaining data words corresponding to operations that did not complete successfully are transferred to the e 1 register. as noted previously, operations may not complete successfully because of certain specification mandated time limits on the power up sequence. at step 1112 , the memory device is ready to power up and/or powers up. alternatively, if at step 1104 , the option bit is not set, then at step 1114 all the contents of the secure memory storage area 932 are re-located directly to the dynamic redundancy register without attempting any of the verify and re-write operations associated with data words stored in the secure memory storage. at step 1116 , the memory device powers down. fig. 12 depicts an exemplary embodiment for a process flow 1200 showing the processing of performing a blind save of the contents of a dynamic redundancy register on power down in an exemplary memory device of the present disclosure. upon receipt of a power down signal 916 at step 1206 , all the contents of the dynamic redundancy register (e.g. the e 1 register) are transferred to secure storage location 932 without attempting to perform any of the operations associated with the data words stored in the e 1 register. at step 1206 , the memory device is then powered off. fig. 13 depicts an exemplary embodiment for a process flow 1300 showing the processing of performing a blind recall of the contents of the memory bank into a dynamic redundancy register on power up in an exemplary memory device of the present disclosure. upon receipt of a power up signal 918 at step 1310 , at step 1312 , all the contents of the secure memory storage area 932 are transferred to the dynamic redundancy register (e.g. the e 1 register) without attempting to perform any of the operations associated with the data words stored in the secure memory storage area. at step 1314 , the memory device is then powered off. fig. 2 depicts an exemplary embodiment for a process flow showing a write operation using an exemplary memory device of the present disclosure and illustrates the high-level write operation performed on a memory device. in step 202 , a write operation to be performed on primary memory (e.g., input register to memory bank 102 ) exists within a memory device. in step 202 , the system write operation may be performed on primary memory. in step 204 , it is determined whether system write operation was successful. for example, a verify operation could determine whether the write operation successfully occurred (for example, whether the data word was written with an acceptable error budget or perfectly) within primary memory. if the write operation was successful, process flow 200 proceeds to end step 210 . on the other hand, if the write operation was unsuccessful, a determination is made whether write operation should be retried in step 206 . one retry is illustrated during process flow 200 of fig. 2 , but as many tries to write data into memory bank may be tried as desired (0 to n retries). if a retry should be tried, the data will be written from e 1 register to primary memory when process flow 200 returns to step 202 . from this description a person having ordinary skill in the art will understand the operation of steps 202 - 206 and 210 . however, in some instances, a write operation from e 1 register to primary memory may be unsuccessful despite the total desired number of retries. in that case, if a determination is made at step 206 that no more tries should be made to write data from e 1 register to primary memory, process flow 200 will proceed to step 208 . in step 208 , data is written to alternate storage (e.g., from e 1 register to e 2 register). fig. 3 is a block diagram of exemplary embodiment of a memory device 300 of the present disclosure having dynamic redundancy registers. fig. 3 is a block diagram of memory device 300 described herein that include memory banks 304 and 306 , pipeline banks 308 and 310 , input register 312 , e 1 register 314 , and e 2 register 316 . memory device 300 communicates using signals 318 - 324 . memory device 300 includes ports 326 - 336 for performing read, write, and verify (or other data manipulation) operations on memory banks 304 and 306 . memory device 300 is described herein to describe aspects of the present disclosure. one of ordinary skill would understand how to modify memory device 300 without departing from the teachings of the present disclosure. thus, for example, the specific signals 318 - 324 may be modified by those with ordinary skill in the art without departing from the teachings of the present disclosure. although shown with only two dynamic redundancy registers here (e 1 register 314 and e 2 register 316 ) and two memory banks (memory banks 304 and 306 ), memory device 300 may comprise two or more dynamic redundancy registers and one or more memory banks. in one embodiment, memory device may only comprise a single dynamic redundancy register as discussed above. memory banks 304 and 306 have previously been described with respect to fig. 1 . memory banks 304 and 306 also include two ports ( 326 and 328 ; 332 and 334 , respectively) for performing read, write, and verify (or other data manipulation) operations. memory bank 304 could, for example, comprise data words having even addresses while memory bank 306 comprises data words having odd addresses. two ports 326 and 328 of memory bank 304 are coupled to bit lines of memory bank 304 . likewise, two ports 332 and 334 of memory bank 306 are coupled to bit lines of memory bank 306 . although shown with one read and one write port per memory bank, memory device 300 may comprise any desired number of read and write ports. for example, in one embodiment, memory device can comprise two write ports and a single read port. in one embodiment, a dual port memory bank is used. thus, each port 326 - 336 could perform simultaneous read and write operations. however, one of ordinary skill in the art will understand that the discussion proceeds with pseudo-dual port memory banks 304 - 306 in mind to highlight specific teachings of the present disclosure. the y-mux structure of the present disclosure allows pseudo-dual port memory banks 304 - 308 to perform simultaneous write and verify operations sharing common row address and different column address. as explained above, a pseudo-dual port memory bank may have one port optimized to perform write operations and another port optimized to perform read operations. as shown in fig. 3 , the memory device may comprise two memory banks. alternatively, the memory device may comprise several memory banks, e.g., 2, 4, 8, 16 etc. in one embodiment, each memory bank will be associated its own respective pipeline. in another embodiment, each memory bank will be associated with a dedicated pipeline and a dedicate device redundancy register. in other words, the memory device will contain an e 1 register for each of the memory banks. if each memory bank has a dedicated e 1 register, the size of each of the e 1 registers will likely be smaller than an e 1 register that services all memory banks. this will likely increase re-write and verify efficiency. with respect to memory bank 304 , write port 326 allows transmission of signals comprising write address and write data to memory bank 304 from pipeline bank 308 . port 328 allows transmission of data signals comprising read address or verify address to memory bank 304 from pipeline bank 308 . port 330 allows transmission of data signals comprising read data word from memory bank 304 to pipeline bank 308 . pipeline banks 308 and 310 comprise data registers for implementing the write, read, and verify (and other data manipulation) operations of the present disclosure. pipeline banks 308 and 310 are coupled to memory banks 304 and 306 , respectively, using pseudo-dual port structures, as explained above, for providing simultaneous write and verify operations. moreover, pipeline banks 308 and 310 are coupled to input register 312 . as explained in connection with fig. 5 , pipeline banks 308 and 310 implement a pipeline structure that allows verify and write operations to be simultaneously performed on memory banks 304 and 306 . moreover, pipeline banks communicate with e 1 register 314 to implement a pipeline structure of the present disclosure. input register 312 comprises data storage elements comprising data bits. input register comprises a data word, an associated addresses within memory banks, and control bits indicating a system operation such as system read or system write. for example, input register 312 may comprise a data word to be written to memory banks (received from data signal 322 ), the address of the data (received from address signal 324 ), and control bits. input register 312 may be coupled to pipeline bank 308 and pipeline bank 310 to communicate a data word, its associated address, and control bits. one of ordinary skill in the art will recognize that other connections are possible and consistent with the teachings of the present disclosure and the specific connections are shown for ease of understanding. for example, input register 312 may be coupled to e 1 register 314 for transferring the associated address of data word to e 1 register 312 and control signals. the e 1 register 314 has been described in connection with fig. 1 , and will also be further described in connection with fig. 7 . the e 1 register 314 is coupled to pipeline banks 308 and 310 and e 2 register 316 . the e 1 register 314 comprises data storage elements comprising data bits. for example, e 1 register 314 may comprise data word and associated addresses for data words that have failed to verify correctly within memory banks 304 and 306 . the e 1 register 314 may comprise data words and associated addresses for data words that have not yet been verified within memory banks 304 and 306 . the e 1 register 314 may also comprise data words and associated addresses for data words that have failed to read from memory banks 304 and 306 within an associated error budget. the e 2 register 316 has been described in connection with fig. 1 , and will also further be described in connection with fig. 8 . the e 2 register 316 may be coupled to e 1 register 314 . as noted above, the e 2 register 316 can, in one embodiment, be optional. the e 2 register 316 comprises data storage elements comprising data bits. the e 2 register 316 comprises data words, associated addresses, and control bits. these data words have typically failed to write to memory banks 304 and 306 . these words may have also been written from e 1 register 314 to e 2 register 316 because of power down of memory device 300 or lack of space within e 1 register. in one embodiment, e 2 register 316 may optionally be coupled to pipeline banks 308 and 310 or memory banks 304 and 306 in order to write data words (or other signals). for example, rather than storing data words and associated address from e 1 register 316 , e 2 register may store remap addresses within memory banks 304 and 306 for writing directly to memory banks through a remap process. in another embodiment, e 2 register 316 writes data to memory banks 304 and 306 during power down. fig. 4 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing a y-mux structure. the y-mux structure of the present disclosure allows pseudo-dual port memory banks to perform simultaneous write and verify operations sharing common row address and different column address. accordingly, the y-mux structure prevents the e 1 register from overflowing by allowing both a write and verify operation to take place in the same cycle (provided they share a common row address). fig. 4 shows portion of memory device 400 comprising memory bank 402 , row decoder 404 , write column decoder and y-mux 406 , read column decoder and y-mux 408 , and muxes 410 - 412 . fig. 4 shows a y-mux structure for decoders 406 - 408 . as mentioned above, the y-mux structure allows simultaneous verify and write operations for data words sharing a common row address (word line) in the memory bank but different column address. in one embodiment, one set of x addresses (common row address) and two sets of y addresses (one for the write and another for the verify operation) are inputted into the y-mux structure. the row address (x address) for both the verify and the write operation need to be the same. further, the addresses for verify and write operations need to address different columns. in other words, the verify and write operation cannot be performed at the same column address. in one embodiment, instead of a pseudo-dual port memory bank utilizing the y-mux structure, a dual ported memory bank can be used that allows two writes or two reads to be performed simultaneously. memory bank 402 is coupled to decoders 404 - 408 . row decoder 404 takes as an input the row of address for data word that is to be written to or read or verified from memory bank 402 . row decoder then determines appropriate row for the data word. in various embodiments, a data word is a pre-defined number of bits for a piece of information handled by a memory device. for example, a data word may comprise 8, 16, 24, etc. bits. the size of a data word is dependent on the memory device and may be varied as necessary. mux 410 is coupled to row decoder 404 . mux 410 takes as inputs the pipeline row address (pipeline_a_row) and read row address (read_a_row). pipeline row address indicates the row address for data words received from the pipeline for either a write or verify operation. typically, the pipeline row address indicates a shared row address between a data word to be written to memory bank 402 and another data word to be simultaneously verified in memory bank 402 . read row address indicates a row address for a data word to be read from memory bank 402 . read row address generally takes precedence over pipeline row address when pseudo-dual port memory bank 402 is used. mux 410 then outputs appropriate row address to row decoder 404 . row address decoder 404 then activates the appropriate row in memory bank 402 . appropriate activation schemes will be known to those with ordinary skill in the art. write column decoder and y-mux 406 is coupled to memory bank 402 . write column decoder and y-mux 406 takes as inputs write address column wr_a_col and write data wr_d, such as data word. write address column indicates a column address for a system write or re-write operation received from the pipeline structure of the present disclosure. write column decoder and y-mux 406 then determines appropriate column address for write operation. write column decoder and y-mux 406 then activates the appropriate column in memory bank 402 . appropriate activation schemes will be known to those with ordinary skill in the art. read column decoder and y-mux 408 is coupled to memory bank 402 . read column decoder and y-mux 408 takes as its input the column address output from mux 412 . read column decoder and y-mux 408 then determines the appropriate column for read operation. read column decoder and y-mux 408 then activates the appropriate column in memory bank 402 . appropriate activation schemes will be known to those with ordinary skill in the art. mux 412 is coupled to read column decoder and y-mux 408 . mux 412 takes as inputs pipeline column address (pipeline_a_col) and read column address (read_a_col). pipeline column address indicates column address of data word that should be verified in memory bank 402 . pipeline column address is received from the pipeline structure. read column address indicates a column address for a data word that should be read from memory bank 402 . typically, read column address takes precedence when a pseudo-dual port memory bank 402 is used. mux 412 outputs signal comprising column address for read operation or verify operation to read column decoder and y-mux 408 . thus, operating together, row and column decoders 404 - 408 perform operation on specific addresses within memory bank 402 (for example, read, write, or verify). one of ordinary skill in the art will understand that the y-mux structure of column decoders and y-mux 406 - 408 allows memory bank 402 to be operated as a pseudo-dual port memory bank. a single port memory cell may thus be used, but memory bank 402 may simultaneously perform verify and write operations when those operations share a common row address but different column addresses. if a dual port memory bank 402 was used, read and write or verify and write operations could be performed simultaneously (and not necessarily on a common row address). further, with a dual port memory bank, two writes or two reads could be performed simultaneously as well. as mentioned above, in one embodiment, the pseudo-dual port of the memory bank is designed so that one port is optimized for a read operation and the other port is optimized for a write operation. the port that is optimized for a write operation can also perform reads because write ports typically require a strong driver. however the read port typically cannot perform writes because the driver does not support write operations with higher current requirements. a memory device with a plurality of memory banks where each memory bank is associated with a corresponding memory instruction pipeline and a dynamic redundancy register fig. 17 illustrates the manner in which a memory bank can be segmented in accordance with an embodiment of the present invention. as shown in fig. 17 , a memory bank can be split into segments, memory bank a 1702 and memory bank b 1703 . instead of being driven by one set of row and column decoders, the memory bank is now split into two and driven from both sides with two sets or row and column decoders. the row decoders 1704 and 1754 perform substantially the same function as the row decoder 404 in fig. 4 . similarly, the two segments can each be driven by a write column decoder and y-mux (e.g., 1706 and 1726 ) and a read column decoder and y-mux (e.g., 1708 and 1728 ). the write column decoder and y-mux and the read column decoder and y-mux structures perform substantially the same function as the write column decoder and y-mux 406 and the read column decoder and y-mux 408 shown in fig. 4 . each of the segments may be considered a separate memory bank. as mentioned above, in an alternate embodiment, the memory device may comprise several memory banks or segments, e.g., 2, 4, 8, 16 etc. in one embodiment, each memory bank or segment will be associated its own pipeline. in another embodiment, each memory segment will be associated with a dedicated pipeline and a dedicated device redundancy register. in other words, the memory device will contain an e 1 register for each of the memory banks or segments. a memory device with a dual y-multiplexer structure for performing two simultaneous operations on the same row of a memory bank fig. 18 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing the operation of a row and column decoder in conjunction with a y-mux structure in accordance with an embodiment of the present invention. as mentioned above, the y-mux structure of the present disclosure allows pseudo-dual port memory banks to perform simultaneous write and verify operations sharing common row address and different column address. fig. 18 shows portion of memory device 1800 comprising memory bank 1802 , row decoder 1804 , write column decoder and y-mux 1806 , and read column decoder and y-mux 1808 . note that memory bank 1802 , row decoder 1804 , write column decoder and y-mux 1806 , and read column decoder and y-mux 1808 perform substantially similar functions as the corresponding components in fig. 4 . further note that write column decoder and y-mux 1806 , row decoder 1804 and read column decoder and y-mux 1808 together comprise a read/write port for the pseudo dual port memory bank. fig. 18 shows a y-mux structure for decoders 1806 and 1808 . memory bank 1850 will typically comprise a plurality of rows and column bit-lines. the y-mux structure allows simultaneous verify and write operations for data words sharing a common row address (word line) in the memory bank but different column address. for example, the row decoder 1804 may activate a row address 1850 (an x address). at the same time, column decoder and y-mux 1806 multiplexes the column bitlines 1851 based on a column address (wr_a_col) to arrive at the column lines associated with the addressed data word in the y-mux. in other words, the wr_a_col signal is used to select the appropriate column bit-lines 1851 to write the data inputted through the wr__d signal. in the same cycle as column decoder and y-mux 1806 are writing a data word to the memory bank 1802 , the read column decoder and y-mux is used to perform the verify operation that shares the common row address (on row 1850 ) as the write operation. for example, the read address 1852 is used to select the appropriate bit-lines for the verify (or read) operation and the result is outputted through the d-out signal. accordingly, the column decoder and y-mux 1806 is used to write a data word into the memory bank 1802 at a row address 1850 in the same cycle as the read column decoder and y-mux 1808 is used to verify (or read) a data word from row address 1850 . fig. 5 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows verification and re-write operations. fig. 5 shows exemplary pipeline 500 for implementing the pipeline flow for system write, re-write, and verify operations, among other data manipulation operations. pipeline 500 is implemented using system operations 502 , input register 504 , memory pipeline 506 , e 1 register 508 , and memory bank 510 . memory pipeline 506 comprises write register 512 , delay register 514 , verify register 516 , and verify results register 518 . moreover pipeline 500 comprises compare memory logic 520 . system operation 502 comprises signals for performing a desired operation such as system write and system read, among other data manipulation operations. as such, system operation 502 typically includes signals indicating a data word, the associated data address within memory bank 510 , and control signals indicating the operation to be performed on memory bank 510 (such as write or chip select signal), among other signals for performing data manipulation operations and maintaining appropriate states. typically, the signals from system operation 502 are stored in input register 504 . other configurations for signals from system operation 502 may be used without departing from the scope of the present disclosure. moreover, other embodiments of pipeline 500 are possible without departing from the teachings of this disclosure. for example, delay register 514 allows delay between write and verify operation on a data word. stt-mram may require a delay between write operations at a particular address and verify operation at the common address. the delay cycle allows data storage elements within memory bank 510 to return to a stable state before performing verify operation. other ram technologies, and in some instances stt-mram itself, may not require such delay and delay register 514 is not necessary. input register 504 is coupled to write register 512 . input register 504 comprises data storage elements comprising data bits. in certain embodiments, input register 504 can include data bits for a data word, associated address, a valid bit, and other desired control bits. the input register 504 comprises the initial stage of the pipeline. in one embodiment, for example, where a pseudo-dual bank memory bank is used, the input register 504 adds a delay in the pipeline that allows the memory device time to search for a data word and an associated address in the e 1 register 508 that shares a common row address with a data word (associated with a write operation) in the input register. for example, a write operation may be received into the input register 504 from system operations 502 along with the data word to be written and its corresponding address. the input register provides the requisite delay to be able to search in the e 1 register for a verify operation that shares a common row address with the data word associated with the write operation. as discussed above, e 1 register 904 can receive a rowchg signal that indicates row address change within a pipeline structure of the present disclosure. the rowchg signal may indicate that another data word and associated address should be transmitted from e 1 register 904 to the pipeline structure for a verify operation. if a pseudo-dual port memory bank is used, e 1 register 904 may choose a data word and an associated address such that they share a common row address with a data word to be written into the write register of the pipeline structure. in this way, a write operation and a verify operation can be simultaneously performed since the data words share a common row address. the input register 504 provides the necessary delay in the pipeline to be able to look for the matching verify operation in the e 1 register before the data word to be written is inserted into the write register 512 . in other words, the delay of input register 504 allows enough time to search for the matching verify operation in the e 1 register prior to inserting the data words to be written and verified into the write register 512 and the verify register 516 respectively. the valid bit indicates whether data manipulation operations such as system write operation should be performed or the register should not be used to perform such operations. for example, valid bits based on a write signal and chip select signal provided by system operation 502 may indicate whether data word in input register is used for write. input register 504 may also be coupled to e 1 register 508 , for example, to transmit associated address and control bits to e 1 register 508 . this associated address and control bits may be used in case of row address change in the pipeline or to invalidate an e 1 register 500 entry with the same associated address, for example. for example, the address and control bits may be used to look for a pending verify operation in the e 1 register that shares a common row address with a data word to be written into the memory bank. an active memory bank of an embodiment of the present disclosure denotes a memory bank in which a system write or system read is taking place. thus, an active bank signal (or an active bank bit) prevents re-writes during that clock cycle, and instead indicates that a system write or read will occur during that clock cycle. for example, an active bank signal indicates that write register 512 will write a data word previously received from input register 504 to memory bank 510 during that clock cycle. thus, e 1 register knows that data word for re-write operation should not be transmitted to write register 512 during that clock cycle. input register 504 transmits data word, associated address, and desired control bits to write register 512 . the e 1 register 508 has previously been described with respect to fig. 1 and will be described in conjunction with fig. 7 . the e 1 register 508 is coupled to input register 504 , write register 512 , delay register 514 , verify register 516 , and verify results register 520 . the e 1 register 508 may supply data word, associated address of a data word within memory bank 510 , and control signals to write register 512 , and verify register 516 . the e 1 register 508 may receive a data word, its associated address, and control signals from delay register 514 and verify results register 518 . the e 1 register 508 may also transmit a physical address within e 1 register 508 in case the data word is already stored within e 1 register 508 . although not shown, if delay register 514 were not used, e 1 register 508 may receive data word, associated address, and control signals from write register 512 . moreover, e 1 register 508 may communicate with input register to receive signals such as data word signal and control signal such as inactive bank signal. write register 512 is coupled to delay register 514 and memory bank 510 . in other embodiments, write register 512 may be coupled to verify register 516 . write register 512 comprises data storage elements comprising data bits. typically, write register 512 comprises data bits for a data word, its associated address, valid bit, and other desired control bits. the valid bit is a valid register bit and may be set to one when write register 512 contents are valid such that write operation may occur. write register 504 receives data word, associated address, and desired control bits from input register 504 for system write operations. for memory bank clock cycles that write register 504 would not otherwise be writing system data words to that memory bank, e 1 register 508 transmits data words, associated address, and desired control bits to write register 512 . this allows write register 512 to attempt re-write operations when write register 512 would not otherwise be writing system data words to memory bank 510 . as previously explained, when pseudo-dual port memory bank 510 is used, read operations generally take precedence over write operations from write register 512 . moreover, when pseudo-dual port memory bank 510 is used, write register 512 may perform write operation simultaneously with verify operation performed by verify register 516 if the operations share a common row address. write register 512 also transmits data word, associated address, and desired control bits to delay register 514 (or verify register 516 if no delay register is used). delay register 514 is coupled to verify register 516 and e 1 register 508 . delay register 514 comprises data storage elements comprising data bits. typically, delay register 514 comprises a data word, associated address bits, a valid bit, and other desired control bits. valid bit indicates if delay register 514 contents are valid. the delay register or multiple delay register could provide more clock cycle delay between write and verify. as previously explained, the delay register 514 is optional for ram technologies that require delay between write and verify operations for a particular address within memory bank 510 . if row address change occurs within memory pipeline 504 , delay register 514 transmits data word, associated address, and desired control bits to e 1 register 508 . thus, data word may be verified on a later clock cycle when write register will write a data word sharing a common row address. in another embodiment, data word may be verified on a later clock cycle when no verify operation will otherwise occur to the memory bank. if no row address change occurs within memory pipeline 504 , after desired delay clock cycles, delay register 514 transmits the data word, associated address, and desired control bits to verify register 516 . verify register 516 is coupled to memory bank 510 and verify results register 520 . verify register 516 comprises data storage elements comprising data bits. typically, verify register 516 comprises a data word, its associated address, valid bit, and other desired control bits. verify register 156 may comprise internal e 1 address if data word was received as a result of re-write operation or verify operation from e 1 register. valid bit indicates whether verify register 516 contents are valid for verify operation. verify register 516 contents, such as data word, can be sourced from either delay register 514 (or write register 512 in case delay register 512 is not used) or e 1 register 508 . verify register 516 would receive contents from delay register 514 if no row address change has occurred. verify register 516 would receive contents from e 1 register 508 if row address change occurred. in one embodiment, verify register 516 receives the data word, its associated address, address within e 1 register, fail count bits, and other desired control bits from e 1 register 508 . verify register 516 transmits the associated address to memory bank 510 for the data word to be verified. verify register 516 transmits the data word, fail count bits, and other desired status bits to compare data logic 520 . verify register 516 transmits the data word and its associated address to verify results register 518 in case of a system write. verify register 516 transmits internal e 1 address in case of re-write operation or verify from e 1 register 508 . thus, if the data word and the associated address already exist e 1 register 508 , verify register 516 need not transmit the data word and the associated address to verify results register 518 . compare memory logic 520 is coupled to verify register 516 . compare memory logic 520 comprises data storage elements comprising data bits. compare memory logic 520 may comprise read or sense amplifiers to read a data word from memory bank 510 . hardware logic for implementing compare memory logic 520 can be used by those with ordinary skill in the art. in the case of verify operation, compare memory logic 520 receives input from verify register 516 and memory bank 510 . memory bank 510 outputs a data word to compare memory logic 520 based on the associated address transmitted from verify register 516 . compare memory logic 520 also receives the data word from verify register 516 . thus, compare memory logic 520 determines whether the write operation passed or failed. compare memory logic 520 makes the pass/fail determination based on methods desired by those with ordinary skill in the art. in one embodiment, compare memory logic 520 determines whether the data word from verify register 516 matches the data word from memory bank 510 . in other embodiments, compare memory logic 520 deems that the operation passed if a predetermined number of bits match. if verify operation passed, compare memory logic 520 passes appropriate control bits to verify results register 518 , for example fail count bits may be set to 0. verify results register 518 may then invalidate the entry within e 1 register if needed. if verify operation failed, verify results register 518 updates fail count bits within e 1 register (in case of re-write or verify from e 1 ) or transmits the data word, the associated address, and control bits to e 1 register (in case of system write). in the case of read operation, memory bank 510 outputs a data word, the associated address, and desired control bits to compare memory logic 520 . compare memory logic 520 determines whether the read operation passed or whether re-write operation should be performed on memory bank 510 because too many errors occurred while reading the data word. in one embodiment, compare memory logic 520 corrects data words using ecc and parity bits associated with data words. if ecc determines that too many errors occurred (e.g., errors above a predetermined threshold), compare memory logic 520 also transmits the data word and control bits to verify results register 518 . verify results register 518 is coupled to compare memory logic 520 and e 1 register 508 . verify results register 518 comprises data storage elements comprising data bits. typically, verify results register 518 comprises data bits for a data word, associated address, valid bit, and desired control bits. valid bit indicates that contents of verify results stage register 518 are valid to be written to e 1 register 508 . verify results register 518 may also comprise internal e 1 address. verify results register 518 transmits data to e 1 register as previously explained. one of ordinary skill in the art will understand that pipeline structure 500 is exemplary and may include more write, delay, verify, verify results registers, and compare logic blocks to allow more re-write attempts before writing failed data words to e 1 register. moreover, more registers and memory banks may be added without departing from the scope of the present disclosure. increased pipeline depth to support pre-read operations in a memory device fig. 14 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows pipestages for performing a pre-read operation for a write operation. fig. 14 shows exemplary pipeline 1400 for implementing the pipeline flow for system pre-read, write, re-write, and verify operations, among other data manipulation operations. pipeline 1400 is implemented using system operations 1402 , input register 1404 , memory pipeline 1406 , e 1 register 1408 , and memory bank 1410 . memory pipeline 1406 comprises pre-read register 1460 , write register 1412 , delay register 1414 , verify register 1416 , and verify results register 1418 . moreover pipeline 1400 comprises compare memory logic 1420 . it should be noted that pipeline 1400 can be distinguished from pipeline 500 in that the memory pipeline 1406 comprises a pre-read register and pipe-stage 1460 prior to the write register 1412 and pipe-stage. system operation 1402 performs substantially the same function as system operations 502 in fig. 5 . for example, system operation 1402 comprises signals for performing a desired operation such as system write and system read, among other data manipulation operations. as such, system operation 1402 typically includes signals indicating a data word, the associated data address within memory bank 1410 , and control signals indicating the operation to be performed on memory bank 1410 (such as write or chip select signal), among other signals for performing data manipulation operations and maintaining appropriate states. typically, the signals from system operation 1402 are stored in input register 1404 . other configurations for signals from system operation 1402 may be used without departing from the scope of the present disclosure. moreover, other embodiments of pipeline 1400 are possible without departing from the teachings of this disclosure. for example, delay register 1414 allows delay between write and verify operation on a data word. stt-mram may require a delay between write operations at a particular address and verify operation at the common address. the delay cycle allows data storage elements within memory bank 1410 to return to a stable state before performing verify operation. other ram technologies, and in some instances stt-mram itself, may not require such delay and delay register 1414 is not necessary. input register 1404 is coupled to pre-read register 1460 . input register 1404 comprises data storage elements comprising data bits. in certain embodiments, input register 1404 can include data bits for a data word, associated address, a valid bit, and other desired control bits. the input register 1404 comprises the initial stage of the pipeline. as mentioned above, in one embodiment, for example, where a pseudo-dual bank memory bank is used, the input register 1404 adds a delay in the pipeline that allows the memory device time to search for a data word and an associated address in the e 1 register 1408 that shares a common row address with a data word (associated with a write operation) in the input register. for example, a write operation may be received into the input register 1404 from system operations 1402 along with the data word to be written and its corresponding address. the input register provides the requisite delay to be able to search in the e 1 register for a verify operation that shares a common row address with the data word associated with the write operation. in this way, a write operation and a verify operation can be simultaneously performed since the data words share a common row address. the valid bit, as discussed above, indicates whether data manipulation operations such as system write operation should be performed or the register should not be used to perform such operations. for example, valid bits based on a write signal and chip select signal provided by system operation 1402 may indicate whether data word in input register is used for write. input register 1404 may also be coupled to e 1 register 1408 , for example, to transmit associated address and control bits to e 1 register 1408 . this associated address and control bits may be used in case of row address change in the pipeline or to invalidate an e 1 register 1400 entry with the same associated address, for example. for example, the address and control bits may be used to look for a pending verify operation in the e 1 register that shares a common row address with a data word to be written into the memory bank. an active memory bank of an embodiment of the present disclosure denotes a memory bank in which a system write or system read is taking place. thus, an active bank signal (or an active bank bit) prevents re-writes during that clock cycle, and instead indicates that a system write or read will occur during that clock cycle. for example, an active bank signal indicates that write register 1412 will write a data word previously received from input register 1404 to memory bank 1410 during that clock cycle. thus, e 1 register knows that data word for re-write operation should not be transmitted to write register 1412 during that clock cycle. input register 1404 transmits data word, associated address, and desired control bits to pre-read register 1460 . a pre-read register 1460 can be used in the pipeline for several purposes. for example, the data word, associated address and control bits received from the input register 1404 could be associated with a write operation. if the information transmitted from input register 1404 into the pre-read register is associated with a write operation, a pre-read register 1460 can be used to reduce power consumption by pre-reading the data word to be written from memory bank 1410 . power consumption is reduced as a result of performing a pre-read because instead of writing the data word received from the input register 1404 directly into the memory bank at the associated address, the current data word stored at the associated address in the memory bank 1410 is pre-read to determine how many bits in the current data word need to be flipped in order to conform it to the newly received data word. for example, if the newly received data word to be written into the memory bank comprises all l′s, but the pre-read operation determines that the data word already written into memory bank at the associated address also comprises all l′s, then power is saved because the newly received data word would not need to be re-written into the memory. accordingly, the pre-read operation reduces power consumption by reducing the number of bits that need to be written for each write operation. in other words, the pre-read operation takes into account that some of the bits in a given word may already be in the correct orientation so a write operation does not need to typically write all the bits in the word. in another embodiment, a pre-read operation is performed as part of a bit-redundancy remapping protocol. examples of on-the-fly bit failure detection and bit redundancy remapping techniques are described in u.s. patent application ser. no. 15/792,672, filed oct. 24, 2017, entitled “on-the-fly bit failure detection and bit redundancy remapping techniques to correct for fixed bit defects” and hereby incorporated by reference in its entirety. in one embodiment, the pre-read register 1460 may require extra bits to carry the information acquired as a result of the pre-read operation. in other words, the pre-read register 1460 not only needs to store the data word, associated address, and desired control bits received from the input register 1404 , but it also needs to store information acquired as a result of the pre-read operation, e.g., the bits read from memory bank 1410 . for example, the pre-read register 1460 may need to store mask bits comprising information regarding the bits in the data word received from the input register that need to be flipped in order to correctly perform the write operation. further, the mask bits also need to store information regarding the direction in which the bits get flipped. in one embodiment of the present invention, pre-read register may also need to store ecc bits in order to perform error correction on the bits that are read from and written to memory bank 1410 . in one embodiment, instead of carrying the additional bits of storage within the pre-read register itself, the memory device can store the additional bits within e 1 register 1408 . however, as shown in fig. 14 , the connection between the pre-read register 1460 and the e 1 register 1408 is optional. in a more typical embodiment, the additional bits will be stored within the pre-read register 1460 , because storing the additional data in the e 1 register may not be desirable in certain circumstances because of size considerations. the e 1 register 1408 performs substantially the same function as the e 1 register described in conjunction with fig. 5 . the e 1 register 1408 is coupled to input register 1404 , write register 1412 , delay register 1414 , verify register 1416 , and verify results register 1420 . the e 1 register may, in one embodiment, be also coupled to pre-read register 1460 . the e 1 register 1408 may supply data word, associated address of a data word within memory bank 1410 , and control signals to write register 1412 , and verify register 1416 . the e 1 register 1408 may receive a data word, its associated address, and control signals from delay register 1414 and verify results register 1418 . the e 1 register 1408 may also transmit a physical address within e 1 register 1408 in case the data word is already stored within e 1 register 1408 . although not shown, if delay register 1414 were not used, e 1 register 1408 may receive data word, associated address, and control signals from write register 1412 . moreover, e 1 register 1408 may communicate with input register to receive signals such as data word signal and control signal such as inactive bank signal. write register 1412 is coupled to delay register 1414 and memory bank 1410 . write register 1412 performs substantially the same function as write register 512 in fig. 5 . delay register 1414 is coupled to verify register 1416 and e 1 register 1408 . delay register 1414 performs substantially the same function as delay register 514 in fig. 5 . verify register 1416 is coupled to memory bank 1410 and verify results register 1420 . verify register 1416 performs substantially the same function as verify register 516 in fig. 5 . compare memory logic 1420 is coupled to verify register 1416 . compare memory logic 1420 performs substantially the same function as compare logic 520 in fig. 5 . verify results register 1418 is coupled to compare memory logic 1420 and e 1 register 1408 . verify results register 1418 performs substantially the same function as verify result register 518 in fig. 5 . one of ordinary skill in the art will understand that pipeline structure 1400 is exemplary and may include more write, delay, verify, verify results registers, and compare logic blocks to allow more re-write attempts before writing failed data words to e 1 register. moreover, more registers and memory banks may be added without departing from the scope of the present disclosure. fig. 19 depicts an exemplary embodiment for a process flow showing the manner in which a pre-read register is used to perform a write operation in an exemplary memory device of the present disclosure. at step 1902 , a data word, an associated address and control bits are received into the input register 1404 from system operations 1402 . at step 1904 , as mentioned above, in one embodiment, the input register 1404 adds a delay in the pipeline that allows the memory device time to search for a data word and an associated address in the e 1 register 1408 that shares a common row address with a data word (associated with a write operation) in the input register. at step 1906 , the input register 1404 transmits data word, associated address, and desired control bits to pre-read register 1460 . as indicated above, the pre-read register 1460 can be used in the pipeline for several purposes. for example, the data word, associated address and control bits received from the input register 1404 could be associated with a write operation. if the information transmitted from input register 1404 into the pre-read register is associated with a write operation, a pre-read register 1460 can be used to reduce power consumption by pre-reading the data word to be written from memory bank 1410 . accordingly, at step 1908 , the data word stored in the memory bank at the associated address received from the input register is pre-read. at step 1910 , the data word pre-read from the memory bank is compared to the data word received from the input register to determine which bits need to be flipped in the data word stored in the memory bank in order to successfully write the new data word received from the input register into the memory bank. the results of the comparison can, in one embodiment, be stored as mask bits in the pre-read register. in one embodiment, compare logic may be built into the pipeline to perform this comparison. as mentioned above, in one embodiment, the pre-read register 1460 may require extra bits to carry the information acquired as a result of the pre-read operation. in other words, the pre-read register 1460 not only needs to store the data word, associated address, and desired control bits received from the input register 1404 , but it also needs to store information acquired as a result of the pre-read operation, e.g., the bits related to the results of the compare operation. at step 1912 , at least the mask bits, the associated address and control bits may be transmitted to the write register. in a different embodiment, the data word to be written to the memory bank (received from the input register) may also be transmitted along with the mask bits. at step 1916 , the write operation is performed using the mask bits. further, if a data word and an associated address is received from the e 1 register at step 1904 , the verify operation that shares a common row address with the write operation is also performed in the same cycle as the write operation. fig. 20 is a block diagram of an exemplary pipeline structure for a memory device that comprises a pre-read pipe-stage for a write operation in accordance with an embodiment of the present invention. as shown in pipeline structure 2000 , at any given slice of time, e.g., t=3, t=4 and t=5, there will be a pre-read operation and a write operation being performed simultaneously. as each write is being performed in the write register, at any given slice of time, another write operation is coming into the pre-read register from the input register. for example, instruction 1 2004 enters the pre-read pipestage at time t=2. at time, t=3, when instruction 1 2004 enters the write register, instruction 2 2005 enters the pre-read register. similarly, at time t=4, instruction 1 2004 enters the delay cycle, instruction 2 enters the write register and new instruction 3 2006 enters the pre-read register. accordingly, a read and a write operation will need to be performed to the memory bank 1410 at any given period of time. the memory device will, therefore, need an extra port into memory bank 1410 . as mentioned earlier, a pseudo-dual port memory bank works in cases where in a single cycle at most a write operation is performed concurrently with a verify operation. the pipeline structure of fig. 14 would require that a read and a write operation be performed concurrently with a verify operation. accordingly, two read ports (one for a verify operation and one for a read operation) and one write port will be needed. increased pipeline depth to support additional write operations in a memory device fig. 15 is a block diagram of exemplary embodiment of a memory device of the present disclosure showing pipeline structure that allows an additional cycle for a write operation for storing a data word. the additional write cycle in fig. 15 allows incoming data words to be written an additional window to be written accurately into the memory bank. fig. 15 shows exemplary pipeline 1500 for implementing the pipeline flow for system write, re-write, and verify operations, among other data manipulation operations. pipeline 1500 is implemented using system operations 1502 , input register 1504 , memory pipeline 1506 , e 1 register 1508 , and memory bank 1510 . memory pipeline 506 comprises write register a 1560 , write register b 1512 , delay register 1514 , verify register 1516 , and verify results register 1518 . moreover pipeline 1500 comprises compare memory logic 1520 . system operation 1502 comprises signals for performing a desired operation such as system write and system read, among other data manipulation operations. as such, system operation 1502 typically includes signals indicating a data word, the associated data address within memory bank 1510 , and control signals indicating the operation to be performed on memory bank 1510 (such as write or chip select signal), among other signals for performing data manipulation operations and maintaining appropriate states. typically, the signals from system operation 1502 are stored in input register 1504 . other configurations for signals from system operation 1502 may be used without departing from the scope of the present disclosure. moreover, other embodiments of pipeline 1500 are possible without departing from the teachings of this disclosure. for example, delay register 1514 allows delay between write and verify operation on a data word. stt-mram may require a delay between write operations at a particular address and verify operation at the common address. the delay cycle allows data storage elements within memory bank 1510 to return to a stable state before performing verify operation. other ram technologies, and in some instances stt-mram itself, may not require such delay and delay register 1514 is not necessary. input register 1504 is coupled to write register 1512 . input register 1504 comprises data storage elements comprising data bits. in certain embodiments, input register 1504 can include data bits for a data word, associated address, a valid bit, and other desired control bits. the input register 1504 comprises the initial stage of the pipeline. in one embodiment, for example, where a pseudo-dual bank memory bank is used, the input register 1504 adds a delay in the pipeline that allows the memory device time to search for a data word and an associated address in the e 1 register 1508 corresponding to a verify operation that shares a common row address with a data word in the input register. the data word in the input register would be associated with a write operation that shares a common row address with the data word for the verify operation in the e 1 register. for example, a write operation may be received into the input register 1504 from system operations 1502 along with the data word to be written and its corresponding address. the input register provides the requisite delay to be able to search in the e 1 register for a verify operation that shares a common row address with the data word associated with the write operation. the input register 1504 provides the necessary delay in the pipeline to be able to look for the matching verify operation in the e 1 register before the data word to be written is inserted into the write register 1512 . in other words, the delay of input register 1504 allows enough time to search for the matching verify operation in the e 1 register prior to inserting the data words to be written and verified into the write register 1512 and the verify register 1516 respectively. the valid bit indicates whether data manipulation operations such as system write operation should be performed or the register should not be used to perform such operations. for example, valid bits based on a write signal and chip select signal provided by system operation 1502 may indicate whether data word in input register is used for write. input register 1504 may also be coupled to e 1 register 1508 , for example, to transmit associated address and control bits to e 1 register 1508 . this associated address and control bits may be used in case of row address change in the pipeline or to invalidate an e 1 register entry with the same associated address, for example. for example, the address and control bits may be used to look for a pending verify operation in the e 1 register that shares a common row address with a data word to be written into the memory bank. an active memory bank of an embodiment of the present disclosure denotes a memory bank in which a system write or system read is taking place. thus, an active bank signal (or an active bank bit) prevents re-writes during that clock cycle, and instead indicates that a system write or read will occur during that clock cycle. for example, an active bank signal indicates that write register 1560 will write a data word previously received from input register 1504 to memory bank 1510 during that clock cycle. thus, e 1 register knows that data word for re-write operation should not be transmitted to write register 1512 during that clock cycle. input register 1504 transmits data word, associated address, and desired control bits to write register a 1560 . the e 1 register 1508 performs substantially the same functions as the e 1 register discussed in conjunction with figs. 5 and 14 . the e 1 register 1508 is coupled to input register 1504 , write register a 1560 , write register b 1512 , delay register 1514 , verify register 1516 , and verify results register 1520 . the e 1 register 1508 may supply data word, associated address of a data word within memory bank 1510 , and control signals to write register a 1560 , write register b 1512 , and verify register 1516 . the e 1 register 508 may receive a data word, its associated address, and control signals from delay register 1514 and verify results register 1518 . the e 1 register 1508 may also transmit a physical address within e 1 register 1508 in case the data word is already stored within e 1 register 1508 . although not shown, if delay register 1514 were not used, e 1 register 1508 may receive data word, associated address, and control signals from one of the write registers. moreover, e 1 register 1508 may communicate with input register to receive signals such as data word signal and control signal such as inactive bank signal. write register a 1560 is coupled to write register b 1512 and to memory bank 1510 . write register 512 comprises data storage elements comprising data bits. typically, write register a 1560 comprises data bits for a data word, its associated address, valid bit, and other desired control bits. the valid bit is a valid register bit and may be set to one when write register a contents are valid such that write operation may occur. write register a 1560 receives data word, associated address, and desired control bits from input register 1504 for system write operations. for memory bank clock cycles that write register a 1560 would not otherwise be writing system data words to that memory bank, e 1 register 1508 transmits data words, associated address, and desired control bits to write register 1560 . this allows write register 1560 to attempt re-write operations when write register 1560 would not otherwise be writing system data words to memory bank 1510 . in one embodiment, write register a 1560 is coupled to another write register b 1512 . accordingly, pipeline 1500 comprises two write stages. the purpose of two write stages in the pipeline is to attempt each write operation at least twice prior to the verification stage. as mentioned earlier, stt-mram may suffer from a high write error rate (wer) and, accordingly, attempting to write each word at least twice prior to verification may reduce the wer associated with the memory. in one embodiment, an extra port in the memory bank will be required to support an additional write operation. fig. 16 is a block diagram of an exemplary pipeline structure for a memory device that comprises an additional write stage in accordance with an embodiment of the present invention. as shown in pipeline structure 1600 , at any given slice of time, e.g., t=3, t=4 and t=5, there will be two write operations being performed simultaneously. each write will be performed twice, however, at any given slice of time, as one write is going through its second cycle in write register b 1512 , a new write will be incoming into write register a 1560 . for example, instruction 1 1605 enters write register a at time t=2. at time t=3, when instruction 1 1605 enters write register b, instruction 2 1604 enters write register a. similarly, at time t=4, instruction 1 1605 enters the delay cycle, instruction 2 enters write register b and new instruction 3 1606 enters write register a. accordingly, two write operations will need to be performed to the memory bank 1510 at any given period of time. the memory device will, therefore, need an extra port into memory bank 1510 . as mentioned earlier, a pseudo-dual port memory bank works in cases where in a single cycle at most a write operation is performed concurrently with a verify operation. the pipeline structure of fig. 15 would require that two write operations be performed concurrently with a verify operation. accordingly, two write ports and a single read (or verify) port into memory bank 1510 will be needed. two write ports are necessary because simply performing one write in a given cycle and inserting the other write into the e 1 register would increase the size of the e 1 register beyond practical limits. in one embodiment, a tri-ported memory bank structure can be obtained by adding an extra write port to the pseudo-dual port memory bank structure using the y-mux structure as explained in conjunction with fig. 4 . in a different embodiment, three separate ports are implemented into the memory bank 1510 , wherein two ports are optimized for write operations and one port is optimized for read operations. as explained earlier, ports that are optimized for write operations will have higher current requirements and occupy more physical space than ports that are optimized for read operations. in one embodiment, the three ports are all implemented using the y-mux structure discussed in conjunction with fig. 4 . in one embodiment, a true dual port memory bank is implemented for the two write operations and an extra port is added using the y-mux structure for the read port. in one embodiment, instead of two separate write stages in the pipeline 1500 , a single write pulse that is double the width of a traditional write pulse can also be used. within the time period of the single write pulse, there can be two attempts at writing the data word into memory bank 1510 . write register a 1560 transmits data word, associated address, and desired control bits to write register b 1512 . this way the same data word can be written twice to the memory bank 1510 in two separate cycles. it should be noted that read operations generally take precedence over write operations from either of write registers. if a read operation occurs, then the pipeline is typically stalled to allow the read operation to terminate. as discussed above, e 1 register 1908 can receive a rowchg signal that indicates row address change within a pipeline structure of the present disclosure. when a rowchng signal is received in the embodiment of fig. 15 , there will be an unfinished write in write register a 1560 and a write that has not been verified yet in write register b 1512 . accordingly, in the embodiment of fig. 15 , the e 1 register will typically be larger than other embodiments because upon receiving a rowchg signal, two entries from the pipeline will be inserted into the e 1 register while the memory operation causing the row change signal to assert is allowed to enter the pipeline. the entry from write register a 1560 will need to be re-written and the entry from write register b 1512 will need to be verified. in one embodiment, if a rowchg signal is received, the data word that has only passed through one write stage can be transferred to the e 1 register through connection 1590 while the other data word that has passed through both write stages can be transferred to the e 1 register through the delay register 1514 . the data word sent to the e 1 register through connection 1590 would need to be re-written while the data word transmitted from the delay register 1514 would need to be verified during a later cycle. further, similar to the embodiments discussed in connection with figs. 5 and 14 , the rowchg signal may also be used to indicate that another data word and associated address should be transmitted from e 1 register 1508 to the pipeline structure for a verify operation. if a pseudo-dual port memory bank is used, e 1 register 1508 may choose a data word and an associated address such that they share a common row address with a data word to be written into the write register of the pipeline structure. in this way, a write operation and a verify operation can be simultaneously performed since the data words share a common row address. the input register 504 provides the necessary delay in the pipeline to be able to look for the matching verify operation in the e 1 register before the data word to be written is inserted into the write register 512 . in other words, the delay of input register 1504 allows enough time to search for the matching verify operation in the e 1 register prior to inserting the data words to be written and verified into the write registers and the verify register 516 respectively. in the embodiment of fig. 15 , since the write operation passes through two stages of the pipeline, the e 1 register has another cycle to be able to look for the matching verify operation. accordingly, the delay in the input register 1504 may not be necessary to provide sufficient time to find a matching verify operation. write register b 1512 is coupled to delay register 1514 and memory bank 1510 . in other embodiments, write register 1512 may be coupled to verify register 1516 . write register 1512 comprises data storage elements comprising data bits. typically, write register 1512 comprises data bits for a data word, its associated address, valid bit, and other desired control bits. the valid bit is a valid register bit and may be set to one when write register 1512 contents are valid such that write operation may occur. write register 1504 receives data word, associated address, and desired control bits from write register a 1560 so that the data word can be written into memory bank 1510 a second time. for memory bank clock cycles that write register 1504 would not otherwise be writing system data words to that memory bank, e 1 register 1508 transmits data words, associated address, and desired control bits to write register 1512 . this allows write register 1512 to attempt re-write operations when write register 1512 would not otherwise be writing system data words to memory bank 1510 . in one embodiment, the e 1 register 1508 can also transmit data words associated with re-write operations to write register a 1560 so that the re-write operations may also be attempted at least twice in the pipeline. delay register 1514 is coupled to verify register 1516 and e 1 register 1508 . delay register 1514 comprises data storage elements comprising data bits. typically, delay register 1514 comprises a data word, associated address bits, a valid bit, and other desired control bits. valid bit indicates if delay register 1514 contents are valid. the delay register or multiple delay register could provide more clock cycle delay between write and verify. as previously explained, the delay register 1514 is optional for ram technologies that require delay between write and verify operations for a particular address within memory bank 1510 . if row address change occurs within memory pipeline 1504 , delay register 1514 transmits data word, associated address, and desired control bits to e 1 register 1508 . thus, data word may be verified on a later clock cycle when write register will write a data word sharing a common row address. in another embodiment, data word may be verified on a later clock cycle when no verify operation will otherwise occur to the memory bank. if no row address change occurs within memory pipeline 1504 , after desired delay clock cycles, delay register 1514 transmits the data word, associated address, and desired control bits to verify register 1516 . the addition of a delay between the write register 1560 and the verify register 1516 also allows the data transferred from the write register 1512 to stabilize before transferring the information to the verify register 1516 . this prevents noise from being injected into the verify cycle. verify register 1516 is coupled to memory bank 1510 and verify results register 1520 . verify register 1516 performs substantially the same function as verify register 516 in fig. 5 . it should be noted that in one embodiment the second write register b 1512 may be placed subsequent to the verify register 1516 . in other words, instead of having two write registers back to back in the pipeline, one of the write registers may follow the verify register 1516 . this way a write operation can be attempted in the first write cycle and verified thereafter to ensure that the operation completed successfully. if the write operation did not complete successfully, then another write cycle subsequent to the verify operation can be used to attempt a re-write. this may be more efficient in certain cases than performing two write operations consecutively on the same data word. similarly, other combinations are possible that attempt one or more re-write operations at different stages of the pipeline. in one embodiment, the pipeline illustrated in fig. 15 could also have a pre-read register that performs substantially the same function as pre-read register 1460 in fig. 14 . compare memory logic 1520 is coupled to verify register 1516 . compare memory logic 1520 performs substantially the same function as compare logic 520 in fig. 5 . verify results register 1518 is coupled to compare memory logic 1520 and e 1 register 1508 . verify results register 1518 performs substantially the same function as verify result register 518 in fig. 5 . one of ordinary skill in the art will understand that pipeline structure 1500 is exemplary and may include more write, delay, verify, verify results registers, and compare logic blocks to allow more re-write attempts before writing failed data words to e 1 register. moreover, more registers and memory banks may be added without departing from the scope of the present disclosure. one of ordinary skill in the art will understand that pipeline structure 1500 is exemplary and may include more write, delay, verify, verify results registers, and compare logic blocks to allow more re-write attempts before writing failed data words to e 1 register. moreover, more registers and memory banks may be added without departing from the scope of the present disclosure. fig. 6 is an exemplary process flow showing an embodiment of a system read operation using an embodiment of memory device of the present disclosure. fig. 6 shows process flow 600 for system read operation of the present disclosure. process flow 600 illustrates the high-level level read operation performed on a memory device. in step 602 , a system read operation to be performed on memory bank exists within a memory device. in step 604 , the valid address stored in both pipeline banks are checked to determine whether the data word associated with system read operation exists there. if no, e 1 register checks address to determine whether the data word associated with system read operation exists there in step 606 . if no, e 2 register checks the address to determine whether the data word associated with system read operation exists there in step 608 . if no, the data word is read from memory bank at the associated address of system read operation in step 610 . if the result of step 608 is yes, the data word is read from e 2 register in step 618 . if the answer to step 604 returned yes, then data word is read from pipeline 614 . if the answer to step 606 is yes, then the data word is read from e 1 register in step 616 . one of ordinary skill in the art may recognize other process flows for system read operations without departing from the teachings of the present disclosure. system read process flow 600 may include additional steps. after step 610 , compare logic may determine whether system data word from memory bank was read within a predetermined error budget in step 612 . if the data word output from memory bank contains errors, such errors may be corrected though ecc. if the data word output from memory bank contained more errors than allowed by a predetermined error budget, the data word may also be corrected and stored in e 1 register in step 619 . in this way, e 1 register may attempt to re-write data word back to memory bank so that the data word may be read within a predetermined error budget on future read operations. the corrected data word and associated address would be stored within e 1 register. it should be noted that as discussed above, in one embodiment, the e 2 register is optional. for memory devices without the additional dynamic redundancy register, the process flows from step 606 directly to step 610 . in other words, at step 606 , e 1 register checks address to determine whether the data word associated with system read operation exists there. if no, then at step 610 , the data word is read from memory bank at the associated address of system read operation in step 610 . fig. 7 is a block diagram of an embodiment of a memory device showing a first level dynamic redundancy register. fig. 7 shows exemplary e 1 register 700 described herein that comprises physical address decoder 702 , cam 704 , mux 706 , ram 708 , status logic 710 , and control logic 712 . one of ordinary skill in the art will recognize that e 1 register 700 is exemplary, and includes features such as cam 704 which are not required for achieving the teachings of the present disclosure. moreover, e 1 register 700 communicates control signals for maintaining consistency of operations both internally and to communicate with components of memory device such as pipeline banks, e 2 register and secure memory storage, e.g., 932 . such control signals may be modified without departing from the teachings of the present disclosure. physical address decoder 702 is coupled to cam 704 , mux 706 , and control logic 712 . physical address decoder 702 receives an address input from control logic 712 . physical address decoder 702 uses the address input to determine the appropriate physical addresses within cam 704 and ram 708 for performing data manipulation operation, such as read and write. physical address decoder 702 selects an entry within cam 704 using decode signal. physical address decoder 702 may also select an entry within ram 708 using decode signal to mux 706 . in one embodiment, physical address decoder 702 may take pointers as input from control logic 712 . different pointers from control logic 712 indicate available addresses for writing data to cam 704 and ram 708 or reading data from cam 704 and ram 708 , or other pointers may be used. for example, pointers from control logic 712 may keep track of lowest open addresses within cam 704 and ram 704 . thus, e 1 register 700 keeps track of addresses for storing new data. pointers from control logic 712 may also keep track of oldest stored data within cam 704 and ram 708 . thus, re-write operations may be tried on a first-in-first-out (fifo) basis. other schemes for addressing data within e 1 register 700 and selecting data for data manipulation operations may be used by those with ordinary skill in the art without departing from the scope of this disclosure. cam 704 is coupled to mux 706 . cam 704 takes as input decode signal from physical address decoder 702 . cam 704 also takes as input an associated address which may be received from input register, delay register, or verify results register of a pipeline structure. cam 704 also takes as input control bits such as read, write, or search signal received from control logic 712 . cam 704 also takes as input other control bits from status logic 710 . the associated address signals indicate addresses within a memory bank. associated address signal is typically received from input register, delay register, or verify results register. thus, e 1 register 700 receives an address within a memory bank where data word should be verified or written. the e 1 register 700 may also receive associated address from input register to be searched for words with matching row addresses which may be verified. as mentioned above, the input register allows a delay period for searching words associated with pending verify operations in the e 1 register that have matching row addresses. cam 704 will typically write associated address from delay register or verify results registers to itself, so that associated address may be used later for re-write or verify operation. status signal, such as valid bit, indicates whether physical address within cam 704 contains valid data for data manipulation operation. cam 704 may receive status signal from status logic 710 . read signal indicates that cam 704 should output an associated address, and ram 708 should output the corresponding data word. cam 704 may use decode and read signal to output an associated address of the data word stored in ram 708 . for example cam 704 may output an associated address of the data word to write register. in this way, write register may write data from e 1 register in a clock cycle during which it would otherwise be inactive. write signal indicates that the associated address should be stored within cam 704 and the corresponding data word should be stored within ram 708 . for example, cam 704 may use the associated address signal, decode signal, and write signal to write the associated address to a physical address within cam 704 . in one embodiment, this may occur because row address change occurred within pipeline structure and delay register sent a data word, an associated address, and control bits to e 1 register 700 for storage. in another embodiment, verify results register may send a data word, an associated address, and control bits to e 1 register 700 for storage because verify operation failed or data was not read within a predetermined error budget. search signal indicates that cam 704 should search itself for an appropriate address. for example, cam 704 uses search signal received from control logic 712 to search itself for an associated address to output to verify register. thus, if row change has occurred in pipeline structure, cam 704 may output the associated address of a data word sharing a common row address with the data word to be written from the pipeline. in addition, e 1 ram 708 outputs a data word matching the associated address within cam 704 to the pipeline. cam 704 outputs associated addresses to the pipeline structure, such as to write register and verify register. cam 704 also outputs associated addresses to e 2 register or to secure memory storage area 932 (as discussed in connection with fig. 9 ). cam 704 may only output a portion of associated address. for example, if row address change occurred and cam 704 searched itself for an appropriate address for verify operation, cam 704 may output only the column address since the row address may be known. cam 704 also outputs match signal to mux 706 . match signal indicates the physical address within ram 708 of a data word that corresponds to the associated address within cam 704 . match signal may be used when reading a data word from ram 708 . mux 706 takes as input read, write, search signal from control logic 712 . mux 706 also takes as input decode signal received from physical address decoder. mux 706 also takes as input match signal from cam 704 . mux then transmits select signal to ram 708 for data manipulation operation. if mux 706 receives read signal, mux 706 typically transmits decode signal to ram 708 because decode signal indicates the physical address within ram 708 for read operation. if mux 706 receives write signal, mux 706 typically transmits decode signal to ram 708 because decode signal indicates the physical address within ram 708 for write operation. if mux 706 receives search signal, mux 706 typically transmits match signal to ram 708 because match signal indicates the physical address within ram 708 for outputting data word. ram 708 takes as input select signal from mux 706 . ram 708 also takes as input a data word received from pipeline structure, such as from delay register or verify results register. ram 708 also takes as input read and write signals received from control logic 712 . select signal from mux 706 indicates the physical address within ram 708 for performing data manipulation operation such as read or write operation. data word signal indicates the data word for storage within ram 708 . read signal indicates whether the physical address signal should be used for read operation such that data should be read from ram 708 and output to pipeline structure or e 2 register or secure memory storage. write signal indicates whether select signal should be used for write operation such that data word signal should be written to ram 708 . ram 708 typically comprises volatile memory such as sram, but may comprise non-volatile memory such as stt-mram. status logic 710 comprises hardware logic that drives the selection of addresses within control logic 710 . status logic 710 takes as input control signals from pipeline structure and e 2 register. control signals may include rowchg flag previously discussed. control signals may also indicate whether data words associated with verify and re-write operations in the e 1 register should be processed prior to re-locating them to secure memory storage or if the contents of the e 1 register should be dumped in their entirety into the secure memory storage area 932 . pipeline structure may also transmit fail count bits to status logic 710 . in one embodiment, status logic 710 updates a valid bit associated with a data word to invalid in the case that status logic 710 receives fail count bits set to 0. that is, because control signals received from verify results register indicated that verify operation passed, e 1 register 700 invalidates the entry associated with data word (associated addresses, data word, any associated control bits). status logic may also take as input inactive signal indicating that memory bank may become inactive during a subsequent clock cycle. thus, e 1 register should output a data word to write register for a re-write operation. status logic 710 may also receive control signals from e 2 register. for example, status logic 710 may receive signal indicating that e 2 register is ready for a new data word. status logic 710 may also receive a signal from the secure memory storage indicating that it is ready for a new data word in embodiments where there is no e 2 register. status logic 710 may also receive decode signal from physical decoder 702 . decode signal will indicate the entry or entries within e 1 register 700 which are being updated. status logic 710 transmits status signals. status logic 710 transmits status signals both internally and externally. status logic 710 transmits status signals to control logic 710 . status logic 710 may also transmit status signals, such as fail count bit, to pipeline structure and e 2 register. thus, control signals from status logic 710 may be used to maintain consistency of operations both within e 1 register 700 and within pipeline structure. control logic 712 comprises hardware logic for determining operations to be performed on cam 704 and ram 708 . control logic 712 also comprises hardware logic for outputting address signal to physical address decoder 702 . control logic 712 takes as input status signals from status logic 710 . status signals drive the selection of addresses by control logic 712 . for example, status signals may indicate that write operation should be performed on cam 704 and ram 708 . control logic may then increment a pointer to next address, indicating empty addresses within cam 704 and ram 708 for writing associated addresses and data words. the address signal output from control logic 712 may comprise pointers that are decoded by physical address decoder 702 to select appropriate physical addresses within cam 704 or ram 708 for performing data manipulation operation. the address signal output from control logic 712 may also be output to the pipeline to indicate physical addresses within e 1 register 700 . in this way, e 1 register 700 may transmit a data word, its associated address, and its physical address within e 1 register 700 to pipeline structure. the physical address within e 1 register 700 may be used to update e 1 register 700 control bits after verify or re-write operation occurs. if the re-write operation failed, for example, fail count bits within e 1 register 700 may be updated using the physical address within e 1 register 700 . smart dynamic redundancy register design to prevent e 1 overflow in one embodiment of the present invention, a memory device may comprise multiple banks or segments. as noted above, the memory bank may comprise stt-mram which suffers from an inherently stochastic write mechanism, wherein bits have certain probability of write failure on any given write cycle. in other words, the memory cells are characterized by having a high write error rate. the dynamic redundancy registers of the present disclosure allow the memory bank to be operated with high wer (write error rate). however, designers of the memory device need to ensure that the size of a dynamic redundancy register or cache memory, e.g., an e 1 register used to store data words associated with pending verify and re-write operations does not exceed practical limitations. accordingly, the e 1 register needs to be designed with a sufficient fixed size so that overflow is avoided in all cases. one of the factors that need to be taken into consideration in determining an optimal size for the e 1 register is the wer. for example, for a higher error rate, the e 1 register will need to be larger than for a lower error rate. in one embodiment, the number of entries in the e 1 register will be at least the wer*the size of the memory bank. further, in one embodiment, the e 1 register will contain at least one entry per row segment. in one embodiment, the e 1 register can contain 2 entries per row segment. for example, if each row segment in a memory bank has a 100 rows, then the size of the e 1 register would be at least 200 entries. in one embodiment, the number of entries the e 1 register needs to contain per row segment is related to the depth of the pipeline. in other words, the number of entries the e 1 register contains is directly proportional to the number of pipeline stages (or pipe-stages). this is because with a longer pipeline, there will be more data words that need to be stored in the e 1 register in case of a row change, e.g., when a rowchg signal is received. for example, as seen in figs. 5, 14 and 15 , the pipeline can have several stages. the more stages the pipeline has, the higher the number of entries that e 1 needs to be designed to contain. if the pipeline has an additional write stage, as shown in fig. 15 , receiving a rowchg signal would mean that the entries in both a write register and a verify register would need to be saved to be verified at a later time. accordingly, additional storage space will be needed in the e 1 register as compared to a case where there's only a single write stage in the pipeline. in one embodiment, if the e 1 register comprises n rows per segment and the pipeline has m number of stages, then, the e 1 register will comprise at least n*m entries. as mentioned above, the number of entries in the e 1 register can also be a function of the wer. in one embodiment, the size of the e 1 register can be at least (n*m)+(wer*number of entries in the memory bank). in one embodiment, the memory device can comprise a plurality of memory banks as discussed above, wherein each of the memory banks (or segments) can have its own pipeline and a dedicated e 1 register. or alternatively, the memory device can comprise a plurality of memory banks, wherein each of the memory banks (or segments) can have its own pipeline, but a single e 1 register serves all the segments (instead of a dedicated e 1 register per segment). in one embodiment, a warning pin or status bit can be used to indicated to the user the occupancy level of the e 1 register. for example, status bits may indicate to a user that the e 1 register is 25%, 50%, 75% or completely full. fig. 21 illustrates a smart design for a dynamic redundancy register in accordance with an embodiment of the present invention. the memory bank 2100 comprises multiple addressable memory cells configured in multiple segments, wherein each segment contains n rows per segment. each of the segments can be associated with its own pipeline. as shown in fig. 21 , segment 1 of memory bank 2100 can be associated with pipeline 2150 while segment 2 can be associated with pipeline 2151 . each pipeline comprises m pipestages and are configured to process write operations for data words addressed to a given segment of a of the memory bank. alternatively, in one embodiment, a single pipeline can service all the segments in the memory bank. in other words, the entire memory bank comprises a single pipeline. the memory device can also comprise a dynamic redundancy register or cache memory e 1 2110 . the number of entries, y, in e 1 is based on m, n and a prescribed word error rate (wer) so as to prevent overflow of the cache memory. in a different embodiment, each of the segments of memory bank 2100 can have its own associated e 1 register. however, in a typical embodiment, a single e 1 register services all the segments of the memory bank. in one embodiment, the number of entries yin e 1 can be calculated using the formula: (n*m+b*e), wherein b indicates the number of rows in the memory bank. in one embodiment, a warning pin(s) or status bit(s) 2105 can be used to indicate to the user the occupancy level of the e 1 register. for example, status bits may indicate to a user that the e 1 register is 25%, 50%, 75% or completely full. one of ordinary skill in the art will understand that the specific control signals, logic and structures disclosed with respect to fig. 7 are merely exemplary, and illustrate one of many possible implementations of e 1 register 700 . other implementations of e 1 register 700 may be used in conjunction with the teachings of the present disclosure. fig. 8 is a block diagram of an embodiment of a memory device of the present disclosure showing a last level dynamic redundancy register. fig. 8 shows exemplary e 2 register 800 described herein that comprises cam/ram/enbl/pointers block 802 , mux 816 , e 2 ram 818 , and physical y-mux 832 , sense amplifier 834 , error correction code bits 836 , write register 838 , and control logic 840 . one of ordinary skill in the art will recognize that e 2 register 800 is exemplary, and includes features such as ram memory bank fc 814 which are not necessary for achieving the teachings of the present disclosure. moreover, e 2 register 800 communicates control signals for maintaining consistency of operations both internally and to communicate with components of memory device such as pipeline banks, memory banks, and e 1 register. such control signals may be modified without departing from the teachings of the present disclosure. cam/ram/enbl/pointers block 802 comprises physical address decoder 804 , address cam 806 , ram update flag 807 , ram enable 808 , ram e 2 fail count 810 , ram used count 812 , and ram memory bank fc 814 . thus, block 802 comprises data storage elements comprising data bits. block 802 is used for storing control bits and associated addresses of data words. physical address decoder 804 receives an address inputs from control logic 840 . as explained in relation to e 1 register and fig. 7 , physical address decoder 804 uses address inputs to determine physical addresses for writing associated addresses and data words to cam 806 and ram 818 , respectively. physical address decoder 804 outputs decode signal to cam 806 and mux 816 . moreover, physical address decoder 804 may output decode signal to physical y-mux 832 . cam 806 stores associated addresses for data words. as explained in relation to e 1 register and fig. 7 , cam 806 may take as inputs various control signals and associated addresses. cam 806 can then write associated addresses to itself or determine appropriate physical address within ram 818 for matching data word. typically, such data word would be output, for example, to pipeline banks or memory banks. ram update flag 807 comprises control bits for determining whether associated data should be updated within ram 818 . for example, control signals received from control logic 840 may indicate that ram 818 entry should be updated based on a new data word. ram update flag 807 thus provides a mechanism to track data words that should be updated in case it is not possible to update the data word immediately. ram enable 808 comprises control bits indicating whether e 2 ram 818 contains a valid data word. ram enable 808 may thus require that all bits be set to one, for example, to provide a stringent mechanism to ensure that ram 818 includes valid data. ram enable 808 may be output to control logic 840 so that control logic may keep track of valid data within block 802 and ram 818 . one of ordinary skill in the art will recognize that other schemes may be used to ensure reliability of data words. for example, multiple copies of data word may be maintained in ram 818 and selected based on a voting scheme. in another scheme, a more stringent error correction code (ecc) scheme may be performed within e 2 register 800 than in memory bank. in another scheme, ram 818 points to particular addresses within main memory for storing data words rather than storing the data words within e 2 register 800 itself. ram e 2 fail count 810 indicates the number of times a data word has failed to write to e 2 ram 818 . for example, ram 818 may comprise non-volatile stt-mram in an embodiment. in that case, e 2 register 800 may write to ram 818 until write operation is successful in order to maintain reliability within e 2 register 800 . thus, e 2 fail count indicates the number of times a data word has failed to write to ram 818 . ram e 2 fail count 810 may be output to control logic 840 , so that control logic 840 may output appropriate addresses for writing to ram 818 . ram used count 812 indicates the number of times that a physical address within e 2 ram 818 has been used. the e 2 register 800 may desire to keep track of the number of times that a particular physical address within ram 818 has been used. for example, the number of times that a read operation has occurred, write operation has occurred, or both to a specific physical address within ram 818 . ram memory bank fc 814 indicates the number of times that a data word has failed to write to a memory bank. for example, e 2 register 800 may desire to keep track of the number of times that a write operation from e 2 register 800 has failed to the memory bank. this may be useful so that only a desired number of re-write operations are tried. the specific components of block 802 are exemplary and may be modified without departing from the teachings of the present disclosure. for example, one of ordinary skill in the art will recognize that ram memory bank fc 814 is optional and provides a mechanism for controlling the number of re-write attempts to memory bank. mux 816 is coupled to cam/ram/enbl/pointers block 802 and e 2 ram 818 . mux 816 takes as input decode signal from physical address decoder 804 indicating physical address within e 2 ram 818 and match signal from cam 806 indicating that match exists within e 2 ram 818 . thus, as explained with respect to e 1 register 700 of fig. 7 , e 2 ram 818 can perform read or write operation. if e 2 ram 818 comprises mram, write operations may be tried a number of times based on ram e 2 fail count 810 . in another embodiment, after a predetermined number of write attempts to physical address within e 2 ram 818 , ram used count 812 may operate to indicate that another location within e 2 ram 818 should be chosen for write operation. the e 2 ram 818 comprises ram data 820 , ram address 822 , ram enable 824 , ram used count 826 , and memory bank fc 830 . the e 2 ram 818 may comprise volatile or non-volatile memory. in one embodiment, the e 2 ram 818 comprises non-volatile memory such as mram so that contents may be saved on during power down. ram data 820 comprises data storage elements comprising data bits storing a data word received from e 1 register. ram address 822 stores an associated address within a memory bank for the data word stored within ram data 820 . for example, cam 806 may store an associated address to ram address 822 . ram enable 824 stores the same enable bits as ram enable 808 . ram used count 826 stores the same used count as in ram used count 812 . memory bank fc 830 stores the same fail count as ram memory bank fc 814 . thus, block 802 comprising volatile storage (e.g., sram) may be backed up to non-volatile storage (e.g., mram). similar to the explanation given with respect to fig. 4 , y-mux 832 allows read and write operations to be performed on ram 818 . sense amplifiers 824 are used to read ram 818 . ecc block 836 allows error correcting on ram 818 . write register 938 may comprise cam for searching write register contents. write register 838 receives data word and address from e 1 register. write register 838 also communicates with e 2 control logic 840 to, for example, send ready e 2 ready signal when write register 838 is ready for new data word from e 1 register. control logic 840 comprises hardware logic. control logic 840 determines appropriate operations (such as read, write, and search) to be performed on e 2 register 800 . control logic 840 also determines addresses. as previously explained in connection with fig. 7 , control logic 840 may use many different addressing schemes. in one embodiment, control logic 840 uses pointers to determine physical addresses within block 802 and ram 818 for writing data words. control logic 840 may also communicate with other components of memory device including pipeline banks, memory banks, and e 1 register. for example control logic 840 transmits e 2 flag to e 1 register to indicate that e 2 register 800 may receive a new data word to write register 838 . the above description and drawings are only to be considered illustrative of specific embodiments, which achieve the features and advantages described herein. modifications and substitutions to specific process conditions can be made. accordingly, the embodiments in this patent document are not considered as being limited by the foregoing description and drawings.
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060-528-245-177-472
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US
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[
"US"
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F16C11/06
| 2007-11-07T00:00:00 |
2007
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[
"F16"
] |
versatile bracket system for display devices
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a versatile bracket system for display devices includes a component that is attached to a backside of the display device. the component is moveable about the attachment between a first position relative to the backside of the display device and a second position relative to the backside of the display device. the first position of the component allows the component to be attached to an underside surface to thereby place the display device in a hanging viewing position. the second position of the component allows the component to cooperate with the display device and a topside surface to thereby place the display device in a standing viewing position.
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1 . a system, comprising: a display device; and a component attached to a backside of the display device, the component being moveable about the attachment between a first position relative to the backside of the display device and a second position relative to the backside of the display device wherein the first position is used to attach the component to one of an underside surface or a wall surface to thereby position the display device in a hanging viewing position and the second position cooperates with the display device and a topside surface to thereby position the display device in a standing viewing position. 2 . the system as recited in claim 1 , wherein the first position comprises the component being disposed at an angle of approximately ninety degrees relative to the backside of the display device. 3 . the system as recited in claim 2 , wherein the second position comprises the component being disposed at an angle of less than ninety degrees relative to the backside of the display device. 4 . the system as recited in claim 3 , wherein the component is further pivotally attached to the backside of the display device such the display device can be rotated left and right relative to the component. 5 . the system as recited in claim 4 , comprising a ball joint used to attach the component to the backside of the display device. 6 . the system as recited in claim 3 , comprising a hinge used to attach the component to the backside of the display device. 7 . the system as recited in claim 3 , wherein the display device comprises a television. 8 . the system as recited in claim 3 , wherein the display device comprises a monitor screen. 9 . the system as recited in claim 3 , wherein the component comprises a plate having a hole for receiving hardware used to attach the component, disposed in the first position, to the underside surface. 10 . the system as recited in claim 9 , wherein the plate comprises a toe portion extending from a bottom of the plate towards the backside of the display device used to support the component, disposed in the second position, upon the topside surface. 11 . the system as recited in claim 10 , wherein the display device comprises a television. 12 . the system as recited in claim 10 , wherein the display device comprises a monitor screen. 13 . the system as recited in claim 5 , wherein the component comprises a rod around which hardware is used to attach the component, disposed in the first position, to the underside surface. 14 . the system as recited in claim 13 , wherein the display device comprises a television. 15 . the system as recited in claim 13 , wherein the display device comprises a monitor screen. 16 . the system as recited in claim 5 , wherein the component comprises a rod having at an end removed from the backside of the display device a pair of feet portions that extend from opposite sides of the rod around which hardware is used to attach the component, disposed in the first position, to the underside surface. 17 . the system as recited in claim 16 , wherein the display device comprises a television. 18 . the system as recited in claim 16 , wherein the display device comprises a monitor screen. 19 . the system as recited in claim 16 , comprising a ball joint used to attach the rod to the feet portions. 20 . the system as recited in claim 19 , wherein the display device comprises a television. 21 . the system as recited in claim 19 , wherein the display device comprises a monitor screen. 22 . the system as recited in claim 1 , wherein the component is adjustable in length.
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background in the art, brackets for display devices, such as televisions, computer monitors, etc., are known in the art. by way of example, u.s. pat. no. d 541,138 illustrates a bracket for use in mounting a display device to a piece of furniture. by way of further example, u.s. pat. no. 5,007,608 illustrates and describes a bracket for attaching a display device to a wall. summary the following describes a versatile bracket system for use in connection with a display device, such as television, computer monitor, and the like. the versatile bracket system includes a component, such as a rod, a plate, or equivalent, that is attached to a backside of the display device, for example using a hinge, a ball joint, or equivalent. in this manner, the component is moveable about the attachment between a first position relative to the backside of the display device and a second position relative to the backside of the display device. the first position of the component allows the component to be attached to an underside surface, or a wall, to thereby position the display device in a hanging viewing position. the second position of the component cooperates with the display device and a topside surface to thereby position the display device in a standing viewing position. a better understanding of the objects, advantages, features, properties and relationships of the subject system will be obtained from the following detailed description and accompanying drawings which set forth illustrative embodiments and which are indicative of the various ways in which the principles of the system may be employed. brief description of the drawings for a better understanding of the versatile bracket reference may be had to the following drawings in which: fig. 1 is a front perspective view showing an exemplary component in the form of a plate being used to support a display device on a surface such as a table top; fig. 2 is a front perspective view showing the exemplary component of fig. 1 being used to mount a display device to a surface such as a cabinet underside or soffit underside; fig. 3 is a rear perspective view showing the exemplary component of fig. 1 again being used to support a display device on the surface such as a table top; fig. 4 is a rear perspective view of the exemplary component shown in each of figs. 1-3 ; fig. 5 is a front perspective view showing a further exemplary component in the form of a rod being used to support a display device on a surface such as a table top; fig. 6 is a front perspective view showing the exemplary component of fig. 5 being used to mount a display device to a surface such as a cabinet underside, soffit underside, or a wall; fig. 7 is a rear perspective view showing the exemplary component of fig. 5 again being used to support a display device on the surface such as a table top; fig. 8 is a front perspective view of the exemplary component shown in each of figs. 5-7 . detailed description with reference to the figures, embodiments of a versatile bracket system for use in connection with a display device, such as a television, computer monitor, or like type of device capable of displaying images and/or video, is hereinafter described. as illustrated, the versatile bracket systems provide a means for both standing a display device upon a topside surface and for hanging the display device from an underside or vertical surface, such as the underside of a cabinet, underside of a soffit, or a wall. turning first to figs. 1-4 , a first exemplary embodiment of the versatile bracket system is illustrated and now described. in particular, the bracket system of figs. 1-4 includes a component, in the form of a plate 10 , that is attached to a backside of a display device 12 . the plate 10 may be attached to the backside of the display device 12 using a hinge 14 or like type of hardware. in this manner, the plate 10 is moveable between a first position, particularly shown in fig. 2 , and a second position, particularly shown in figs. 1 and 3 . in the first position, the plate 10 extends generally horizontally from the backside of the display device 12 , i.e., the plate 10 will form an angle of approximately ninety degrees relative to the backside of display device 12 , whereupon the plate 10 may be attached to an underside surface, such as the bottom side of a cabinet, soffit, or the like, to thereby place the display device 12 into a hanging viewing position. in the second position, the plate 10 extends downwardly from the backside of the display device 12 at an angle of less than ninety degrees whereupon the plate 10 and bottom of the display device 12 cooperate to place the display device 12 into a standing viewing position upon a topside surface. in the first position, the top of the display device is preferably no higher than the surface of the plate 10 that is to be positioned against the underside surface to thereby allow the display device to be mounted entirely under the underside surface if so desired. in the second position, the plate 10 is used to prop up the display device 12 much like an easel back leg. for mounting the plate 10 to the underside surface, the plate 10 may include one or more holes 16 though which conventional mounting hardware may be passed as shown by line 18 . it will also be appreciated that, in either the first or second positions of the plate 10 , the hole 16 may be used to pass through wiring 20 associated with the display device, such as a power cable, video cable(s), speaker cable(s), etc. to assist in maintaining the display device 12 in the standing viewing position upon a topside surface, the plate 10 may also be provided with a toe portion 22 that extends outwardly from the end of the plate 10 whereupon toe portion 22 will engage with the topside surface when the plate 10 is appropriately positioned. in some circumstances, the toe portion 22 can be sized and provided with mounting hardware accepting openings whereupon the toe portion 22 can be attached to a wall surface, with the plate 10 being placed in the first position, to thereby attach the display device 12 to a wall in a hanging viewing position. in still further circumstances, the plate 10 can be further pivotally attached to the backside of the display device 12 using conventional hardware to thereby allow the display device 12 to be rotated left and right relative to the plate 10 . turning now to figs. 5-8 , a second exemplary embodiment of the versatile bracket system is illustrated and now described. in particular, the bracket system of figs. 5-8 includes a component, in the form of a rod 50 , that is attached to a backside of a display device 12 . the rod 50 may be attached to the backside of the display device 12 using a hinge to provide up and down movement of the rod 50 relative to the display device 12 or may be attached to the backside of the display device 12 using a ball joint 52 and cooperating ball joint socket to provide up and down movement of the rod 50 relative to the display device 12 as well as left and right movement of the display device 12 relative to the rod 50 . in this manner, the rod 50 is at least moveable between a first position, particularly shown in fig. 6 , and a second position, particularly shown in figs. 5 and 7 . in the first position, the rod 50 extends generally horizontally from the backside of the display device 12 , i.e., the rod 50 will form an angle of approximately ninety degrees relative to the backside of display device 12 , whereupon the plate 10 may be attached to an underside surface, such as the bottom side of a cabinet, soffit, or the like or to a wall, to thereby place the display device 12 into a hanging viewing position. in the second position, the rod 50 extends downwardly from the backside of the display device 12 at an angle of less than ninety degrees whereupon the rod 50 and bottom the display device 12 cooperate to place the display device 12 into a standing viewing position upon a topside surface. in the first position, the top of the display device is preferably no higher than the surface of the rod 50 that is to be positioned against the underside surface to thereby allow the display device 12 to be mounted entirely under the underside surface if so desired. in the second position, the rod 50 is used to prop up the display device 12 much like an easel back leg. for mounting the rod 50 to the underside surface, conventional attachment hardware, for example u-shaped brackets, may be used to engage the rod 50 and mount the rod 50 to the underside surface. still further, the rod 50 may include a pair of feet portions 54 that extend from opposite sides of an end of the rod 50 which pair of feet portions may be attached to an underside surface or a wall surface using conventional attachment hardware, such as a u-shaped bracket. it will also be appreciated that the feet portions 54 may additionally assist in maintaining the display device 12 in the standing viewing position upon a topside surface. in some circumstances, the rod 50 may be connected to the feet portions 54 using a ball joint and corresponding ball joint socket 56 , together with or in lieu of the ball joint 52 , to again provide up and down/left and right movement of the display device relative to the feet portions 54 . it will also be appreciated that the component that attaches to the back of the display device 12 may be adjustable in length. by way of example only, the rod 50 may be provided with telescoping parts and a locking mechanism whereby the rod 50 may be set to a desired length. in this manner, the rod 50 may be adjusted in length so that the rod 50 could be made longer for tabletop use while being made shorter for under-cabinet mounting. while specific embodiments of the versatile bracket have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any equivalents thereof.
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061-534-100-818-782
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US
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G01N21/27,G01N21/25,B44F1/02,G07D7/12,G01N21/84,B67C3/00,G01N21/55,B42D25/378,G06K9/78,G07D7/1205,G01J3/46,A47K5/12
| 2010-09-10T00:00:00 |
2010
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[
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signal and detection system for keying applications
|
systems and methods for differentiating the spectral response of various optical coatings between a transmitter and receiver. the system is effective in determining if an optical coating produces an authorized spectral response for determining if a product having that optical coating is authorized to be used with another product.
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1 - 22 . (canceled) 23 . a second product comprising an optical coating on a substrate, wherein the second product is a consumable product shaped to engage with a first product, the first product being a dispenser having a receiver and a transmitter and configured to direct light to the optical coating, and wherein the second product is configured such that the optical coating is positionable between the optical transmitter and the receiver of the first product while authorizing pairing of a first product with a second product such that: the optical coating partially reflects light received from the transmitter to the receiver to enable the first product to: interpret reflected light received at the receiver against an authorized signal by analysis of the spectral response including analysis of the degree of absorption of the reflected light at the optical coating, to thereby determine whether the reflected light received at the receiver matches the authorized signal; in response to determining that the reflected light received at the receiver matches the authorized signal, authorize pairing of the second product with the first product to allow the dispensing of the second product by the first product; and in response to determining that reflected light received at the receiver does not match the authorized signal, prevent pairing of the second product with the first product to prevent the dispensing of the second product by the first product. 24 . the keying system of claim 23 , wherein the transmitter is an led light source. 25 . the keying system of claim 23 , wherein the second product comprises two or more optical coatings and the first product comprises an optical splitter positioned adjacent the transmitter and configured to split the first light signal to separate optical paths for directing to the first and second optical coatings. 26 . the keying system of claim 25 , wherein the system includes at least two transmitters located on the first product and each transmitter transmits a different wavelength of light against the at least two optical coatings. 27 . the keying system of claim 25 , wherein each of the at least two optical coatings is paired with a corresponding transmitter and receiver pair. 28 . the keying system of claim 27 , wherein each transmitter of each transmitter and receiver pair emits different wavelength light. 29 . the keying system as in claim 25 , wherein the at least two optical coatings comprise coatings with different absorption properties. 30 . the keying system of claim 23 , wherein the optical coating is on a rotating substrate and at least one of the at least two optical coatings rotates past a reflection point of the transmitter and receiver pair on the substrate. 31 . the keying system of claim 23 , wherein each of the optical coating are painted stripes. 32 . the keying system of claim 23 , wherein each of the optical coating have substantially the same color and different absorption properties. 33 . the keying system of claim 23 , wherein the first light signal is pulsed. 34 . the keying system of claim 23 , wherein the consumable product is a cartridge. 35 . the keying system of claim 23 , wherein the code comprises a single paint. 36 . the keying system of claim 23 , wherein the code comprises pigments configured to match a color of the substrate or product such that, to the naked eye, the code is not distinguishable from the substrate or product. 37 . a keying system for interpreting a code based on a spectral response of one or more optical coatings on a substrate between at least one optical transmitter and at least one receiver while authorizing pairing of a first product with a second product to allow or prevent dispensing of the second product by the first product, the system comprising: a transmitter located on the first product, the transmitter configured to transmit at least a first light signal against one or more optical coatings of the code located on the second product when the first product and the second product are being paired, wherein the first product is a dispenser and the second product is a cartridge or other container containing a consumable component; a receiver operatively located on the first product, the receiver configured to receive reflected light by the one or more optical coatings of the code; and receiver electronics operatively connected to the receiver and configured to: interpret reflected light received at the receiver against an authorized signal by analysis of the spectral response including analysis of the degree of absorption of the reflected light at the one or more optical coatings, to thereby determine whether the reflected light received at the receiver matches the authorized signal; in response to determining that the reflected light received at the receiver matches the authorized signal, authorize pairing of the second product with the first product to allow the first product to dispense the second product by using the consumable component from within the cartridge or other container; and in response to determining that reflected light received at the receiver does not match the authorized signal, prevent pairing of the second product with the first product to prevent the dispensing of the second product by the first product. 38 . the keying system of claim 37 , wherein the system includes at least two transmitters located on the first product and each transmitter transmits a different wavelength of light against the at least two optical coatings. 39 . the keying system as in claim 37 , wherein the optical coatings comprise at least two coatings with different absorption properties. 40 . the keying system of claim 37 , wherein the one or more optical coatings is on a rotating substrate and at least one of the one or more optical coatings rotates past a reflection point of the transmitter and receiver pair on the substrate. 41 . the keying system of claim 37 , wherein each of the optical coatings comprise at least two coatings having substantially the same color and different absorption properties. 42 . the keying system of claim 37 , wherein the code comprises a single paint.
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cross-reference to related applications this application is a continuation of currently pending u.s. patent application ser. no. 13/791,073 filed mar. 8, 2013, which in turn is a continuation of international patent application pct/ca2011/001008 filed sep. 9, 2011, which claims benefit of u.s. provisional patent application ser. no. 61/381,671 filed sep. 10, 2010. all prior applications are herein incorporated by reference. technical field systems and methods for differentiating the spectral response of various optical coatings between a transmitter and receiver are described. the systems and methods are effective in determining if an optical coating produces an authorized spectral response that can be used in a number of applications including determining if a product having that optical coating is authorized to be used with another product. background in today's competitive marketplace, the costs for companies to create, maintain and grow new markets and market share is becoming increasingly expensive. as such, there is an increasing demand for technologies that provide a low cost means of ensuring that a company's (a “first company”) investment into a product and/or marketplace is protected against newcomers that may be attempting to get into that marketplace by following the lead of the first company. that is, there exists a need for companies to have a means of protecting the products they develop from being counterfeited and/or being undercut by newcomers who, by utilizing the research and development of the first company, can produce a counterfeit or cheaper product without the same degree of development work. in addition, it is also very important for the first company, who may also have invested substantially in the brand name and/or goodwill associated with a product to protect the brand name and/or goodwill and the associated revenue stream by reducing the ability of competitors to create and market products that provide similar or confusingly similar products that can be used with the first company's products. the above is particularly important for companies selling consumable products and the case where a competitor may wish to sell a competing “re-fill” type product for use with a particular apparatus of the first company. for example, the first company may have developed a dispensing product that includes a dispensing apparatus that incorporates a consumable component in the form of a cartridge or other container. in this case, the consumable component is replaced at regular intervals after the consumable is used up and the first company looks to re-coop its development costs for the dispensing apparatus through the repeated sales of the consumable component. often, a competitor will seek to undercut the pricing of the consumable component by producing an “unauthorized” consumable component that can be used with the first company's dispensing product without incurring the development costs of either the more expensive dispensing product and/or the consumable component. in the past, while there have been various solutions developed to make it more difficult for the competitor to successfully integrate an unauthorized consumable product with various dispensing apparatus, there continues to be a particular need for lower cost solutions that prevent the use of unauthorized products within certain apparatus in order to protect the brand name and/or revenue stream of the authorized product. in addition, a lower cost solution may expand the number of products in which an authentication process could be implemented between the different product pairs. past systems have included a variety of technologies that provide primary product/consumable product matching that limits or prevents the ability to use unauthorized consumable products with a primary product. such technologies have included bar code systems, radio frequency identification systems and the like. while each of these technologies can be effective, as noted above, there continues to be a need for technologies providing a lower cost solution. a review of the prior art indicates that the use of light-emitting diode (led) transmitters and receivers have not been used in the past as a means for providing keying between primary product/consumable product pairs. for example, us patent publication 2009/0177315 (goeking) discloses a method of dispensing authorized product loaded into a dispenser by optically identifying a reference indication associated with the product. the reference indications include one or more marks that phosphorescence when in the presence of light from a light source. us patent publication 2010/0147879 (ophardt) discloses a replaceable keying component which includes a waveguide having a photochromic portion. operation involves the input of electromagnetic radiation through one end of the waveguide and detecting electromagnetic radiation at the output of the waveguide to determine if the material contains one or more compatible photochromic compounds. us patent publication 2010/0036528 (minard) discloses a dispenser utilizing a control system that receives package-specific information via an optical scanner or a radio frequency sensor. the radio frequency sensor is included in a data input system employing radio frequency identification (rfid) technology. radio scanners receive and analyze the radio signals emitted by an rfid tag. u.s. pat. no. 5,862,844 (perrin) discloses a system for controlling a dispensing apparatus with one or more illumination sources and one or more optical sensors along with a control circuit. the control circuit responds to at least one of the optical sensors to initiate dispensing of the material. the control circuit is designed to actuate a dispensing appliance from above when a container is presented directly below an outlet. u.s. pat. no. 7,621,426 (reynolds) discloses a system for dispensing product by utilizing an electronically powered key device and/or identification code from an authenticated refill container. the system utilizes a near field frequency response to determine the compatibility of the refill container. us patent publication 2009/0276091 (duha) discloses an apparatus for analyzing readable tags to ensure the use of authenticated paint in paint dispensers. summary in accordance with the invention, systems and methods for differentiating the spectral response of various optical coatings between a transmitter and receiver are described. the systems described herein are effective in determining if an optical coating produces an authorized spectral response for then determining if a product having that optical coating is authorized to be used with another product. in accordance with a first aspect, there is provided a system for differentiating the spectral response of one or more optical coatings on a substrate between a transmitter and receiver comprising: a transmitter operatively located adjacent the optical coating for transmitting a first light signal against an optical coating; a receiver operatively located adjacent the optical coating for receiving reflected light off the optical coating; and, receiver electronics operatively connected to the receiver for interpreting reflected light at the receiver against an authorized signal and determining if the optical coating is an authorized or unauthorized optical coating. in a preferred embodiment, the transmitter is an led light source. in another embodiment the system includes at least two transmitters and each transmitter transmits a different wavelength of light against the optical coating. in one embodiment, the transmitter transmits light against a common optical coating and the optical coating has different reflection properties to each wavelength of light. in another embodiment, the authorized signal is a combination of received signals from each transmitter. in yet another embodiment, the optical coating includes at least two optical coatings and each optical coating is paired with a corresponding transmitter and receiver pair. in another embodiment, each transmitter of each transmitter and receiver pair emits different wavelength light. the at least two optical coatings may also have different reflective properties. in another embodiment, the optical coating includes at least two spatially distinct optical coatings and a single transmitter and receiver pair and wherein light from the transmitter is diverted through an optical system to each of the at least two spatially distinct optical coatings and reflected light from each of the at least two spatially distinct optical coatings is received in the receiver of the transmitter and receiver pair. in one embodiment, each of the at least two spatially distinct optical coatings has different reflection properties. in yet another embodiment, the substrate is a rotating substrate and the rotating substrate includes at least one optical coating that rotates past a reflection point of the transmitter and receiver pair on the substrate. the substrate may also include at least two optical coatings that have different reflection properties. in one embodiment, the at least two optical coatings have substantially the same color and different reflection properties. in another embodiment, the led is a multi-color led enabling sequenced generation of at least two wavelengths within the led and wherein the receiver receives a corresponding reflected signal of the at least two wavelengths. in another embodiment, the input light signal(s) is/are pulsed. in another aspect, the invention provides a system for differentiating the spectral response of at least two optical coatings on a substrate comprising at least one transmitter and receiver pair including a transmitter and a receiver, the transmitter for transmitting a light signal against first and second optical coatings on the substrate, the system including an optical element positioned adjacent the transmitter for diverting a portion of the light signal against the second optical coating, wherein the receiver is operatively located adjacent the first and second optical coating for receiving reflected light off the first and second optical coatings. in yet another aspect, the invention provides a method of evaluating a substrate having an optical coating in relation to a primary apparatus comprising the steps of: a) positioning the optical coating of the substrate in an operative position relative to the primary apparatus; b) transmitting a first light signal against the optical coating from the primary apparatus; c) receiving a reflected light signal on the primary apparatus from light reflected off the optical coating; d) comparing the reflected light signal to a pre-determined signal pattern and determining if the reflected light signal matches the pre-determined signal pattern; e) providing a response signal based on the result of step d). in another embodiment, step b) includes at least a second light signal. in yet another embodiment, the optical coating is at least two optical coatings and wherein each optical coating is paired with a corresponding transmitter and receiver pair such that steps a)-c) includes positioning, transmitting and receiving across corresponding transmitter and receiver pairs. in yet another embodiment, each of the at least two optical coatings has different reflection properties. brief description of the drawings the invention is described with reference to the accompanying figures in which: fig. 1 is a sketch of a keying system in accordance with a first embodiment of the invention with an authorized optical coating; fig. 1a is a sketch of a keying system in accordance with a first embodiment of the invention with an un-authorized optical coating; fig. 2 is a sketch of a keying system in accordance with a second embodiment of the invention with an authorized optical coating; fig. 2a is a sketch of a keying system in accordance with a second embodiment of the invention with an un-authorized optical coating; fig. 3 is a sketch of a keying system in accordance with a third embodiment of the invention with an authorized optical coating; fig. 3a is a sketch of a keying system in accordance with one embodiment of the invention having optics enabling a single transmitter/receiver pair to be used with two distinct optical coatings; fig. 3b is a sketch of a keying system in accordance with one embodiment of the invention having a rotating substrate enabling a more complex code to be paired with a single transmitter/receiver; fig. 4 is a sketch of a keying system in accordance with one embodiment of the invention as a product pair; and, fig. 5 is a spectral reflection profile for a representative paint showing three possible wavelengths that could be used in an embodiment of the invention. detailed description with reference to the figures, signal and detection systems for keying applications are described in which the reflectivity properties of various optical coatings including but not limited to inks, paints, pigments, and dyes are used to signal if an item on which the optical coating is placed is an authorized item or not. the system is described with reference to various examples in which underlying concepts of operation are described. as explained in greater detail, the concepts described herein may be used in different embodiments and applications in order to achieve the objectives of the invention. in more specific aspects, the invention describes the use of one or more led transmitters, receivers and optical coatings including paints that can deployed in a number of configurations for keying applications. these embodiments utilize the absorption and reflection properties of the optical coatings allowing for the analysis of spectral responses. by combining one or multiple led light sources with one or more optical coatings, a reflected signal pattern may be comprised of a variety of spectral features that can be used to define a specific authorized signal pattern. importantly, the subject system can provide a number of advantages over other systems including lower power levels to achieve keying as well as lower material costs generally by using reflectance instead of fluorescence or phosphorescence for labelling or keying purposes. in the context of this invention, any number of codes between two related products can potentially be established using the principles described herein that can be used by manufacturers/users to signal a wide number of meanings and initiate various actions. similarly, the electronics used in signal generation and signal interpretation and any subsequent actions that associated electronics may initiate are highly variable but readily integrated to the technology described herein as understood by those skilled in the art. in accordance with the invention and as shown in figs. 1a and 1b , in a first embodiment, a system 10 includes a transmitter 12 and a receiver 14 . generally, the transmitter emits light of a particular wavelength against an optical coating 16 whereupon the light is reflected towards a receiver 14 . based on the properties of the optical coating 16 (see fig. 5 ), the signal received at the receiver will vary as a result of the degree of reflection and/or absorbance of light at the optical coating. by way of example, in fig. 1 , the transmitter emits a yellow beam of light 12 a and the optical coating 16 has been engineered to reflect yellow light such that the transmitted signal 12 a is substantially the same as received signal 14 a at the receiver as shown by the solid line. a representative signal pattern for the transmitted and received signals are shown as signals 12 b , 14 b in which the both the wavelength and signal strength are shown to be substantially identical. in contrast, as shown in fig. 1a , if the optical coating 16 a has properties that absorb yellow light, then the received signal 14 c , 14 d will be representative of the yellow light being absorbed by the optical coating. the partially absorbed signal is shown by the dotted line. similarly, if transmitter 12 is changed to emit red light while the optical coating is designed to reflect yellow light a different received signal will be observed. as a result, by altering the color of the transmitted light and/or the optical coating, and monitoring the reflection off the optical coating, the relative differences or similarities in spectral reflectivity, can be used to determine if the optical coating is authorized or not as may be interpreted by associated electronics. thus, if the optical coatings are applied to products, the technology can be used to create coded information that can effectively allow or prevent the use of one product with another product (or other functions) when paired with the appropriate electronics. in addition, the basic concepts described above can be expanded to create more complex signal responses and, hence, the relative degree of complexity in coding between two products as explained in greater detail below. as shown in figs. 2, 2a, and 3 , the system can be expanded to include illumination using more than one light sources and/or optical coating to allow for more complex system responses. with reference to fig. 2 , a configuration 20 is described having two transmitters 22 a , 22 b in which transmitter 22 a emits light of one color (e.g. orange) and transmitter 22 b emits infra-red. in this case, the optical coating 24 is reflective of orange light but not infra-red. as shown, the transmission signal 26 may comprise alternate pulses of orange 26 a and infra-red 26 b such that the received signal 28 is comprised of higher intensity 28 a (corresponding to the orange light received) and lower 28 b intensity (corresponding to the infra-red light) signals received at receiver 30 . in this case, the alternating high and low intensity signals may be indicative of an authorized optical coating. in comparison, as shown in fig. 2a , a non-authorized optical coating 42 may absorb orange light and be partially reflective of infra-red resulting in a received signal 44 that does not match the authorized signal pattern. as such, the associated electronics would not recognize this signal as an authorized signal. as shown in fig. 3 , a further combination 50 is described. in this case, distinct optical coatings on the same substrate 51 are provided with distinct transmitter and receiver pairs. a first optical coating 52 is paired with a first transmitter 54 and first receiver 56 and a second optical coating 58 is paired with a second transmitter 60 and second receiver 62 . in this example, transmitters 54 and 60 emit the same light against different optical coatings 52 and 58 such that 64 and 66 transmit signals are identical but received signals 68 and 70 are different. as a result, the associated electronics would determine if the signals received for both transmitter/receiver pairs matched the authorized signal. importantly, the color and appearance of optical coatings can appear substantially identical to the naked eye such that in the absence of relatively sophisticated equipment, it becomes difficult for persons attempting to replicate the optical coating to do so. moreover, as is understood by those skilled in the art, relatively minor differences in optical coating chemistry and the physical separation/positioning of the optical coatings can be sufficient to substantially alter the spectral response such that replication or duplication of the optical coating can be difficult. in further examples, other combinations can be utilized. for example, systems can incorporate a greater number of transmitters against a single optical coating, different transmitters against spatially separated optical coatings and/or a different number of receivers. in other embodiments, duplicate transmitter and receiver systems could be employed in which both received signals would have to match within a threshold value to ensure authorization. fig. 4 shows a representative deployment of the system in which a first product 80 is paired with a second product 82 . as shown, the first product includes electronics 84 to provide a transmit signal and receiver electronics 86 to receive and interpret the receive signal in order to determine if the optical coating 80 a on second product 82 , and hence second product 82 is authorized for use with first product 80 . as noted above, electronics 84 and receiver electronics 86 can be designed to provide a wide variety of functions as understood by those skilled in the art. examples example 1 signal strength signal strength experiments were conducted to determine the voltage response of reflected led light against a reflective paint substrate. an led (3.5v; 5 ma) was positioned adjacent a reflective paint containing 10c873 pigment (shepard color company). reflected light was received by a light-to-voltage (ltv) converter (ts252 with a 10 k.omega. load) having an integrated lens and optimized for a visible light and near ir response. a 3.5 v signal was received by the ltv convertor thereby demonstrating that a significant signal can be received at the ltv. example 2 led sensor module a photodiode (hamamatsu s2386-18l) having a similar spectral sensitivity to the photodiode of example 1 was tested with 410 and 680 nm and 430 and 650 nm leds respectively. the photodiode showed significant signal can be received at the photodiode. example 3 use of two paints having similar appearance but different reflecting characteristics two black paints, black 30c591 and black 20f944 (shepard color company) were deposited on a substrate in a side-by-side alignment and illuminated using a 950 nm led. the received signal at the ltv was measured at 3.25 v with black 30c591 and 1.25v with black 20f944 thus indicating that substrates having substantially similar colors can provide a distinct reflectivity pattern from different regions of a coated substrate with a fixed input wavelength of light. example 4 two color illumination paints having an uneven spectral curve of reflectivity were illuminated with two distinct wavelengths and the reflected signals were compared. brown 10c873 (shepard color company) was illuminated with orange led light (595 nm) and ir led light (950 nm). a tsl 252 photosensor was used to detect reflected light. the results showed that 595 nm light produced almost no reflected signal whereas the 950 nm light produced a significant reflected signal. these results showed that a single paint can provide a distinct reflectivity pattern from different led light sources. in a second experiment, yellow 10p270 pigment (shepard color company) was illuminated with a blue led (470 nm) and red led (650 nm). the results indicated that reflection at 640 nm was approximately 6 fold higher than reflection at 470 nm. in this experiment, a control substrate (paper surface having no paint) was compared to the painted test substrates and revealed that the reflectivity of the unpainted substrate at both 470 nm and 650 nm was substantially similar (.+−0.5%). example 5 rotating substrate with reference to fig. 3b , one embodiment 70 of the keying system is described in which the substrate is incorporated onto a rotating surface 73 with a transmitter 71 and receiver 72 positioned to transmit 71 a and receive 72 a light to and from the rotating surface. importantly, this embodiment allows significantly more complex codes to be incorporated with the substrate without the need or complexity of additional transmitter/receiver pairs. for example, the substrate may include a plurality of stripes 74 on the outer or inner surface of the rotating substrate such that each stripe will pass the reflection point of the transmitter/receiver pair as the substrate rotates. thus, as can be understood, the relative complexity of codes that can be incorporated onto a rotating substrate can be substantially increased by varying such parameters as the paint (i.e. type) of the stripes, the width of stripes and/or the shape of the substrate. as a representative example, fig. 3b shows an input signal 71 that based on the properties of the stripes may produce a received signal 72 b having the profile characteristics as shown. in this example, both the width of the stripes and the paint types has been varied to produce the authorized signal that is recognized and interpreted by the associated electronics. as above, each of the stripes may be substantially identical in color to any underlying substrate and to each other and thus can be effectively indistinguishable to the naked eye as representing a code. example 6 three color illumination the potential for using a single paint (eg. yellow 10p270) was examined for use with three different colored leds. in this case, the spectral profile of reflectivity of the paint could be used to monitor differential signal patterns from the various input wavelengths. as shown in fig. 5 , the reflective profile of the paint has a various peaks and valleys that can be “matched” to the input led wavelengths such that ranges of input wavelengths can be utilized to establish reflectivity responses that provide expected absolute or differential signals. for example, for the reflective profile, input wavelengths of 400-470 nm will provide an expected 10% reflection response whereas a 690-700 nm and 940-950 nm input will provide an expected 60% and 90% reflection response respectively. as such, the absolute values and/or ratios of the responses can be compared to establish an authorized code signal. implementation examples three-color led a single three color led may be utilized to effect a more complex code signal as described in relation to fig. 5 in a more compact package. for example, three color (red, green, blue) leds can be configured to provide a sequenced and patterned output of different colored light along a common beam path. as such, the light can be readily directed against a common substrate requiring only a single receiver to receive the signal from each color. moreover, more than one three-color leds may be paired with corresponding receivers and paints to generate additional reflectance codes that may be combined together to represent an authorized signal. “invisible” bar code a bar code type system can be designed using a combination of paints having a substantially identical appearance to the naked eye but that provide a specific reflection response under specific illumination. in this case, as noted above, paints can be selected to substantially match the color of the underlying substrate/product such that the “code” is effectively not visible to the casual observer. this implementation was tested in which a bar code was designed using two black paints (black 30c591 (termed 0) and black 20f944 (termed 1)) in which three alternating bands of each paint were painted on a substrate and illuminated with a 950 nm led. that is, the bar code had the pattern 010101. the code was read by consecutive displacement of the bar code relative to the led/sensor pair. the results showed a reflection pattern discernable as a corresponding “high” voltage signal x and “low” voltage signal y, i.e. xyxyxy. in various embodiments of the bar code, the associate electronics can be designed in accordance with the physical characteristics of a product pair and/or the relative complexity of the code. that is, a bar code can be implemented utilizing a single led/sensor pair in which the code is read by movement of led/sensor pair relative to the code or where multiple led/sensor pairs are oriented above each bar code element (i.e. color or stripe). importantly, it is understood that based on these principles, a wide range of signal patterns can be created that utilize various combinations of parameters of the leds, sensors, paints, physical orientation and movement of the elements, and size and shape of the substrate paints. it is also understood that the associated electronics can be designed to provide various functions to a specific embodiments such as including power saving strategies that minimize or reduce power consumption through proximity switches and/or pulsed signals. in various embodiments, the system may also include one or more optical elements 61 that allow a single light source to be directed against different optical coatings as shown in fig. 3a . in this case, the optical elements may be used to split the transmitter light to separate optical paths that are directed to the different optical coatings. depending on the geometry and reception characteristics of the receiver, a single receiver may be utilized to receive reflected light from both optical coatings. product pair relationship the physical relationship between a product pair will contribute to the type of code that may be implemented. generally, the physical space that is available, the separation and/or the movement of one component relative to another may determine the specific design of keying system. features such as proximity switches and pulsed powered may be utilized to minimize power consumption as understood by those skilled in the art. paints in accordance with the invention, as described above, a number of different paints can be utilized to exploit the reflective properties of the paints. the ultimate selection of paints, as understood by those skilled in the art, will based on the desired keying application and consider a number of factors relevant to that application including but not limited to factors such as the level of desired security, the form and size of the substrate and the color of the substrate. paints can be applied to substrates using a variety of known production techniques. leds factors used in selecting suitable leds include but are not limited to the spectral emission profile, the spatial dimensions (eg. angular dimensions) of the emission profile, and the emission colors. photo sensors photo sensors may be selected based on factors including but not limited to spectral sensitivity (e.g. visible, near ir), the spatial dimensions of response, size (e.g. profile size and dimensions) and speed. photo sensors can include photodiodes, phototransistors and light-to-voltage converters. although the present invention has been described and illustrated with respect to preferred embodiments and preferred uses thereof, it is not to be so limited since modifications and changes can be made therein which are within the full, intended scope of the invention as understood by those skilled in the art.
|
062-202-293-880-552
|
IT
|
[
"IT",
"US"
] |
F16K17/20,F17D5/06,F16K31/02,G08B21/00
| 2009-04-14T00:00:00 |
2009
|
[
"F16",
"F17",
"G08"
] |
device for detecting leaks of fluids
|
a device for detecting leaks of fluids includes means for metering flow of a fluid towards a premises, shut-off means for the fluid, operable between a delivery configuration of the fluid and a closed configuration to allow/prevent its transit towards the premises, and a management and control unit, able to act in conjunction with the metering means of the flow and to send a signal to the shut-off means to switch from the delivery to the closed configuration. the management and control unit comprises enabling means, able to allow or prevent the signal to be sent to the shut-off means. the device comprises, in addition, means for detecting the presence of a user in the premises, operatively connected to the enabling means in such a way that these allow the signal to be sent to the switch if the presence detector means detect the absence of the user in the premises.
|
1 . a device for detecting leaks of, for example, hydraulic fluids, comprising: metering means of the flow of a fluid towards a premises, such as a habitation; shut-off means of the fluid, operable between a delivery configuration of the fluid and a closed configuration to allow/prevent its transit towards the premises; and a management and control unit, able to act in conjunction with the metering means of the flow and to send the shut-off means a signal to switch from the delivery to the closed configuration; wherein the management and control unit comprises enabling means, able to allow/prevent sending of the switch signal to the shut-off means; wherein the device comprises, in addition, presence detector means of a user in the premises, operatively connected to the enabling means in such a way that these enable the switch signal to be sent if the presence detector means detect the absence of the user on the premises. 2 . device according to claim 1 , wherein the enabling means comprise a timer device which, when the presence detector means detect the absence of the user on the premises, is able to send the switch signal in the case in which the deliveries of fluid are contrary to pre-set temporal or flow criteria for example. 3 . device according to claim 1 , wherein the presence detector means comprise movement sensor devices, for example volumetric. 4 . device according to claim 1 , wherein the metering means of the flow comprise at least one turbine which, moved by the transit of the fluid, generates electric signals received by the management and control unit. 5 . device according to claim 1 , wherein the shut-off means of the fluid comprise at least one motorised valve, solenoid valve or similar, and/or check valve. 6 . device according to claim 1 , wherein the management and control unit comprises at least one microprocessor, alarm device and means of communication, such as towards a user, to signal an anomalous situation. 7 . device according to claim 1 , comprising, in addition, seismic detection devices, able to detect telluric quakes, operatively connected to the management and control unit. 8 . device according to claim 1 , comprising, in addition, heat detection devices, able to detect the temperature of the fluid, operatively connected to the management and control unit. 9 . device according to claim 1 , wherein: the shut-off means are positioned on a first duct; the metering means of the flow are positioned on a second duct in fluidic connection with the first; the first duct having a bigger through section than the second duct. 10 . device according to claim 1 , comprising: seismic detection devices, able to detect telluric quakes, operatively connected to the management and control unit; heat detection devices, able to detect the temperature of the fluid, operatively connected to the management and control unit; and wherein the shut-off means are positioned on a first duct; the metering means of the flow are positioned on a second duct in fluidic connection with the first; the first duct having a bigger through section than the second duct. 11 . a device for detecting leaks of, for example, hydraulic fluids, comprising: metering means of the flow of a fluid towards a premises, such as a habitation; shut-off means of the fluid, operable between a delivery configuration of the fluid and a closed configuration to allow/prevent its transit towards the premises; and a management and control unit, able to act in conjunction with the metering means of the flow and to send the shut-off means a signal to switch from the delivery to the closed configuration; wherein the shut-off means are positioned on a first duct, the metering means of the flow are positioned on a second duct in fluidic connection with the first duct, and the first duct has a bigger through section than the second duct.
|
field of the invention the present invention relates to a device for detecting the leakage of fluids, such as hydraulic fluids. description of the prior art the use of systems to detect leaks of fluid, especially hydraulic, in the home is known of. the active systems are usually composed of a flow meter, able to send a signal to stop the delivery of water when the flow of the same is above a certain preset value, and by at least one solenoid or motorised valve to shut off the water, commanded by the signals of the flow meter between a configuration in which water is delivered and a closed configuration to allow/prevent transit of the same towards a premises. the known systems present a number of drawbacks however. in particular, such systems are programmed to react to an anomalous leak in a single mode only, that is to say by emitting an alarm signal or stopping the water delivery. it is therefore not unusual, during ordinary daily events, such as when the shower and the dishwasher or irrigation system of the garden are in contemporary use, for the systems to inopportunely stop the water delivery, mistakenly interpreting such increased demand of water as the breakage of a pipe. summary of the invention the present invention therefore sets out to resolve the drawbacks of the prior art and, in particular, those mentioned above. such purpose is achieved by a device for detecting leaks of, for example, hydraulic fluids, comprising: metering means of the flow of a fluid towards a premises, such as a habitation;shut-off means of the fluid, operable between a delivery configuration of the fluid and a closed configuration to allow/prevent its transit towards the premises; anda management and control unit, able to act in conjunction with the metering means of the flow and to send the shut-off means a signal to switch from the delivery to the closed configuration; wherein the management and control unit comprises enabling means, able to allow/prevent sending of the switch signal to the shut-off means; wherein the device comprises, in addition, presence detector means of a user in the premises, operatively connected to the enabling means in such a way that these enable the switch signal to be sent if the presence detector means detect the absence of the user on the premises. brief description of the drawings fig. 1 shows a block diagram of the device which the invention relates to, according to one possible embodiment. fig. 2 shows a schematic diagram of the disposition of the flow detection devices and shut-off devices, according to an advantageous embodiment of the invention and wherein the arrow shows the direction of transit of the fluid. detailed description of the preferred embodiments with reference to the attached drawings, reference numeral 1 globally denotes, in its entirety, a device for detecting leaks of fluid, such as hydraulic leaks. preferably, the device 1 is suitable for detecting water leaks, for example domestic. the device 1 comprises metering means 2 of the flow of a fluid towards a premises, such as a habitation. according to a preferred embodiment, the metering means 2 of the flow comprise at least one turbine which, moved by the transit of the fluid, generates electric signals received by a management and control unit 5 . advantageously, the metering means 2 of the flow comprise a micro-flow detector, that is to say a detector able to detect small flows of fluid, to the order of 1 litre/hour. this way, advantageously, the device according to such variation is able to detect even small leaks from a circuit, such as those caused by a dripping tap, and not just big flows caused by a broken pipe. the device 1 comprises in addition shut-off means 3 , 4 of the fluid, which can be activated between a delivery configuration of the fluid and a closed configuration to allow/prevent its transit towards the premises. in other words, when the shut-off means 3 , 4 are positioned in the delivery configuration of the fluid, they identify a route for the passage of the fluid towards the premises. when, rather, they are positioned in the closed configuration, the fluid is prevented from transiting towards the premises. preferably, the shut-off means 3 , 4 of the fluid comprise at least one motorised valve 3 , solenoid valve or similar, and/or a check valve 4 . even more preferably, the shut-off means 3 , 4 comprise a motorised valve 3 and a check valve 4 , such as illustrated in the schematic diagram in fig. 2 . according to one possible variation, the shut-off means 3 , 4 are positioned downstream of the metering means 2 of the flow in the direction of transit of the fluid. according to one advantageous variation, the shut-off means 3 , 4 are positioned on a first duct 11 , the metering means 2 of the flow are positioned on a second duct 12 in fluidic connection with the first, the latter having a greater through section than the second duct 12 . in other words, according to this embodiment, the second duct 12 , which the metering means 2 are positioned on, acts as a by-pass in relation to the first delivery duct 11 of the fluid, achieving a dual advantage. the first advantage lies mainly in the fact that, the second duct 12 having a smaller through section than the first 11 , the metering means 2 positioned on it are more sensitive to detecting small capacity flows. in addition, for the embodiments which envisage a check valve 4 , positioned on the first duct 11 and by-passed by the second duct 12 , it is mainly such valve which receives the oscillation resonances of the fluid at the end of each delivery, and not the metering means 2 , as happens rather in the devices of the prior art. this way, advantageously, the metering means 2 do not run the risk of generating false detection of leaks of the fluid caused by the aforesaid resonance. the device 1 comprises, in addition, a management and control unit 5 , able to act in conjunction with the metering means 2 of the flow and to send the shut-off means 3 , 4 a signal to switch from the delivery to the closed configuration. in other words, when the metering means 2 of the flow detect a transit of fluid, such as through the turbine, they send a signal to the management and control unit 5 which, in turn, sends a signal to the shut-off means 3 , 4 to switch from the delivery to the closed configuration, preventing transit of the fluid towards the premises. according to one advantageous variation, the management and control unit 5 comprises at least one microprocessor, to process the signal coming from the metering means and from the presence detector means 7 , and to formulate a counter measure, if deemed necessary. according to a further advantageous variation, the management and control unit 5 comprises alarm devices, such as a siren, and means of communication, for example towards a user, to signal an anomalous situation. this way, advantageously, the device which the invention relates to is able to warn a user in any circumstances, whether on the premises or elsewhere, for example by sending an sms or making an emergency call to the user's mobile or to an emergency service number. according to one embodiment variation, the means of communication comprise a telephone module, such as a gsm. the management and control unit 5 comprises enabling means 6 , able to allow/prevent sending of the switch signal to the shut-off means 3 , 4 . in other words, the enabling means 6 act as a filter of the switch signal towards the shut-off means 3 , 4 , that is the enabling means 6 use advanced criteria, of which more will be the later, to establish the effective need to position the shut-off means 3 , 4 in the closed configuration. consequently, advantageously, the interruption of the delivery of the fluid towards the premises cannot occur inadvertently, as a result of an episodic increased demand of fluid. in fact, the enabling means 6 make it possible to reduce the occurrence of false alarms and, as a result, inconvenience to the user. the device 1 comprises lastly, presence detector means 7 of a user in the premises, operatively connected to the enabling means 6 so that this allows the switch signal to be sent if the presence detector means 7 detect absence of a user in the premises. consequently, in the absence of the user inside the premises, when the metering means 2 detect a delivery of the fluid, such as below or above a pre-set threshold, they send a signal to the management and control unit 5 . in response to such signal, the management and control unit 5 prepares to send the switch signal to the shut-off means 3 , 4 . however, for the switch signal to be effectively sent, the enabling means 6 need to have been enabled to send a signal by the presence detector means 7 , which detect the presence or absence of the user on the premises. consequently, if the presence detector means 7 detect that there is a user on the premises, the switch signal is blocked by the enabling means 6 . for the embodiments envisaging such, the management and control unit 5 can, if necessary, activate the alarm devices, for example warning the user by means of a siren positioned on the premises. according to a further variation, if the presence detector means 7 detect that there is a user on the premises, subsequent to blocking of the switch signal by the enabling means 6 , the device 1 does not take any further action. vice versa, if the presence detector means 7 detect the absence of the user on the premises, the enabling means 6 allow the switch signal to be sent to the shut-off means 3 , 4 , which position themselves in the closed configuration, stopping delivery of the fluid. furthermore, for the embodiments envisaging such, the management and control unit 5 can send a signal to the means of communication, which deals with sending an emergency call or sms to alert, for example the user, a watchman or an emergency service number. according to one embodiment variation, the presence detector means 7 comprise movement sensor devices, for example volumetric. according to a further variation, the movement sensor devices are of the infra-red, microwave or combined type, such as the type typically used in anti-intrusion or security systems. advantageously, this way, the device which the invention relates to is able to interface with devices probably already present on the premises, such as the sensors of a conventional alarm system. preferably, the presence detector means 7 are in wireless communication with the management and control unit 5 . this way, advantageously, the installation of the device which the invention relates to does not entail making special raceways for the passage of cables converging towards the management and control unit, or the unattractive presence of wires for the transit of the signals. preferably the enabling means 6 comprise, in addition, a timer device which, when the presence detector means 7 detect the absence of the user on the premises, is able to send the switch signal in the case in which the delivery of fluid is contrary to pre-set temporal or flow criteria for example. consequently, when the presence detector means 7 detect the absence of the user on the premises, the timer device acts as a supplementary filter to sending of the switch signal, sending such signal conditional to verification of the pre-set criteria. if, for example, the user turns on a dishwasher or a washing machine before leaving the premises, in the absence of the timer device, the enabling means 6 , having ascertained the absence of the user, send the switch signal to the shut-off means 3 , 4 . however, the timer device is able to verify if the delivery of fluid, detected by the metering means 2 , is compatible with the delivery of water used by a dishwasher, in that such delivery occurs, for example, at regular intervals compatible with the filling and rinsing phases. according to a further example, the timer device is programmable so as to block the switch signal in the case in which a system is provided for watering the garden, active at certain times of the day, not necessarily coinciding with the presence of the user on the premises. preferably, the device 1 comprises, in addition, a seismic detection device, able to detect telluric quakes, operatively connected to the management and control unit 5 . consequently, the seismic detection device is able to send a danger signal to the management and control unit 5 , the size of which is assessed by the latter, which deals with sending the switch signal in the case in which there is a risk of the pipes breaking. advantageously, this way, the device which the invention relates to is able to ensure the safety of the premises, including in relation to natural events. according to embodiment variations of the invention, the seismic detection device comprises a geophone, a seismometer, a vertical sensor, a simple suspension, a lacoste suspension and/or leaf spring suspension, a long or short-period horizontal sensor, and/or a force-feedback sensor. preferably, the seismic detection device comprises an accelerometer, for example with an electronic detection circuit. even more preferably, the device 1 comprises, in addition, a heat detection device, able to detect the temperature of the fluid, operatively connected to the management and control unit 5 . in other words, the heat detection device, for example a thermometer, a thermocouple or similar, is able to check that the temperature of the fluid does not fall below its melting temperature, making it solid and causing the potential bursting of pipes, for example if the fluid should freeze and thereby increase in volume. according to one embodiment variation, the device 1 comprises, in addition, a damp and/or wetness sensor device operatively connected to the management and control unit 5 . preferably, the damp and/or wetness sensor is positioned at the main fluidic and preferably water utilities on the premises, such as in the bathrooms and/or kitchen. advantageously, the damp and/or wetness sensor device is able to detect leaks on the premises not detectable by the metering means 2 , in as much as only indirectly linked to the delivery of water. imagine for example a leak from the storage tank of a boiler or an immersion heater, where the leakage of liquid may not result in the delivery of further liquid, measurable by the metering means 2 . for example, this would be the case in which the supply valve of the liquid to the storage tank were closed. the present invention relates, in addition, to a method for detecting leaks of, for example, hydraulic fluids. such method comprises the phases of measuring the flow of a fluid to a premises, detecting the presence of a user on the premises, sending a signal to the shut-off means 3 , 4 of the fluid to switch from a delivery configuration of the fluid to a closed configuration to prevent the transit of the fluid to the premises, if the absence of the user on the premises is detected, and to switch the shut-off means 3 , 4 from the delivery configuration of the fluid to the closed configuration. according to one advantageous variation of the method, the phase of switching the shut-off means 3 , 4 is preceded by a phase of verifying that the deliveries of fluid are contrary to pre-set temporal or flow criteria for example. according to a further variation, the phase of detecting the presence of a user comprises a phase of detecting their movement, for example volumetrically. according to yet a further variation the method comprises, in addition, a detection phase of telluric quakes, and/or a detection phase of the temperature of the fluid. the present invention also relates to an it product which can be directly loaded into the internal memory of a processing unit and comprising portions of software code able to enact a method of detecting leaks of fluids according to any of the previous embodiments, when the portions of software code are run by the processing unit. the present invention relates lastly to a detection group 10 of leaks of, for example, hydraulic fluids, comprising a management and control unit 5 able to act in conjunction with metering means 2 of the flow of a fluid to a premises and to send a signal to the shut-off means 3 , 4 of the fluid to switch from a delivery configuration of the fluid to a closed configuration to prevent the transit of the fluid to the premises. the management and control unit 5 comprises enabling means 6 , able to allow/prevent sending of the switch signal to the shut-off means 3 , 4 of the fluid. in addition, the enabling means 6 can be operatively connected to the presence detector means 7 of a user in the premises, in such a way that the enabling means 6 permit the switch signal to be sent if the presence detector means 7 detect the absence of the user on the premises. innovatively, the device which the invention relates to makes it possible to avoid creating false alarms relative to leaks or dripping by detecting the presence of a user on the premises where the fluid is delivered. a person skilled in the art may make variations to the aforesaid embodiments of the device, of the group and of the method for detecting leaks and substitute elements with others functionally equivalent so as to satisfy specific requirements. such variations also remain within the sphere of protection as defined by the appended claims. moreover, each variation described as belonging to a possible embodiment may be realised independently of the other variations described.
|
062-639-487-241-013
|
US
|
[
"US"
] |
C08F220/12,C08F230/08,G02B1/04
| 1972-06-16T00:00:00 |
1972
|
[
"C08",
"G02"
] |
oxygen permeable contact lens composition, methods and article of manufacture
|
contact lenses are fabricated from a copolymer of a polysiloxanylalkyl acrylic ester and an alkyl acrylic ester. the copolymer has increased oxygen permeability.
|
1. a new composition of matter specially adapted for the production of contact lenses having increased oxygen permeability, said new composition being a solid copolymer of comonomers consisting essentially of: (a) about 10 to 60 parts by weight of a polysiloxanylalkyl ester of the structure ##str4## wherein: (1) x and y are selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups, phenyl groups and z groups, (2) z is a group of the structure ##str5## (3) a is selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups and phenyl groups, (4) r is selected from the class consisting of methyl groups and hydrogen, (5) m is an integer from one to five, and (6) n is an integer from one to three; and (b) about 40 to 90 parts by weight of an ester of a c.sub.1 -c.sub.20 monohydric alkanol and an acid selected from the class consisting of acrylic and methacrylic acids..]. 2. as a new article of manufacture, a contact lens having increased oxygen permeability .iadd.in comparison with poly(methylmethacrylate).iaddend., said lens being fabricated from .[.the copolymer composition of claim 1,.]. .iadd.a solid copolymer of comonomers consisting essentially of: (a) about 10 to 60 parts by weight of a polysiloxanylalkyl ester of the structure ##str6## wherein (1) x and y are selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups, phenyl groups and z groups, (2) z is a group of the structure ##str7## (3) a is selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups and phenyl groups, (4) r is selected from the class consisting of methyl groups and hydrogen, (5) m is an integer from one to five, and (6) n is an integer from one to three; and (b) about 40 to 90 parts by weight of an ester of a c.sub.1 -c.sub.20 monohydric alkanol and an acid selected from the class consisting of acrylic and methacrylic acids, said lens .iaddend.having a refractive index of from 1.35 to 1.50. .iadd. 3. the contact lens of claim 2 wherein said solid copolymer of comonomers includes as a comonomer a minor amount of a crosslinking monomer. .iaddend. .iadd. 4. the contact lens of claim 3 wherein said cross-linking monomer is a polyol dimethacrylate or a polyol diacrylate. .iaddend..iadd. 5. the contact lens of claim 3 wherein said cross-linking monomer is present in an amount equal to about 0.01% to about 2% by weight of said copolymer. .iaddend..iadd. 6. the contact lens of claim 5 wherein said cross-linking monomer is a polyol dimethacrylate or a polyol diacrylate. .iaddend. .iadd. 7. the contact lens of claim 3 wherein said solid copolymer of comonomers includes as a comonomer a minor amount of a wetting monomer. .iaddend. .iadd. 8. the contact lens of claim 7 wherein said wetting monomer is methacrylic acid. .iaddend..iadd. 9. the contact lens of claim 7 wherein said wetting monomer is present in an amount equal to about 0.1% to about 10% by weight of said copolymer. .iaddend..iadd. 10. the contact lens of claim 9 wherein said wetting monomer is methacrylic acid. .iaddend..iadd. 11. the contact lens of claim 2 wherein said solid copolymer of comonomers includes as a comonomer a minor amount of a wetting monomer. .iaddend..iadd. 12. the contact lens of claim 11 wherein said wetting monomer is methacrylic acid. .iaddend..iadd. 13. the contact lens of claim 11 wherein said wetting monomer is present in an amount equal to about 0.1% to about 10% by weight of said copolymer. .iaddend..iadd. 14. the contact lens of claim 13 wherein said wetting monomer is methacrylic acid. .iaddend. .iadd. 15. the contact lens of claims 2 or 3 wherein a wetting agent is applied to the surface of said lens. .iaddend..iadd. 16. the contact lens of claim 15 wherein said wetting agent is a dilute aqueous solution of an alkyldimethylbenzylammonium chloride. .iaddend..iadd. 17. the contact lens of claims 2 or 3 wherein the wettability of the surface of said lens is improved by exposure of the surface to a corona discharge. .iaddend..iadd. 18. the contact lens of claims 2 or 3 wherein the wettability of the surface of said lens is improved by treatment of the surface with a strong oxidizing agent. .iaddend..iadd. 19. the contact lens of claim 18 wherein said strong oxidizing agent is nitric acid. .iaddend.
|
this invention relates to novel copolymer compositions. in another aspect, the invention relates to methods for increasing the oxygen permeability of polymerized acrylates and methacrylates. in still another respect, the invention concerns contact lenses having increased oxygen permeability. in yet another respect, the invention relates to wettable contact lens materials. in a further aspect, the invention concerns oxygen-permeable, wettable transparent copolymers which can be cast, molded or machined to provide improved contact lenses. the prior art teaches the use of many different polymeric materials in contact lenses. however, although these polymers possess the optical clarity necessary for corrective lenses, they suffer from other characteristics which reduce their potential utility. polymethylmethacrylate is rigid and durable but relatively impermeable to oxygen. the hydrogel materials based on hydrophilic polymers such as polyhydroxyethylmethacrylate are soft and have poor durability. in addition, they provide an environment which is favorable for bacterial growth and are also relatively impermeable to oxygen. silicone rubber is soft and resilient and is highly permeable to oxygen. however, due to the low strength of polysiloxanes, a filler which increases the refractive index of the mixture, must be added to improve the durability. further, the precision machining and polishing which is necessary in the fabrication of a corrective contact lens is extremely difficult with the elastomeric silicone rubbers. accordingly, it would be highly desirable to provide a polymeric material suitable for use in fabricating contact lenses having increased oxygen permeability, improved mechanical strength, and which is sufficiently rigid to permit precision machining and polishing. i have now discovered novel copolymer materials which possess these properties. the novel copolymers which i have discovered are prepared by copolymerizing a polysiloxanylalkyl ester of acrylic or methacrylic acid with an alkanol ester of acrylic or methacrylic acid. the polysiloxanylalkyl ester monomer has the structural formula ##str1## wherein x and y are selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups, phenyl groups and z groups; z is a group of the structure ##str2## a is selected from the class consisting of c.sub.1 -c.sub.5 alkyl groups and phenyl groups; r is selected from the class consisting of methyl groups and hydrogen; m is an integer from one to five; and n is an integer from one to three. in the alkanol ester comonomers, the alkyl group contains from 1 to 20 carbon atoms. representative polysiloxanylalkyl ester comonomers which may be employed in the practice of the invention include: ##str3## representative alkanol ester comonomers which may be employed in the practice of the invention include: methyl acrylate and methacrylate ethyl acrylate and methacrylate propyl acrylate and methacrylate isopropyl acrylate and methacrylate butyl acrylate and methacrylate amyl acrylate and methacrylate hexyl acrylate and methacrylate heptyl acrylate and methacrylate octyl acrylate and methacrylate 2-ethylhexyl acrylate and methacrylate nonyl acrylate and methacrylate decyl acrylate and methacrylate undecyl acrylate and methacrylate lauryl acrylate and methacrylate cetyl acrylate and methacrylate octadecyl acrylate and methacrylate the novel copolymers of the present invention comprise about 10-60 parts by weight of one or more of the polysiloxanylalkyl ester monomers copolymerized with about 40-90 parts by weight of one or more of the alkanol ester comonomers. at present it is preferred to employ polysiloxanyl acrylate and methacrylate esters which have a straight or branched siloxane chain containing two to four silicon atoms having methyl or phenyl substituents and one to three ethylene groups connecting the siloxanyl chain to the acryloxy or methacryloxy group. best results are obtained if the polysiloxanyl ester content of the comonomer is up to 35% by weight and correspondingly less, e.g., 10-15%, as the silica content of the ester is increased. if one employs a branched chain alkanol ester, e.g., 2-ethylhexyl acrylate, one preferably, employs a lower polysiloxanyl ester comonomer, e.g., pentamethyldisiloxanylmethyl acrylate. the copolymers of the invention are prepared by contacting the mixture of comonomers with a free radical generating polymerization initiator of the type commonly used in polymerizing ethylenically unsaturated compounds. representative free radical polymerization initiators include: acetyl peroxide lauroyl peroxide decanoyl peroxide caprylyl peroxide benzoyl peroxide tertiarybutyl peroxypivalate diisopropyl peroxycarbonate tertiarybutyl peroctoate .alpha.,.alpha.'-azobisisobutyronitrile conventional polymerization techniques can be employed to produce the novel copolymers. the comonomer mixture containing between about 0.05-2% by weight of the free radical initiator is heated to a temperature between 30.degree. c.-100.degree. c., preferably below 70.degree. c., to initiate and complete the polymerization. the polymerization can be carried out directly in a contact lens mold to form a lens generally having the desired configuration. alternatively, the polymerization mixture can be heated in a suitable mold or container to form discs, rods or sheets which can then be machined to the desired shape using conventional equipment and procedures employed for fabricating lenses from polymethyl methacrylate. the temperature is preferably maintained below 70.degree. c. in order to minimize the formation of bubbles in the copolymer. instead of employing the bulk polymerization techniques described above, one can employ solution, emulsion or suspension polymerization to prepare the novel copolymers, using techniques conventionally used in the preparation of polymers from ethylenically unsaturated monomers. the copolymer thus produced may be extruded, pressed or molded into rods, sheets or other convenient shapes which are then machined to produce the contact lenses. the novel copolymers have vastly increased oxygen permeability in comparison to conventional contact lens materials. for example, a copolymer comprising 35 parts pentamethyldisiloxanylmethyl methacrylate and 65 parts of methyl methacrylate has an oxygen permeability of 500 cc.-mil/100 in..sup.2 /24 hr./atm. compared to an oxygen permeability of 34 for polymethyl methacrylate and 13 for polyhydroxyethylmethacrylate. these oxygen permeability values were determined in accordance with astm d1434, using a tester which has a 3 "dow" cell pressure change detection units. discs were cut to proper size to fit the tester, placed in the apparatus and conditioned a minimum of 16 hours under both vacuum and oxygen. immediately following the conditioning period, the test was performed by plotting a curve of cell pressure versus time. the slope of the curve was then used to calculate the oxygen transmission rate. in general, the oxygen permeability of the copolymers of the invention is at least 4 times to as much as several hundred times higher than that of lenses prepared from polymethylmethacrylate or the so-called "hydrogel" lenses prepared from polyhydroxyethylmethacrylate. while some of the novel copolymers are inherently wettable by human tears, it may be necessary to improve the wettability of others. this can be accomplished by several alternate methods. for example, wettability can be imparted to the copolymer by the addition of from about 0.1% to about 10% by weight of one or more hydrophilic monomers to the copolymerization mixture. such monomers include hydroxyalkyl acrylates and methacrylates wherein the alkyl group contains 1 to 4 carbon atoms, acrylic and methacrylic acid, acrylamide, methacrylamide, n-methylolacrylamide, n-methylolmethacrylamide, glycidyl acrylate and methacrylate and n-vinylpyrrolidone. alternatively, the wettability of the surface of contact lenses made from the novel copolymers can be improved by the application of a wetting agent such as, for example, a dilute aqueous solution of alkyldimethylbenzylammonium chloride, by exposure of the surface to a corona discharge or by chemical treatment of the surface with a strong oxidizing agent such as nitric acid. the rigidity of the contact lenses prepared from materials useful in the practice of this invention may be varied by changing the ratio of comonomers and/or their chemical composition. thus, contact lenses prepared from acrylate monomers are more flexible than those prepared from methacrylate monomers. a copolymer of a polysiloxanylalkyl methacrylate and an alkyl methacrylate may be fabricated into a contact lens which is more rigid than a lens prepared from the copolymer of the corresponding acrylates. the lower the alkyl methacrylate content of the copolymer the more flexible the contact lens prepared therefrom. the rigidity of a contact lens prepared from the materials useful in the practice of this invention may be increased, if desired, by the incorporation into the copolymer composition of 0.01% to about 2% by weight of a crosslinking monomer such as a polyol dimethacrylate or diacrylate or a polyol acrylic ester of higher functionality, for example, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate and pentaerythritol triacrylate or tetra-acrylate. the refractive index is an important but noncritical characteristic of a contact lens. thus, the refractive index of polymethylmethacrylate, the polymer most widely used in the fabrication of contact lenses, is 1.49. the refractive indices of the copolymers useful in the practice of this invention may be varied between 1.35 and 1.50 by varying the ratio and nature of the comonomers. in general, increasing the polysiloxanyl monomer content of the copolymer will decrease its refractive index. the nature of the substituents on the silicon atoms of the polysiloxanyl monomer also importantly affects the refractive index of the copolymer. lower straight chain alkyl substituents produce copolymers of lower refractive index while polysiloxanyl monomers having phenyl substituents on the silicon atoms yield copolymers having a higher refractive index. the following examples are presented to illustrate the practice of the invention and not as an indication of the limits of the scope thereof. example 1 this example illustrates the synthesis of a representative polysiloxanylalkyl ester comonomer, pentamethyldisiloxanylmethyl methacrylate. synthesis of dimethylchloromethylchlorosilane distilled trimethylchlorosilane (635 ml., 5 moles), b.p. 59.9.degree. c., is placed in a 1-liter, 3-necked, round-bottom flask equipped with a magnetic stirrer, a thermometer, a gas inlet tube and a dry-ice cooled reflux condenser whose outlet is connected to a water scrubber. after flushing the apparatus with dry nitrogen for 15 minutes, chlorine gas is introduced through the gas inlet tube and the flask is irradiated by ultraviolet light from a general electric 15-watt germicidal lamp placed at a distance of 6 in. from the flask. gaseous hydrogen chloride is evolved and absorbed in the water scrubber which contains a caustic soda solution and a small amount of phenolphthalein. the temperature is maintained in the range 30.degree.-40.degree. c. while chlorine is bubbled through the reaction mixture. after 30 hours of photochlorination, 5 moles of hydrogen chloride is evolved, as indicated by the discharge of the pink color in the water scrubber. the product is distilled through a column with 18 theoretic plates and the fraction distilling at 115.degree. c. is collected. the yield of dimethylchloromethylchlorosilane (d.sup.25 =1.07) is 30%. synthesis of pentamethylchloromethyldisiloxane 134 ml. dimethylchloromethylchlorosilane (1 mole) and 127 ml. (1 mole) of trimethylchlorosilane are mixed and shaken thoroughly. when 600 ml. of distilled water is added, exothermic hydrolytic reactions occur immediately. the mixture is shaken on a mechanical shaker overnight to complete hydrolysis. the upper oily layer is separated and is dried over anhydrous sodium carbonate. after drying, the product is distilled through a column of 13 theoretical plates and the fraction which distills at 151.degree.-152.degree. c. is collected. the yield of pentamethylchloromethyldisiloxane (b.p. 151.8.degree. c., d.sup.25 =0.910, n.sub.d.sup.20 =1.4106) is 30%. synthesis of pentamethyldisiloxanylmethyl methacrylate 30 ml. pentamethylchloromethyldisiloxane (0.14 mole), 13.8 ml. (0.16 mole) distilled methacrylic acid, 21.0 ml. (0.15 mole) triethylamine, 30 ml. xylene and 0.8 g. hyroquinone are mixed and refluxed for 16 hours. triethylamine hydrochloride precipitates and is filtered. the filtrate is mixed with 1 g. of hydroquinone and 1 g. of copper powder. xylene is distilled from the mixture at atmospheric pressure. the distillation apparatus is then connected to a vacuum line and the fraction which distills at 73.degree.-75.degree. c. under 4-5 mm. hg pressure is collected. the yield of pentamethyldisiloxanylmethyl methacrylate (b.p. 73.degree.-74.degree. c./4 mm. hg, d.sup.20 =0.910, n.sub.d.sup.20 =1.420) is 45%. the disiloxane monomer recovered by distillation contains co-distilled hydroquinone. purification is accomplished by washing the monomer with aqueous alkali solution containing 25% sodium carbonate and 1% sodium hydroxide until the aqueous layer is colorless. the oily monomer layer is then washed with water until neutral and dried over anhydrous sodium carbonate. the dried monomer is refrigerated until used. example 2 this example illustrates the preparation of a representative oxygen-permeable copolymer. a mixture of 35 parts of the disiloxane monomer of example 1, 65 parts of methyl methacrylate and 0.004 ml. of tert-butyl peroxypivalate per ml. of monomer mixture is placed in a polypropylene petri dish to a height of one-eighth of an inch. the dish is covered and placed in a vacuum oven which has been purged with nitrogen. the oven is closed and the temperature is maintained at 45.degree. c. for 20 hours. the copolymer disc is hard, colorless, transparent and rigid. the oxygen permeability is 500 cc.-mil/100 in..sup.2 /24 hr./atm. the oxygen permeability of a disc of polymethylmethacrylate is 34 cc.-mil/100 in..sup.2 /24 hr./atm. while that of a disc of polyhydroxyethylmethacrylate is 13 cc.-mil/100 in..sup.2 /24 hr./atm. a cylindrical plug having dimensions of 1/4 inch thickness and 1/2 inch diameter is prepared by copolymerizing the 35/65 disiloxane monomer/methyl methacrylate mixture in a polyethylene cap at 45.degree. c. for 20 hours. the plug is machined, cut, polished and finished to a concavo-convex lens. examples 3-9 these examples illustrate the preparation and properties of copolymers containing varying proportions of a siloxanyl monomer, methyl methacrylate, and a hydrophilic monomer (hydroxyethyl methacrylate). mixtures of the disiloxane monomer of example 1 (dsm), methyl methacrylate (mma), hydroxyethyl methacrylate (hema) and tert-butyl peroxy pivalate (0.004 ml. per ml. of monomer mixture) is polymerized in polyethylene caps under the conditions shown in the following table: ______________________________________ composition, wt. % temp. time example dsm mma hema .degree.c. hr. properties* ______________________________________ 3 20 75 5 50 6.5 t, h, r 4 35 60 5 45 20 t, h, r 5 44 50 6 50 48 t, h, sr 6 45 50 5 45 20 t, h. sr 7 45 49 6 70 1 t, h, sr 50 16 8 51 40 9 75 2.5 t, h. sr 9 65 30 5 60 4 nt, s, e ______________________________________ *t = transparent; h = hard; r = rigid; sr = semirigid; nt = hazy; s = soft; e = elastomeric the polymerized plugs are machined and finished in the usual manner to lenses with a concave surface on one side and a convex surface on the opposite side. the lenses are easily wetted by water and an aqueous saline solution. example 10 this example illustrates the preparation and properties of a wettable oxygen-permeable terpolymer. a disc is prepared in the manner described in example 2 from a mixture of 45 parts of the disiloxane monomer of example 1, 50 parts of methyl methacrylate and 5 parts of hydroxyethylmethacrylate using tert-butyl peroxypivalate as catalyst. the polymerization is carried out at 45.degree. c. for 20 hours. the resultant disc is colorless, transparent, hard and semi-rigid. the surface of the disc is readily wetted by water and saline solution. the oxygen permeability of the terpolymer is 765 cc.-mil/100 in..sup.2 /24 hr./atm. example 11 this example illustrates the preparation and properties of a wettable oxygen-permeable terpolymer. a disc prepared in the same manner described in example 2 by polymerizing a mixture of 20 parts of the disiloxane monomer of example 1, 75 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate and 0.004 ml. of tert-butyl peroxypivalate per ml. of monomer mixture, at 50.degree. c. has an oxygen permeability of 135 cc.-mil/100 in..sup.2 /24 hr./atm. lenses cut and machined from the disc are transparent, hard and rigid. examples 12-14 these examples illustrate the preparation and properties of copolymers of a siloxanyl monomer with various proportions of other methacrylate ester comonomers. cylindrical plugs are prepared in the manner described in example 3 from mixtures of the disiloxane monomer (dsm) of example 1, methyl methacrylate (mma), octadecyl methacrylate (odma), hydroxyethyl methacrylate (hema) and ethylene glycol dimethacrylate (egdma) by polymerization at 70.degree. c. for 2.5 hours using tert-butyl peroxypivalate as catalyst. the properties of lenses prepared from the plugs are shown in the following table: ______________________________________ ex- am- composition, wt. % prop- ple dsm mma odma hema egdma erties ______________________________________ 12 35 30 30 5 0 t, h, e 13 45 30 20 5 0 t, s, e 14 45 38 10 5 2 t, s, r ______________________________________ example 15 this example illustrates the synthesis of 1,1,1-tris(trimethylsiloxy)methacrylatopropylsilane. 23.8 g. (13.0 ml.) of concentrated sulfuric acid is added slowly with stirring to a mixture of 11.6 g. (14.7 ml.) of absolute ethanol and 16.5 ml. of water. the mixture is cooled in a water bath. methacrylatopropyltrimethoxysilane (0.1 mole, 24.8 g.), is mixed with 0.3 mole (39.6 g.) of trimethylacetoxysilane in a flask equipped with a magnetic stirrer. ethylsulfuric acid (6.5 g.), prepared as described above, is added dropwise from a dropping funnel into the stirred mixture. the flask is cooled during the addition of the ethylsulfuric acid catalyst solution in an ice water bath. after completion of the catalyst addition, the solution is stirred at room temperature for two days. the upper oily layer is then separated, washed with sodium bicarbonate solution, washed with water and then dried over anhydrous sodium sulfate. the produce is distilled under vacuum to remove ethyl acetate. the distillation flask is immersed in a water bath whose temperature is maintained at 40.degree.-45.degree. c. to prevent premature polymerization of the monomer. the yield of tris(trimethylsiloxy)methacrylatopropylsilane is 86% and the density of the monomer is 0.989 g./cc. at 20.degree. c. the monomer is refrigerated until used. example 16 this example illustrates the preparation of a copolymer of methyl methacrylate with the novel polysiloxanyl ester of example 15. a cylindrical plug is prepared by polymerizing a mixture of 40 parts of tris(trimethylsiloxy)-.alpha.-methacryloxypropylsilane and 60 parts of methyl methacrylate in the presence of tert-butyl peroxypivalate at 50.degree. c. lenses prepared from the plug are hard, transparent and oxygen permeable. examples 17-28 this example illustrates the preparation of various copolymers of polysiloxanyl esters and various alkyl acrylates or methacrylates. the polysiloxanyl ester comonomers are prepared according to the general techniques of examples 1 and 15. the copolymer is prepared according to the general technique of example 2. all copolymers resulting are transparent, hard and rigid so as to be suitable for contact lens manufacture. the oxygen permeability of the copolymers varies from 300-500 cc.-mil/100 in..sup.2 /24 hr./atm. as measured by the technique previously described. __________________________________________________________________________ polysiloxanyl ester alkanol ester wt. % in wt. % in .iadd.example.iaddend. copolymer monomer copolymer monomer __________________________________________________________________________ 17 35 heptamethyltrisiloxanylethyl acrylate 65 2-ethylhexyl acrylate 18 30 isobutylhexamethyltrisiloxanylmethyl methacrylate 70 t-butyl methacrylate 19 30 n-propyloctamethyltetrasiloxanylpropyl methacrylate 70 decyl methacrylate 20 25 tri-i-propyltetramethyltrisiloxanylethyl acrylate 75 isopropyl acrylate 21 25 t-butyltetramethyldisiloxanylethyl acrylate 75 methyl acrylate 22 20 n-pentylhexamethyltrisiloxanylmethyl methacrylate 80 ethyl methacrylate 23 20 phenyltetramethyldisiloxanylethyl acrylate 80 octadecyl acrylate 24 20 phenyltetraethyldisiloxanylethyl methacrylate 80 hexyl methacrylate 25 15 triphenyldimethylsiloxanylmethyl acrylate 85 methyl acrylate 26 15 tris(trimethylsiloxy)-.gamma.-methacryloxypropylsilane 85 methyl methacrylate 27 15 methyldi(trimethylsiloxy)-methacryloxymethylsilane 85 n-propyl methacrylate 28 10 pentamethyldi(trimethylsiloxy)-acryloxymethylsilane 90 ethyl acrylate __________________________________________________________________________ as illustrated by examples 17-28, it is preferred to use a straight chain alkanol ester monomer if the polysiloxanyl ester monomer is a branched chain compound, and vice versa. also, it is preferred to employ two acrylate or two methacrylate comonomers to prepare the copolymer, rather than an acrylate monomer and a methacrylate monomer. finally, where more complex polysiloxanyl ester comonomers are employed, the proportion of polysiloxanyl ester is lower, e.g., 10-20%, than if simpler polysiloxanyl esters are employed. in general, the presence of larger, more complex substituents on the interior silicon atoms tend to increase the refractive index of the copolymer, all other factors being equal.
|
062-909-826-416-912
|
US
|
[
"US",
"CN"
] |
G06F11/10,G11C11/406,G11C11/408,G11C29/42,H03M13/09,H04L1/00,H04L45/7453,H04L47/125
| 2020-03-11T00:00:00 |
2020
|
[
"G06",
"G11",
"H03",
"H04"
] |
error check and scrub for semiconductor memory device
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methods, systems, and apparatuses for a memory device (e.g., dram) including an error check and scrub (ecs) procedure in conjunction with refresh operations are described. the ecs procedure may include read/modify-write cycles when errors are detected in code words. in some embodiments, the memory device may complete the ecs procedure over multiple refresh commands, namely by performing a read (or read/modify) portion of the ecs procedure while a first refresh command is executed, and by performing a write portion of the ecs procedure while a second refresh command is executed. the ecs procedure described herein may facilitate avoiding signaling conflicts or interferences that may occur between the ecs procedure and other memory operations.
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1. a method comprising: receiving, at a memory device, a first refresh command directed to a bank of memory cells; in response to receiving the first refresh command, activating a target row of the bank of memory cells and retrieving data from the target row, the data comprising a code word corresponding to an address associated with the target row; detecting at least one error in the code word of the retrieved data; receiving, at the memory device, a second refresh command directed to the bank of memory cells; and in response to receiving the second refresh command, activating the target row and writing at the address the code word with the at least one error corrected. 2. the method of claim 1 , further comprising: deactivating the target row of the bank of memory cells before receiving, at the memory device, the second refresh command. 3. the method of claim 1 , further comprising: correcting the at least one error in the code word based at least in part on detecting the at least one error, wherein detecting and correcting the at least one error in the code word comprises using an error-correction code (ecc) circuit of the memory device. 4. the method of claim 3 , further comprising: writing a register with an indication that the code word has been corrected based on correcting the at least one error in the code word. 5. the method of claim 1 , further comprising: writing the data that include the code word with the at least one error corrected in one or more registers coupled with the bank of memory cells. 6. the method of claim 1 , further comprising: determining that a write command has not been executed to the address, wherein writing at the address the code word with the at least one error corrected is based on the determination. 7. a method comprising: receiving, at a memory device, a first refresh command directed to a bank of memory cells that includes a plurality of rows; and in response to receiving the first refresh command: activating a first row of the plurality of rows; retrieving a first code word from the first row, the first code word corresponding to an address associated with the first row; checking for one or more errors in the first code word using an error-correction code (ecc) circuit of the memory device; and deactivating the first row before activating a second row of the plurality of rows. 8. the method of claim 7 , further comprising: correcting at least one error in the first code word; and storing the first code word with the at least one error corrected in one or more registers coupled with the bank of memory cells. 9. the method of claim 7 , further comprising: receiving, at the memory device, a second refresh command directed to the bank of memory cells; and in response to receiving the second refresh command: determining that the first code word includes no error; activating the second row; retrieving a second code word from the second row; and checking for one or more errors in the second code word using the ecc circuit. 10. the method of claim 7 , further comprising: correcting at least one error in the first code word using the ecc circuit when the ecc circuit detects the at least one error based on checking for the one or more errors in the first code word; and setting an indication that the first code word has been corrected. 11. the method of claim 10 , further comprising: receiving, at the memory device, a second refresh command directed to the bank of memory cells; and in response to receiving the second refresh command: activating the first row; and writing at the address, based at least in part on the indication, the first code word with the at least one error corrected. 12. the method of claim 11 , further comprising: determining that a write command has not been executed at the address, wherein writing at the address the first code word with the at least one error corrected is based on the determination. 13. the method of claim 10 , further comprising: receiving, at the memory device, a second refresh command directed to the bank of memory cells; and in response to receiving the second refresh command: determining that at least one write command has been executed at the address; activating the second row; retrieving a second code word from the second row; and checking for one or more errors in the second code word using the ecc circuit. 14. a memory device comprising: a memory array including a bank of memory cells; an error-correction code (ecc) circuit coupled with the memory array; and circuitry coupled with the memory array and the ecc circuit, the circuitry configured to: receive, from a host device, a first refresh command directed to the bank of memory cells; in response to receiving the first refresh command, activate a target row of the bank of memory cells and retrieving data from the target row, the data comprising a code word corresponding to an address associated with the target row; detect at least one error in the code word using the ecc circuit; receive, at the memory device, a second refresh command directed to the bank of memory cells; and in response to receiving the second refresh command, activate the target row and writing at the address the code word with the at least one error corrected. 15. the memory device of claim 14 , wherein the circuitry is further configured to deactivate the target row of the bank of memory cells before receiving, from the host device, the second refresh command. 16. the memory device of claim 14 , wherein the circuitry is further configured to correct the at least one error in the code word using the ecc circuit based at least in part on detecting the at least one error. 17. the memory device of claim 16 , wherein the circuitry is further configured to write a register with an indication that the code word has been corrected based on correcting the at least one error in the code word. 18. the memory device of claim 14 , wherein the circuitry is further configured to write the data that include the code word with the at least one error corrected in one or more registers coupled with the bank of memory cells. 19. the memory device of claim 18 , wherein the one or more registers are configured to have a data dimension corresponding to a first number of bits in the code word and a second number of bits in a parity field associated with the code word. 20. the memory device of claim 14 , wherein the circuitry is further configured to determine whether one or more write commands have been executed to the address.
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technical field the present disclosure generally relates to a memory device, and more specifically, relates to error check and scrub for a semiconductor memory device. background memory devices are widely used to store information related to various electronic devices such as computers, wireless communication devices, cameras, digital displays, and the like. memory devices may be volatile or non-volatile and can be of various types, such as magnetic hard disks, random access memory (ram), read only memory (rom), dynamic ram (dram), synchronous dynamic ram (sdram), and others. information is stored in various types of ram by charging a memory cell to have different states. improving ram memory devices, generally, can include increasing memory cell density, increasing read/write speeds or otherwise reducing operational latency, increasing reliability, increasing data retention, reducing power consumption, or reducing manufacturing costs, among other metrics. brief description of the drawings the present disclosure will be understood more fully from the detailed description given below and from the accompanying drawings of various embodiments of the disclosure. fig. 1 illustrates a simplified block diagram schematically illustrating a memory device in accordance with an embodiment of the present technology. fig. 2 is a simplified block diagram of an example memory device illustrating various components for performing an error check and scrub (ecs) procedure in accordance with an embodiment of the present disclosure. fig. 3 is an example flow diagram for performing an ecs procedure in accordance with an embodiment of the present disclosure. fig. 4 is a simplified block diagram schematically illustrating an example memory system in accordance with an embodiment of the present disclosure. fig. 5 is a block diagram of an example computer system in accordance with an embodiment of the present disclosure. figs. 6 and 7 are flowcharts of methods for performing an ecs procedure in accordance with some embodiments of the present disclosure. detailed description methods, systems, and apparatuses for memory devices (e.g., dram) are disclosed, which include an error check and scrub (ecs) procedure that may be performed concurrently or in conjunction with other operations (e.g., refresh operations). the described ecs procedure may be regarded as a background operation that the memory devices perform because the memory devices may perform the ecs procedure while carrying out other operations (foreground operations). also, the described ecs procedure may be referred to as an automatic ecs mode because the memory devices may spontaneously perform the ecs procedure—e.g., without receiving, from a host device coupled with the memory devices, a command directed to performing the ecs procedure. such a background operation that the memory devices perform may be beneficial in several aspects, for example, to reduce power consumption of the system including the memory devices (e.g., when using an on-die error correction code (ecc) engine such that energy associated with data traveling to/from the host device for the ecs procedure may be reduced), to enhance production yield of the memory devices (e.g., by reducing and maintaining bit error rates below a threshold using the ecs procedure), to improve bandwidths of the memory devices (e.g., by making certain resources (e.g., interfaces and/or buses) available to other operations of the memory devices, and the like. some semiconductor memory devices, such as dram, store information as charge accumulated in cell capacitors (“cells”), with the cells organized into rows. the charge accumulated in the cell capacitors may escape from the cell capacitor (which may be referred to as “leakage”) to surrounding components connected to the cell capacitor (e.g., metal lines, semiconductor junctions of switching transistors), due to a voltage difference between the capacitor and the surrounding components, in some cases. certain instances of leakage may be exacerbated when a row of memory cells experiences “row hammering,” which refers to a row of memory cells being repeatedly driven to an active level within a certain duration (e.g., over a duration less than that between sequential refresh operations). row hammering may accelerate leakage in memory cells coupled with one or more rows (which may be referred to as victim rows) that are adjacent to the row experiencing the row hammering. a refresh operation, which may be initiated in response to a refresh command issued to the memory device or triggered by a measure of mitigating row hammering issues, or other circumstances, can correct for leakage in a row of memory cells (a memory row), preventing the information from being lost. in some embodiments, a refresh operation includes an operation activating (opening) a memory row (e.g., activate command), which senses or “reads” the information stored in a memory row. as a result of activate command, the memory cells coupled with the memory row may be refreshed (e.g., establishing full or nearly full cell charges corresponding to either logic 1 or logic 0 status). the refresh operation also includes another operation deactivating the open memory row (e.g., precharge command), in some embodiments. thus, refresh operations can help prevent bit errors by renewing cell charges before they degrade to a point where the charge level no longer corresponds to the original stored bit value. in some embodiments, a refresh command may be issued to the memory device regularly—e.g., every refresh interval time (t_refi)—to limit an amount of leakage within a certain level correlated to the refresh interval time. further, a refresh command may be associated with a duration (e.g., t_rfc), during which the refresh command is executed. in some embodiments, durations associated with refresh commands may be determined based on a memory capacity of the memory device and a quantity of memory cells to be refreshed in response to the refresh command—e.g., a first duration correlated to refreshing memory cells of one or more memory rows of all banks of the memory array, a second duration correlated to refreshing memory cells of one or more memory rows of a single bank of the memory array, etc. refresh operations, however, do not correct errors that may occur if a cell's charge has changed enough that the charge is interpreted as a wrong logic value (i.e., the bit has “flipped” from a correct logic value, resulting in a bit “flip” error or bit error). in some cases, memory devices may be configured to perform an ecc function (e.g., using an on-die ecc engine or ecc circuit) that can detect and correct one or more errors in data stored in the memory array (e.g., a code word). in some cases, however, checking for and correcting such errors (i.e., ecs procedure) may be delayed until the memory device is accessed, e.g., during a read operation, to avoid an overhead associated with performing the ecs procedure alone. this delay, however, can increase the likelihood of having a quantity of errors in the data (e.g., the code word) that exceeds the correction capacity of the ecc function. accordingly, in some embodiments, the memory device may incorporate the ecs procedure into refresh operations—i.e., a memory device may perform the ecs procedure (as a background operation) concurrently or in conjunction with refresh operations (as a foreground operation). performing an ecs procedure during a refresh operation provides greater opportunity for discovering bit flip errors before they are compounded by additional bit flips beyond the correction capacity of the ecc function. in some cases, however, an ecs procedure for a group of code words (e.g., 128 code words associated with a memory row) may take a certain duration—e.g., reading a code word from an address of an activated memory row, detecting and correcting an error in the code word, and storing the corrected code word back to the address (which may be collectively referred to as a read-modify-write cycle), and moving on to a next address of the activated memory row until the entire code words of the group (e.g., 128 code words) are checked for errors and corrected if necessary. when the duration of performing the ecs procedure (a background operation) exceeds a time window (e.g., a time window or a duration related to t_rfc) associated with a refresh command (a foreground operation), a signaling conflict or interference may occur between the ecs procedure and other memory operations that may be initiated subsequently to the refresh command. by way of example, a refresh command may refresh all code words of a specific row of all banks of a memory array (e.g., one row per bank for all banks of a memory array)—e.g., a ref_ab command. such a refresh command may include a time window (e.g., a duration of approximately 300 nsec for a 16 gb memory array) that may be enough to perform at least one ecs procedure for the code words. in other cases, a refresh command may be associated with refreshing all code words of a row of a single bank of a memory group of the memory array—e.g., a ref_sb command. such a refresh command may include a shorter time window (e.g., a duration of approximately 100 nsec or less for the 16 gb memory array) that may be insufficient to perform at least one ecs procedure for the code words. accordingly, an ecs procedure incorporated into a refresh command associated with a relatively shorter time window (e.g., the ref_sb command) may result in signaling conflicts and/or interferences with operations that could occur in other banks within the bank group. as such, the ecs procedure may be segmented into two or more portions such that each portion of the ecs procedure may be completed within a time window associated with a refresh command (e.g., the ref_sb command) such that the memory device may avoid the signaling conflicts and/or interferences that may occur otherwise. in some embodiments, the memory device may perform a first portion of an ecs procedure that may include reading (retrieving) a code word from an address (a target scrub address) of a row of memory cells that has been activated in response to a first refresh command (e.g., a first ref_sb command). in addition, the memory device may send the retrieved code word to an ecc engine (e.g., an on-die ecc engine) configured to check for an error in the code word. the ecc engine may correct one or more errors if discovered (i.e., modify the code word) and store the outcome of correction (i.e., a corrected code word and associated parity bits) in one or more registers (e.g., ecs registers). in some embodiments, the memory device may write a register with an indication (e.g., setting a flag) that the code word has been corrected. in this manner (i.e., without performing writing the corrected code word at the address), the memory device may complete the first portion of the ecs procedure (e.g., an ecs-read portion) before a time window of the first refresh command expires to avoid the signaling conflicts and/or interferences. in some embodiments, the first portion of the ecs procedure (e.g., an ecs-read/modify portion) may include the modifying function (e.g., checking for errors in the code word, correcting the errors if discovered, storing the corrected code word in the ecs registers, or a combination thereof) if the memory device is configured to facilitate the modifying function within the time window of the first refresh command—e.g., the ecc engine may be configured to handle a large quantity of code words (i.e., multiple code words) read from the row simultaneously. in some embodiments, the memory device may perform the modifying function (or some aspects of the modifying function) outside the time window of the first refresh command—e.g., the ecc engine may be configured to handle a few code words read from the row at a time. when the code word includes no error, then the first portion of the ecs procedure does not include the modifying function. the memory device may perform a second portion of the ecs procedure (e.g., an ecs-write portion) in response to a second refresh command (e.g., a second ref_sb command) directed to the same bank as the first refresh command. the second portion of the ecs procedure may vary depending on whether writing the corrected code word at the target scrub address is desired or not. for example, when no error has been detected in the code word read during the first portion of the ecs procedure (e.g., the ecs-read portion), the memory device does not need to perform the second portion of the ecs procedure (e.g., the ecs-write portion)—e.g., the memory device may proceed to perform the first portion of the ecs procedure (e.g., the ecs-read portion) at a different row of the same bank. when at least one error has been detected and corrected, however, the memory device may further determine whether a write command has been performed at the target scrub address since the first refresh command has been completed (or any time prior to receiving the second refresh command). if at least one write command has been performed at the target scrub address (i.e., the target scrub address may include a different code word as a result of the write command), then the memory device may not perform the ecs-write portion because the corrected code word stored in the ecs registers may be no longer valid for the target scrub address. if no write command has been performed at the target scrub address since the first refresh command has been completed, then the memory device may perform the ecs-write portion to write at the target scrub address the corrected code word while the second refresh command is being executed. in this manner (i.e., having performed reading and checking for errors in the code words), the memory device may complete the second portion of the ecs procedure (e.g., the ecs-write portion) before a time window of the second refresh command expires to avoid the signaling conflicts and/or interferences. accordingly, the first portion (e.g., the ecs-read portion, the ecs-read/modify portion) and the second portion (e.g., the ecs-write portion) of the ecs procedure may be combined over two refresh commands (e.g., two ref_sb commands) to perform the ecs procedure in its entirety for the code words associated with the refresh commands (e.g., code words of the row in the bank aimed to be refreshed with the ref_sb commands) without incurring the signaling conflicts and/or interferences with other operations within the same bank group. fig. 1 illustrates a simplified block diagram schematically illustrating a memory device 100 in accordance with an embodiment of the present technology. the memory device 100 may include an array of memory cells, such as memory array 150 . the memory array 150 may include a plurality of banks (e.g., banks 0-15 in the example of fig. 1 ), and each bank may include a plurality of word lines (wl), a plurality of bit lines (bl), and a plurality of memory cells arranged at intersections of the word lines and the bit lines. the selection of a word line wl may be performed by a row decoder 140 , and the selection of a bit line bl may be performed by a column decoder 145 . sense amplifiers (samp) may be provided for corresponding bit lines bl and connected to at least one respective local i/o line pair (liot/b), which may in turn be coupled to at least one respective main i/o line pair (miot/b), via transfer gates (tg), which can function as switches. the memory device 100 may employ a plurality of external terminals that include command and address terminals coupled to a command bus and an address bus to receive command signals cmd and address signals addr, respectively. the memory device may further include a chip select terminal to receive a chip select signal cs, clock terminals to receive clock signals ck and ckf, data clock terminals to receive data clock signals wck and wckf, data terminals dq, rdqs, dbi (for data bus inversion function), and dmi (for data mask inversion function), power supply terminals vdd, vss, vddq, and vssq, and on-die termination terminal(s) odt. the command terminals and address terminals may be supplied with an address signal and a bank address signal from outside. the address signal and the bank address signal supplied to the address terminals can be transferred, via a command/address input circuit 105 , to an address decoder 110 . the address decoder 110 can receive the address signals and supply a decoded row address signal (xadd) to the row decoder 140 , and a decoded column address signal (yadd) to the column decoder 145 . the address decoder 110 can also receive the bank address portion of the addr input and supply the decoded bank address signal (badd) and supply the bank address signal to both the row decoder 140 and the column decoder 145 . the command and address terminals may be supplied with command signals cmd, address signals addr, and chip select signals cs, from a memory controller. the command signals may represent various memory commands from the memory controller (e.g., including access commands, which can include read commands and write commands). the select signal cs may be used to select the memory device 100 to respond to commands and addresses provided to the command and address terminals. when an active cs signal is provided to the memory device 100 , the commands and addresses can be decoded and memory operations can be performed. the command signals cmd may be provided as internal command signals icmd to a command decoder 115 via the command/address input circuit 105 . the command decoder 115 may include circuits to decode the internal command signals icmd to generate various internal signals and commands for performing memory operations, for example, a row command signal to select a word line and a column command signal to select a bit line. the internal command signals can also include output and input activation commands, such as clocked command cmdck (not shown in fig. 1 ). the command decoder 115 , in some embodiments, may further include one or more registers 118 a for tracking various counts or values (e.g., counts of refresh commands received by the memory device 100 or self-refresh operations performed by the memory device 100 ). in some embodiments, a subset of registers 118 a may be referred to as mode registers and configured to store user-defined variables to provide flexibility in performing various functions, features, and modes. for example, the memory device may receive a signaling from a host device at the mode registers indicating whether an ecc mode of the memory device is enabled or disabled. in some embodiments, the memory device 100 may include an ecs circuit 175 . the ecs circuit 175 may include an ecc engine, in some cases. the ecs circuit (in conjunction with the address/command input circuit 105 ) may be configured to receive refresh commands (e.g., from a host device or controller coupled with the memory device 100 ) directed to the memory array 150 and perform an ecs procedure. in some embodiments, the memory device 100 may perform the ecs procedure in an automatic ecs mode as a background operation. as set forth above, the ecs circuit may perform the ecs-read portion of the ecs procedure while a first refresh command is being executed. in some cases, the ecs circuit 175 may utilize the ecc engine to detect and correct (e.g., modify) one or more errors in a code word retrieved from the memory array 150 . further, the ecs circuit 175 may store the code word with the one or more errors corrected (i.e., a corrected code word) in one or more registers 118 b (e.g., ecs registers). additionally, the ecs circuit 175 may perform the ecs-write portion of the ecs procedure while a second refresh command is being executed. in some cases, the ecs circuit 175 may write the corrected code word back in the memory array 150 . in other cases, the ecs circuit 175 may omit writing the corrected code word back in the memory array 150 as described in more detail herein. when a read command is issued to a bank with an open row and a column address is timely supplied as part of the read command, read data can be read from memory cells in the memory array 150 designated by the row address (which may have been provided as part of the activate command identifying the open row) and column address. the read command may be received by the command decoder 115 , which can provide internal commands to input/output circuit 160 so that read data can be output from the data terminals dq, rdqs, dbi, and dmi via read/write amplifiers 155 and the input/output circuit 160 according to the rdqs clock signals. the read data may be provided at a time defined by read latency information rl that can be programmed in the memory device 100 , for example, in a mode register (e.g., the register 118 a ). the read latency information rl can be defined in terms of clock cycles of the ck clock signal. for example, the read latency information rl can be a number of clock cycles of the ck signal after the read command is received by the memory device 100 when the associated read data is provided. when a write command is issued to a bank with an open row and a column address is timely supplied as part of the write command, write data can be supplied to the data terminals dq, dbi, and dmi according to the wck and wckf clock signals. the write command may be received by the command decoder 115 , which can provide internal commands to the input/output circuit 160 so that the write data can be received by data receivers in the input/output circuit 160 , and supplied via the input/output circuit 160 and the read/write amplifiers 155 to the memory array 150 . the write data may be written in the memory cell designated by the row address and the column address. the write data may be provided to the data terminals at a time that is defined by write latency wl information. the write latency wl information can be programmed in the memory device 100 , for example, in the mode register (e.g., register 118 a ). the write latency wl information can be defined in terms of clock cycles of the ck clock signal. for example, the write latency information wl can be a number of clock cycles of the ck signal after the write command is received by the memory device 100 when the associated write data is received. the power supply terminals may be supplied with power supply potentials vdd and vss. these power supply potentials vdd and vss can be supplied to an internal voltage generator circuit 170 . the internal voltage generator circuit 170 can generate various internal potentials vpp, vod, vary, vperi, and the like based on the power supply potentials vdd and vss. the internal potential vpp can be used in the row decoder 140 , the internal potentials vod and vary can be used in the sense amplifiers included in the memory array 150 , and the internal potential vperi can be used in many other circuit blocks. the power supply terminal may also be supplied with power supply potential vddq. the power supply potential vddq can be supplied to the input/output circuit 160 together with the power supply potential vss. the power supply potential vddq can be the same potential as the power supply potential vdd in an embodiment of the present technology. the power supply potential vddq can be a different potential from the power supply potential vdd in another embodiment of the present technology. however, the dedicated power supply potential vddq can be used for the input/output circuit 160 so that power supply noise generated by the input/output circuit 160 does not propagate to the other circuit blocks. the on-die termination terminal(s) may be supplied with an on-die termination signal odt. the on-die termination signal odt can be supplied to the input/output circuit 160 to instruct the memory device 100 to enter an on-die termination mode (e.g., to provide one of a predetermined number of impedance levels at one or more of the other terminals of the memory device 100 ). the clock terminals and data clock terminals may be supplied with external clock signals and complementary external clock signals. the external clock signals ck, ckf, wck, wckf can be supplied to a clock input circuit 120 . the ck and ckf signals can be complementary, and the wck and wckf signals can also be complementary. complementary clock signals can have opposite clock levels and transition between the opposite clock levels at the same time. for example, when a clock signal is at a low clock level a complementary clock signal is at a high level, and when the clock signal is at a high clock level the complementary clock signal is at a low clock level. moreover, when the clock signal transitions from the low clock level to the high clock level the complementary clock signal transitions from the high clock level to the low clock level, and when the clock signal transitions from the high clock level to the low clock level the complementary clock signal transitions from the low clock level to the high clock level. input buffers included in the clock input circuit 120 can receive the external clock signals. for example, when enabled by a cke signal from the command decoder 115 , an input buffer can receive the ck and ckf signals and the wck and wckf signals. the clock input circuit 120 can receive the external clock signals to generate internal clock signals iclk. the internal clock signals iclk can be supplied to an internal clock circuit 130 . the internal clock circuit 130 can provide various phase and frequency controlled internal clock signal based on the received internal clock signals iclk and a clock enable signal cke from the command decoder 115 . for example, the internal clock circuit 130 can include a clock path (not shown in fig. 1 ) that receives the internal clock signal iclk and provides various clock signals to the command decoder 115 . the internal clock circuit 130 can further provide input/output (io) clock signals. the 10 clock signals can be supplied to the input/output circuit 160 and can be used as a timing signal for determining an output timing of read data and the input timing of write data. the 10 clock signals can be provided at multiple clock frequencies so that data can be output from and input to the memory device 100 at different data rates. a higher clock frequency may be desirable when high memory speed is desired. a lower clock frequency may be desirable when lower power consumption is desired. the internal clock signals iclk can also be supplied to a timing generator 135 and thus various internal clock signals can be generated. memory devices such as the memory device 100 of fig. 1 can be configured to perform an ecs procedure, as background operations in an automatic ecs mode, on portions of the memory array 150 in response to receiving refresh commands from a connected host device or memory controller. as set forth herein, when the memory device 100 receives a first refresh command directed to a bank of memory cells (e.g., the bank 0 of memory array 150 ), the memory device 100 can, in response to receiving the first refresh command, activate a target row of the bank of memory cells and retrieve data from the target row, the data including a code word. the code word may correspond to an address associated with the target row that may be configured with a set of addresses including the address of the code word. subsequently, the memory device 100 (e.g., the ecs circuit 175 ) may detect and correct one or more errors in the code word of the retrieved data. in some embodiments, the memory device 100 may utilize an ecc circuit (e.g., the ecc engine included in the ecs circuit 175 ) to detect and correct the one or more errors. in some cases, the ecc circuit may be configured to concurrently perform the ecc function on multiple code words. the memory device 100 may store the code word with the one or more errors corrected (a corrected code word) in one or more registers (e.g., the registers 118 b ). such registers may be configured to store multiple code words that each have been corrected for errors detected in the code words. in some cases, the memory device 100 may not detect any error in the code word. the memory device 100 may deactivate the target row of the bank (e.g., via precharge command) as the memory device 100 completes operations associated with the first refresh command. when the memory device 100 receives a second refresh command directed to the bank of memory cells (e.g., the bank 0 of memory array 150 ), the memory device 100 can, in response to receiving the second refresh command, activate the target row of the bank and write at the address the corrected code word stored in the one or more registers (e.g., the register 118 b ). in this regard, the memory device 100 (e.g., the ecs circuit 175 ) may have determined that no write command has been executed at the address before receiving the second refresh command. on the contrary, when the memory device 100 (e.g., the ecs circuit 175 ) determines that at least one write command has been executed at the address before receiving the second refresh command, the memory device 100 (e.g., the ecs circuit 175 ) may omit writing the corrected code word at the address. the memory device 100 may deactivate the target row of the bank (e.g., via precharge command) as the memory device 100 completes operations associated with the second refresh command. fig. 2 is a block diagram 200 schematically illustrating a memory device 210 in accordance with an embodiment of the present technology. the block diagram 200 also illustrates a host device 205 coupled with the memory device 210 . the memory device 210 may be an example of or include aspects of the memory device 100 described with reference to fig. 1 . the memory device 210 may include an ecs circuit 275 (which may be an example of or include aspects of the ecs circuit 175 ), one or more registers 218 (which may be an example of or include aspects of the registers 118 ), an ecc circuit 220 (which may be an example of or include aspects of the ecc engine described with reference to fig. 1 ), a refresh component 230 , and a memory array 250 (which may be an example of or include aspects of the memory array 150 ). further, the ecc circuit 220 may be configured to concurrently perform the ecc function on one or more code words. also, the one or more registers 218 may be configured to store one or more code words that each have been corrected for errors detected in the code words. the memory array 250 may be configured to include a quantity of bank groups 251 (e.g., bank groups 251 a through 251 n ). each individual bank group 251 may include a set of banks of memory cells (e.g., banks 252 a through 252 k in the bank group 251 a ). each individual bank of memory cells (e.g., the bank 252 a ) may include a set of rows, where each row includes a set of addresses that each may correspond to a code word. for example, a row may include 128 addresses that each correspond to a code word with eight (8) bytes. that is, the row may include 1,024 bytes of data, in this example. the refresh component 230 may be configured to control various aspects of refresh commands that the memory device 210 may receive from the host device 205 . in some embodiments, the refresh component 230 may maintain a quantity of counters that each may identify one or more rows of individual banks to perform refresh operations upon receiving a refresh command from the host device 205 . for example, one of such counters of the refresh component 230 may be associated with the bank 252 a and indicate a row 25 out of 1,024 rows that the bank 252 a may include. when the memory device 210 receive a refresh command (e.g., a first ref_sb command) directed to the bank 252 a , the refresh component 230 may perform refresh operations (e.g., activate command, precharge command) on the row 25 based on the information in the counter. the refresh component 230 may, upon completing the refresh command, update the counter to indicate a next row (e.g., a row 26 , a row different than the row 25 ) such that a next refresh command (e.g., a second ref_sb command) directed to the bank 252 a may be executed on the next row (e.g., the row 26 , the row different than the row 25 ), and so on. in this manner, the refresh component 230 may facilitate evenly distributing refresh operations across all rows of individual banks (e.g., the bank 252 a ) to avoid a subset of rows violating a refresh cycle requirement. further, the refresh component 230 may maintain another set of counters (or as part of the quantity of counters) as part of the quantity of counters, which may identify one or more banks of the memory array 250 to perform refresh operations. the ecs circuit 275 may perform ecs procedures, in some cases, in conjunction with the refresh component 230 . in this regard, the ecs circuit 275 may control aspects of operations that the refresh component 230 performs and/or operate independent of the refresh component 230 . for example, the ecs circuit 275 may perform a first portion of the ecs procedure (e.g., the ecs-read portion) that may be incorporated into a first refresh command (e.g., a first ref_sb command) aimed to refresh a row (e.g., the row 25 as indicated by the counter of the refresh component 230 ). the ecs circuit 275 , may detect (and correct) an error in a code word from the row while the first refresh command is executed. the ecs circuit 275 may identify the address of the code word with the error as a target scrub address and store the code word with the error corrected (a corrected code word) in the one or more registers 218 (e.g., ecs registers). upon receiving a second refresh command (e.g., a second ref_sb command) and determining that no write command has been executed to the target scrub address since the first refresh command has been completed, the ecs circuit 275 may, in conjunction with the refresh component 230 in some cases, activate the row including the target scrub address (e.g., the row 25 ) to perform a second portion of the ecs procedure (e.g., the ecs-write portion) such that the ecs circuit 275 may write the corrected code word at the target scrub address. in some cases, the ecs circuit 275 may be configured to control certain counters of the refresh component 230 (e.g., as part of the quantity of counters of the refresh component 230 ) to keep track of the rows including one or more target scrub addresses. in some cases, the ecs circuit 275 may include a set of counters to keep track of the rows including one or more target scrub addresses, which may facilitate the ecs circuit 275 to operate independent of the refresh component 230 . in some cases, the ecs circuit 275 may identify that one or more rows of a bank (e.g., row 88 of the bank 252 a ) includes one or more code words that are more prone to the leakage than remaining rows of the bank—e.g., due to normal variations in process conditions, and maintain a list of target scrub addresses corresponding to such code words. the ecs circuit 275 may, in response to receiving a refresh command, determine to perform the ecs procedure on the target scrub addresses by activating one of the rows (e.g., the row 88 ) including the target scrub address, which may be different than the row that the refresh component 230 indicates to refresh next. in some cases, the ecs circuit 275 may identify victim rows (e.g., rows 111 and 113 ) of a bank upon determining that an adjacent row (e.g., row 112 ) of the bank has experienced the row hammering. the ecs circuit may, in response to receiving a refresh command, determine to perform the ecs procedure on one of the victim rows by activating one of the victim rows (e.g., row 111 , row 113 ), which may be different than the row that the refresh component 230 indicates to refresh next. in some embodiments, the ecs circuit 275 may be configured to receive, from the host device 205 , a first refresh command (e.g., a first ref_sb command) directed to a bank of memory cells (e.g., memory cells of the bank 252 a of the bank group 251 a ). the ecs circuit 275 may, in response to receiving the first refresh command, activate a target row of the bank of memory cells (e.g., the bank 252 a ) and retrieve data from the target row, where the data include a code word corresponding to an address associated with the target row (e.g., one of the 128 addresses of the target row, which may be referred to as a target scrub address). the ecs circuit 275 may detect at least one error in the code word using the ecc circuit 220 . further, the ecs circuit 275 may correct the at least one error in the code word using the ecc circuit 220 based on detecting the at least one error. upon correcting the at least one error in the code word, the ecs circuit 275 may write a register (e.g., the register 118 a , the register 118 b , the register 218 ) with an indication that the code word has been corrected. in some embodiments, the ecs circuit 275 may set a flag to indicate that the code word has been corrected. moreover, the ecs circuit 275 may write (e.g., store) the data that include the code word with the at least one error corrected (i.e., a corrected code word) in one or more registers 218 (e.g., ecs registers) coupled with the memory array 250 . in some embodiments, the one or more registers 218 may be configured to have a data dimension (e.g., a width of the ecs registers) corresponding to a first number of bits in the code word (e.g., sixty-four (64) bits in an 8-bytes long code word) and a second number of bits in a parity field (e.g., eight (8) bits) associated with the code word. in some cases, such configuration of the registers 218 facilitates the memory device 210 to perform the first portion of the ecs procedure (e.g., the ecs-read portion) in a similar manner as a normal read operation, but as a single step in process, such that the read portion of the ecs procedure may not interfere with operations that may occur in other banks (e.g., banks 252 b through 252 k ) within the same bank group (e.g., the bank group 251 a ). in some embodiments, the ecs circuit 275 may deactivate the target row of the bank (e.g., precharge command) before receiving a second refresh command (e.g., a second ref_sb command) from the host device 205 . in some embodiments, the ecs circuit 275 may determine whether one or more write commands have been executed to the address since the first refresh command has been completed. when the ecs circuit 275 determines that no write command has been executed to the address (e.g., the target scrub address), the ecs circuit 275 may, in response to receiving the second refresh command (e.g., the second ref_sb command directed to the bank 252 a ), activate the target row and write at the address the code word with the at least one error corrected (i.e., the corrected code word stored in the ecs registers). in contrast, when the ecs circuit 275 determines that one or more write commands have been executed to the address (e.g., the target scrub address) since the first refresh command has been completed, the ecs circuit 275 may not write at the address the corrected code word because the corrected code word may be no longer valid at the address. fig. 3 is an example flow diagram 300 for illustrating an overall synopsis of a method of performing an ecs procedure in accordance with an embodiment of the present disclosure. the method may be an example of or include aspects of a method that a memory device (e.g., the memory device 100 or 210 ) may perform. such a memory device (e.g., the memory device 100 or 210 ) may include an ecs circuit (e.g., the ecs circuit 175 or 275 ), an ecc engine (e.g., the ecc circuit 220 ), and a memory array (e.g., the memory array 150 or 250 ). the memory array may include a bank of memory cells (e.g., the bank 252 a of the bank group 251 a ), where the bank of memory cells has a set of rows that each are associated with a set of addresses. further, the memory device may maintain one or more registers (e.g., the registers 118 , the registers 218 , the ecs registers) configured to store a code word having at least one error corrected (i.e., a corrected code word). although shown in a particular sequence or order, unless otherwise specified, the order of the processes can be modified. thus, the illustrated embodiments should be understood only as examples, and the illustrated processes can be performed in a different order, and some processes can be performed in parallel. additionally, one or more processes can be omitted in various embodiments. thus, not all processes are required in every embodiment. other process flows are possible. at block 302 , the memory device can receive, from a host device or a controller coupled with the memory device, a first refresh command (e.g., a first ref_sb command) directed to a bank of memory cells (e.g., the bank 252 a ) that includes a set of rows. at block 304 , the memory device may, in response to receiving the first refresh command, activate a target row (i.e., a row of the set of rows) of the bank of memory cells and retrieve data from the target row, where the data include a code word. the code word may correspond to an address (e.g., a target scrub address) associated with the target row. at block 306 , the memory device may determine whether the code word of the retrieved data includes at least one error. in some embodiments, the memory device may utilize the ecc engine to detect the at least one error in the code word. when the memory device determines that there is no error in the code word, the memory device may move on to the next address in the target row when the target row includes additional code words to check for errors. in some cases, the memory device may deactivate the target row to move on a next row when the first refresh command is configured to refresh more than one row (e.g., two or more target rows). in some cases, the memory device may proceed to execute normal operations as indicated at block 322 when the memory device completes checking for errors for code words in the target row. at block 308 , on the contrary, when the memory device detected the at least one error at block 306 , the memory device (in conjunction with the ecc engine) may correct the at least one error in the code word. at block 310 , the memory device may write a register (e.g., the registers 118 , the registers 218 ) with an indication that the code word has been corrected—e.g., setting a flag (or an indication) to indicate that the code word has been corrected. at block 312 , the memory device may write (e.g., store) the data that include the code word with the at least one error corrected (i.e., a corrected code word) in one or more registers (e.g., the registers 218 , the ecs registers) coupled with the bank of memory cells. in some embodiments, the memory device may be configured to repeat the steps including blocks 304 (e.g., retrieving data from the activated target row) through 312 until all code words of the activated target row are read, checked for errors and corrected if discovered. the steps including blocks 304 through 312 may be referred to as a first portion of an ecs procedure that includes a modifying function (e.g., checking for and correcting errors in the code words). in such embodiments, the first portion of the ecs procedure may be referred to as an ecs-read/modify portion. in some embodiments, the memory device may be configured to perform the ecs-read/modify portion before a time window associated with the first refresh command expires—e.g., the ecs-read/modify portion is incorporated into the first refresh command. in some embodiments, however, the memory device may be configured to read all code words of the activated target row during the first portion of the ecs procedure before the time window associated with the first refresh command expires, and perform the modifying function (e.g., checking for and correcting errors in the code words) or some aspects of the modifying function outside the time window associated with the first refresh command. in such embodiments, the first portion may be referred to as an ecs-read portion. at block 314 , the memory device may receive a second refresh command (e.g., a second ref_sb command) directed to the bank (e.g., the bank 252 a ). at block 316 , the memory device may determine whether a write command has been executed to the address (e.g., the target scrub address) since the first refresh command for the target row has completed. if at least one write command has been executed to the address, the code word corresponding to the address may be different from the corrected code word stored in the one or more registers (e.g., the ecs registers)—i.e., the corrected code word may have become invalid for the address. as such, the memory device may not write the corrected code word at the address and may proceed to the next operation—e.g., executing normal operations as indicated at block 322 . on the contrary, if no write command has been executed to the address since completing the first refresh command for the target row, at block 318 , the memory device may write the corrected code word at the address when the target row is activated in response to receiving the second refresh command. subsequently, at block 320 , the memory device may indicate that the corrected code word has been written (e.g., resetting the flag) based on writing the corrected code word at the address. in some embodiments, the memory device may be configured to repeat the steps including blocks 316 through 320 in response to receiving the second refresh command directed to the bank of memory cells (e.g., the bank 252 a ) until all code words of the target row that requires writing corrected code words. subsequently, at block 322 , the memory device may proceed to execute normal operations. the steps including blocks 316 through 320 may be referred to as a second portion of the ecs procedure, which may be referred to as an ecs-write portion. the memory device may complete the second portion of the ecs procedure for all code words in the target row before the time window associated with the second refresh command expires—e.g., the ecs-write portion is incorporated into the second fresh command. in this manner, the memory device may complete a full ecs procedure over multiple (e.g., two as illustrated in the flow diagram 300 ) refresh commands—e.g., completing the ecs-read portion (or the ecs-read/modify portion) incorporated into a first refresh command, and completing the ecs-write portion incorporated into a second refresh command. fig. 4 is a simplified block diagram schematically illustrating a memory system 400 in accordance with an embodiment of the present technology. memory system 400 includes a host device 410 operably coupled to a memory module 420 (e.g., a dual in-line memory module (dimm)). memory module 420 can include controller circuitry 430 operably connected by a bus 440 to a plurality of memory devices 450 . in accordance with one aspect of the present disclosure, the memory devices 450 can perform an ecs procedure while multiple (e.g., two) refresh operations are executed by the host device 410 —e.g., performing a first portion (e.g., the ecs-read portion, the ecs-read/modify portion) of the ecs procedure incorporated into a first refresh command, and performing a second portion (e.g., the ecs-write portion) incorporated into a second refresh command. fig. 5 illustrates an example machine of a computer system 500 within which a set of instructions, for causing the machine to perform any one or more of the methodologies discussed herein, can be executed. in alternative embodiments, the machine can be connected (e.g., networked) to other machines in a lan, an intranet, an extranet, and/or the internet. the machine can operate in the capacity of a server or a client machine in client-server network environment, as a peer machine in a peer-to-peer (or distributed) network environment, or as a server or a client machine in a cloud computing infrastructure or environment. the machine can be a personal computer (pc), a tablet pc, a set-top box (stb), a personal digital assistant (pda), a cellular telephone, a web appliance, a server, a network router, a switch or bridge, or any machine capable of executing a set of instructions (sequential or otherwise) that specify actions to be taken by that machine. further, while a single machine is illustrated, the term “machine” shall also be taken to include any collection of machines that individually or jointly execute a set (or multiple sets) of instructions to perform any one or more of the methodologies discussed herein. the example computer system 500 includes a processing device 502 , a main memory 504 (e.g., read-only memory (rom), flash memory, dynamic random access memory (dram) such as synchronous dram (sdram) or rambus dram (rdram), etc.), a static memory 506 (e.g., flash memory, static random access memory (sram), etc.), and a data storage system 518 , which communicate with each other via a bus 530 . in accordance with one aspect of the present disclosure, the main memory 504 can perform an ecs procedure over multiple refresh operations—e.g., performing a first portion (e.g., the ecs-read portion, the ecs-read/modify portion) of the ecs procedure in a background while a first refresh command is executed (i.e., the first portion of the ecs procedure is incorporated in the first refresh command), and performing a second portion (e.g., the ecs-write portion) in a background while a second refresh command is executed (i.e., the second portion of the ecs procedure is incorporated in the second refresh command). processing device 502 represents one or more general-purpose processing devices such as a microprocessor, a central processing unit, or the like. more particularly, the processing device can be a complex instruction set computing (cisc) microprocessor, reduced instruction set computing (risc) microprocessor, very long instruction word (vliw) microprocessor, or a processor implementing other instruction sets, or processors implementing a combination of instruction sets. processing device 502 can also be one or more special-purpose processing devices such as an application specific integrated circuit (asic), a field programmable gate array (fpga), a digital signal processor (dsp), network processor, or the like. the processing device 502 is configured to execute instructions 526 for performing the operations and steps discussed herein. the computer system 500 can further include a network interface device 508 to communicate over the network 520 . the data storage system 518 can include a machine-readable storage medium 524 (also known as a computer-readable medium) on which is stored one or more sets of instructions 526 or software embodying any one or more of the methodologies or functions described herein. the instructions 526 can also reside, completely or at least partially, within the main memory 504 and/or within the processing device 502 during execution thereof by the computer system 500 , the main memory 504 and the processing device 502 also constituting machine-readable storage media. while the machine-readable storage medium 524 is shown in an example embodiment to be a single medium, the term “machine-readable storage medium” should be taken to include a single medium or multiple media that store the one or more sets of instructions. the term “machine-readable storage medium” shall also be taken to include any medium that is capable of storing or encoding a set of instructions for execution by the machine and that cause the machine to perform any one or more of the methodologies of the present disclosure. the term “machine-readable storage medium” shall accordingly be taken to include, but not be limited to, solid-state memories, optical media, and magnetic media. fig. 6 is a flowchart 600 illustrating a method of operating a memory device in accordance with an embodiment of the present technology. the flowchart 600 may be an example of or include aspects of a method that the memory device 100 (or the ecs circuit 275 ) may perform as described with reference to figs. 1 through 5 . the method includes receiving, at the memory device, a first refresh command directed to a bank of memory cells (box 610 ). in accordance with one aspect of the present technology, the receiving feature of box 610 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the command/address input circuit 105 as described with reference to figs. 1 through 5 . the method further includes, in response to receiving the first refresh command, activating a target row of the bank of memory cells and retrieving data from the target row, where the data comprise a code word corresponding to an address associated with the target row (box 615 ). in accordance with one aspect of the present technology, the activating and retrieving feature of box 615 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the row decoder 140 and the column decoder 145 as described with reference to figs. 1 through 5 . the method further includes detecting at least one error in the code word of the retrieved data (box 620 ). in accordance with one aspect of the present technology, the detecting feature of box 620 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the ecc circuit 220 as described with reference to figs. 1 through 5 . the method further includes receiving, at the memory device, a second refresh command directed to the bank of memory cells (box 625 ). in accordance with one aspect of the present technology, the receiving feature of box 625 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the command/address input circuit 105 as described with reference to figs. 1 through 5 . the method further includes, in response to receiving the second refresh command, activating the target row and writing at the address the code word with the at least one error corrected (box 630 ). in accordance with one aspect of the present technology, the activating and writing feature of box 630 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the row decoder 140 and the column decoder 145 as described with reference to figs. 1 through 5 . in some embodiments, the method may further include deactivating the target row of the bank of memory cells before receiving, at the memory device, the second refresh command. in some embodiments, the method may further include correcting the at least one error in the code word based on detecting the at least one error, where detecting and correcting the at least one error in the code word comprises using an ecc circuit of the memory device. in some embodiments, the method may further include writing a register with an indication that the code word has been corrected based on correcting the at least one error in the code word. in some embodiments, the method may further include writing the data that include the code word with the at least one error corrected in one or more registers coupled with the bank of memory cells. in some embodiments, the method may further include determining that a write command has not been executed to the address, where writing at the address the code word with the at least one error corrected is based on the determination. fig. 7 is a flowchart 700 illustrating a method of operating a memory device in accordance with an embodiment of the present technology. the flowchart 700 may be an example of or include aspects of a method that the memory device 100 (or the ecs circuit 275 ) may perform as described with reference to figs. 1 through 5 . the method includes receiving, at the memory device, a first refresh command directed to a bank of memory cells that includes a set of rows (box 710 ). in accordance with one aspect of the present technology, the receiving feature of box 710 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the command/address input circuit 105 as described with reference to figs. 1 through 5 . the method further includes, in response to receiving the first refresh command, activating a first row of the set of rows (box 715 ), retrieving a first code word from the first row, where the code word corresponds to an address associated with the first row (box 720 ), checking for one or more errors in the first code word using an ecc circuit of the memory device (box 725 ), and deactivating the first row before activating a second row of the set of rows (box 730 ). in accordance with one aspect of the present technology, the activating feature of box 715 and the retrieving feature of box 720 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the row decoder 140 and the column decoder 145 as described with reference to figs. 1 through 5 . in accordance with one aspect of the present technology, the checking feature of box 725 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the ecc circuit 220 as described with reference to figs. 1 through 5 . in accordance with one aspect of the present technology, the deactivating feature of box 730 can be performed by an ecs circuit (e.g., the ecs circuit 175 or 275 ) and/or the row decoder 140 as described with reference to figs. 1 through 5 . in some embodiments, the method may further include correcting at least one error in the first code word. in some embodiments, the method may further include storing the first code word with the at least one error corrected in one or more registers coupled with the bank of memory cells. in some embodiments, the method may further include receiving, at the memory device, a second refresh command directed to the bank of memory cells. in some embodiments, the method may further include, in response to receiving the second refresh command, determining that the first code word includes no error, activating the second row, retrieving a second code word from the second row, and checking for one or more errors in the second code word using the ecc circuit. in some embodiments, the method may further include correcting at least one error in the first code word using the ecc circuit when the ecc circuit detects the at least one error based on checking for the one or more errors in the first code word. in some embodiments, the method may further include setting an indication that the first code word has been corrected. in some embodiments, the method may further include receiving, at the memory device, a second refresh command directed to the bank of memory cells. in some embodiments, the method may further include, in response to receiving the second refresh command, activating the first row, and writing at the address, based on the indication, the first code word with the at least one error corrected. in some embodiments, the method may further include determining that a write command has not been executed at the address, where writing at the address the first code word with the at least one error corrected is based on the determination. in some embodiments, the method may further include receiving, at the memory device, a second refresh command directed to the bank of memory cells. in some embodiments, the method may further include, in response to receiving the second refresh command, determining that at least one write command has been executed at the address, activating the second row, retrieving a second code word from the second row, and checking for one or more errors in the second code word using the ecc circuit. some portions of the preceding detailed descriptions have been presented in terms of algorithms and symbolic representations of operations on data bits within a computer memory. these algorithmic descriptions and representations are the ways used by those skilled in the data processing arts to most effectively convey the substance of their work to others skilled in the art. an algorithm is here, and generally, conceived to be a self-consistent sequence of operations leading to a desired result. the operations are those requiring physical manipulations of physical quantities. usually, though not necessarily, these quantities take the form of electrical or magnetic signals capable of being stored, combined, compared, and otherwise manipulated. it has proven convenient at times, principally for reasons of common usage, to refer to these signals as bits, values, elements, symbols, characters, terms, numbers, or the like. it should be borne in mind, however, that all of these and similar terms are to be associated with the appropriate physical quantities and are merely convenient labels applied to these quantities. the present disclosure can refer to the action and processes of a computer system, or similar electronic computing device, that manipulates and transforms data represented as physical (electronic) quantities within the computer system's registers and memories into other data similarly represented as physical quantities within the computer system memories or registers or other such information storage systems. the present disclosure also relates to an apparatus for performing the operations herein. this apparatus can be specially constructed for the intended purposes, or it can include a general purpose computer selectively activated or reconfigured by a computer program stored in the computer. such a computer program can be stored in a computer readable storage medium, such as, but not limited to, any type of disk including floppy disks, optical disks, cd-roms, and magnetic-optical disks, read-only memories (roms), random access memories (rams), eproms, eeproms, magnetic or optical cards, or any type of media suitable for storing electronic instructions, each coupled to a computer system bus. the algorithms and displays presented herein are not inherently related to any particular computer or other apparatus. various general purpose systems can be used with programs in accordance with the teachings herein, or it can prove convenient to construct a more specialized apparatus to perform the method. the structure for a variety of these systems will appear as set forth in the description below. in addition, the present disclosure is not described with reference to any particular programming language. it will be appreciated that a variety of programming languages can be used to implement the teachings of the disclosure as described herein. the present disclosure can be provided as a computer program product, or software, that can include a machine-readable medium having stored thereon instructions, which can be used to program a computer system (or other electronic devices) to perform a process according to the present disclosure. a machine-readable medium includes any mechanism for storing information in a form readable by a machine (e.g., a computer). in some embodiments, a machine-readable (e.g., computer-readable) medium includes a machine (e.g., a computer) readable storage medium such as a read only memory (“rom”), random access memory (“ram”), magnetic disk storage media, optical storage media, flash memory components, etc. in the foregoing specification, embodiments of the disclosure have been described with reference to specific example embodiments thereof. it will be evident that various modifications can be made thereto without departing from the broader spirit and scope of embodiments of the disclosure as set forth in the following claims. the specification and drawings are, accordingly, to be regarded in an illustrative sense rather than a restrictive sense. those skilled in the art will appreciate that the components and blocks illustrated in figs. 1-6 described above, may be altered in a variety of ways. for example, the order of the logic may be rearranged, substeps may be performed in parallel, illustrated logic may be omitted, other logic may be included, etc. in some implementations, one or more of the components described above can execute one or more of the processes described below. reference in this specification to “implementations” (e.g. “some implementations,” “various implementations,” “one implementation,” “an implementation,” etc.) means that a particular feature, structure, or characteristic described in connection with the implementation is included in at least one implementation of the disclosure. the appearances of these phrases in various places in the specification are not necessarily all referring to the same implementation, nor are separate or alternative implementations mutually exclusive of other implementations. moreover, various features are described which may be exhibited by some implementations and not by others. similarly, various requirements are described which may be requirements for some implementations but not for other implementations. as used herein, being above a threshold means that a value for an item under comparison is above a specified other value, that an item under comparison is among a certain specified number of items with the largest value, or that an item under comparison has a value within a specified top percentage value. as used herein, being below a threshold means that a value for an item under comparison is below a specified other value, that an item under comparison is among a certain specified number of items with the smallest value, or that an item under comparison has a value within a specified bottom percentage value. as used herein, being within a threshold means that a value for an item under comparison is between two specified other values, that an item under comparison is among a middle specified number of items, or that an item under comparison has a value within a middle specified percentage range. relative terms, such as high or unimportant, when not otherwise defined, can be understood as assigning a value and determining how that value compares to an established threshold. for example, the phrase “selecting a fast connection” can be understood to mean selecting a connection that has a value assigned corresponding to its connection speed that is above a threshold. as used herein, the word “or” refers to any possible permutation of a set of items. for example, the phrase “a, b, or c” refers to at least one of a, b, c, or any combination thereof, such as any of: a; b; c; a and b; a and c; b and c; a, b, and c; or multiple of any item such as a and a; b, b, and c; a, a, b, c, and c; etc. any patents, patent applications, and other references noted above are incorporated herein by reference. aspects can be modified, if necessary, to employ the systems, functions, and concepts of the various references described above to provide yet further implementations. if statements or subject matter in a document incorporated by reference conflicts with statements or subject matter of this application, then this application shall control.
|
063-397-800-808-512
|
US
|
[
"EP",
"US",
"WO"
] |
C07D213/56,A61K31/16,A61K31/335,A61K31/336,A61P35/00,C07D213/81,C07D303/02,C07D303/04,C07D241/12,A61K45/06,C07D213/64,C07D213/76,C07D237/08,C07D239/26,C07D241/18,C07D401/04,C07D405/10,C07D413/04
| 2017-11-14T00:00:00 |
2017
|
[
"C07",
"A61"
] |
novel substituted biaryl compounds as indoleamine 2,3-dioxygenase (ido) inhibitors
|
disclosed herein is a compound of formula (i), or a pharmaceutically acceptable salt thereof. also disclosed herein are uses of a compound disclosed herein in the potential treatment or prevention of an ido-associated disease or disorder. also disclosed herein are compositions comprising a compound disclosed herein. further disclosed herein are uses of a composition in the potential treatment or prevention of an ido-associated disease or disorder.
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1. a compound of formula (i), or a pharmaceutically acceptable salt thereof: wherein: n is 1; p is selected from 0 and 1; each occurrence of a is independently selected from —ch═ and —n═, provided that at least one a is —ch═; m is selected from —o—, —s— and —cr a r b —, each of r a and r b is independently selected from h, halogen, —oh, and —c 1-8 alkyl; or alternatively, r a and r b together with the carbon to which they are attached form a c 3-4 carbocyclic ring, optionally substituted with 1-2 substituents independently selected from halogen and c 1-4 alkyl; r 1 is selected from: (1) phenyl, and (2) a 6-membered monocyclic heterocyclyl; wherein each of the phenyl of (1) and the heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-8 cycloalkyl, optionally substituted with —oh, (c) —cn, (d) —o—c 1-8 alkyl, optionally substituted with 1-5 halogens, (e) —o—c 3-8 cycloalkyl, (f) —c 1-8 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)r c , and —s(o) 2 —c 1-8 alkyl, wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl, (g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl, (h) —c(o)—oh, (i) aryl, optionally substituted with 1-3 halogens and (j) heterocyclyl, optionally substituted with 1-3 substituents independently selected from halogen and —c 1-8 alkyl; r 2 is selected from: (1) c 3-8 carbocyclyl, and (2) aryl, wherein each of the c 3-8 carbocyclyl of (1), and the aryl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-8 cycloalkyl, (c) —cn, (d) —o—c 1-8 alkyl, optionally substituted with 1-3 halogens and (e) —c 1-8 alkyl, optionally substituted with 1-3 substituents independently selected from halogen, —oh, and —nh 2 ; and r 3 is selected from h, halogen and —c 1-8 alkyl. 2. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: n is 1; p is 0 or 1; m is selected from —o— and —cr a r b —, each of r a and r b is independently selected from h, halogen, —oh and —c 1-6 alkyl; r 1 is selected from: (1) phenyl, and (2) a 6-membered monocyclic heterocyclyl; wherein each of the phenyl of (1) and the heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, optionally substituted with —oh, (c) —cn, (d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, (e) —o—c 3-6 cycloalkyl, (f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)r c , and —s(o) 2 —c 1-6 alkyl, wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl, (g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl, (h) —c(o)—oh, and (i) heterocyclyl, optionally substituted with 1-3 substituents independently selected from halogen and —c 1-6 alkyl; r 2 is selected from: (1) c 3-6 carbocyclyl, and (2) aryl, wherein each of the c 3-6 carbocyclyl of (1), and the aryl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, (c) —cn, (d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, and (e) —c 1-6 alkyl, optionally substituted with 1-3 substituents independently selected from halogen, —oh, and —nh 2 ; and r 3 is selected from h and halogen. 3. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: n is 1; p is 0 or 1; each a group is —ch═; or alternatively, one a group is —n═ and the three other a groups are each —ch═; and m is selected from —o—, —ch 2 —, —cf 2 —, and —ch(ch 3 )—. 4. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein r 3 is selected from h and halogen. 5. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: r 1 is selected from: (1) phenyl, and (2) a 6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s; wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl optionally substituted with —oh, (c) —cn, (d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, (e) —o—c 3-6 cycloalkyl, (f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl, (g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl, (h) —c(o)—oh, and (i) a 5-6 membered monocyclic ring containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl. 6. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: r 1 is a 6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) cyclopropyl, optionally substituted with —oh, (c) cyclobutyl, optionally substituted with —oh, (d) —cn, (e) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens, (f) —o-cyclopropyl, (g) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh and —s(o) 2 —c 1-4 alkyl, (h) —c(o)—oh, and (i) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl. 7. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: r 2 is selected from: (1) c 3-6 carbocyclyl, and (2) phenyl; wherein each of the c 3-6 carbocyclyl of (2) and the phenyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, (c) —cn, and (d) —c 1-4 alkyl, optionally substituted with 1-3 substituents independently selected from halogen and —oh. 8. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: r 2 is selected from: (1) 5-6 membered bridged bicyclic carbocyclyl, and (2) phenyl; wherein each of the 5-6 membered carbocyclyl of (1) and the phenyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —cn, and (c) —c 1-4 alkyl, optionally substituted with 1-3 halogens. 9. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: n is 1; p is 0 or 1; each a group is —ch═; or alternatively, one a group is —n═ and the three other a groups are each —ch═; m is selected from —o—, —ch 2 —, —cf 2 —, and —ch(ch 3 )—; r 1 is selected from: (1) phenyl, and (2) a 6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s; wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, optionally substituted with —oh, (c) —cn, (d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, (e) —o—c 3-6 cycloalkyl, (f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl, (g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl, (h) —c(o)—oh, and (i) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl; r 2 is selected from: (1) c 3-6 carbocyclyl, and (2) phenyl; wherein each of the c 3-6 carbocyclyl of (2) and the phenyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, (c) —cn, and (d) —c 1-4 alkyl, optionally substituted with 1-3 substituents independently selected from halogen and —oh; and r 3 is selected from h and halogen. 10. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, wherein: n is 1; p is 0 or 1; each a group is —ch═; or alternatively, one a group is —n═ and the three other a groups are each —ch═; m is selected from —o—, —ch 2 —, and —ch(ch 3 )—; r 1 is a 6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; each of which is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) cyclopropyl, optionally substituted with —oh, (c) cyclobutyl, optionally substituted with —oh, (d) —cn, (e) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens, (f) —o-cyclopropyl, (g) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh and —s(o) 2 —c 1-4 alkyl, (h) —c(o)—oh, and (i) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl; r 2 is selected from: (1) a 5-6 membered bridged bicyclic carbocyclyl, and (2) phenyl; wherein each of the 5-6 membered carbocyclyl of (1) and the phenyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —cn, and (c) —c 1-4 alkyl, optionally substituted with 1-3 halogens; and r 3 is selected from h and halogen. 11. the compound of claim 1 having formula (ii), or a pharmaceutically acceptable salt thereof, wherein: p is 0 or 1; r 1 is selected from: (1) phenyl, and (2) a 6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s; wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) —c 3-6 cycloalkyl, optionally substituted with —oh, (c) —cn, (d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, (e) —o—c 3-6 cycloalkyl, (f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl, (g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl, (h) —c(o)—oh, and (i) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl; r 3 is selected from h and halogen; r a is selected from (a) h and (b) c 1-4 alkyl; and r d is selected from: (a) h, (b) halogen, and (c) —cn. 12. the compound of claim 11 , or a pharmaceutically acceptable salt thereof, wherein: p is 0 or 1; r 1 is a 6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; each of which is optionally substituted with 1-3 substituents independently selected from: (a) halogen, (b) cyclopropyl, (c) —cn, (d) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens, (e) —o-cyclopropyl, (f) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-4 alkyl, (g) —nh—s(o) 2 —c 1-4 alkyl, (h) —nh—s(o) 2 -cyclopropyl, (i) —c(o)—oh, and (j) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl; r 3 is selected from h and halogen; r c is selected from (a) h and (b) —ch 3 ; and r d is selected from (a) halogen and (b) —cn. 13. the compound of claim 1 , or a pharmaceutically acceptable salt thereof, selected from the group consisting of: 4-cyano-n-(1-(4-(6-methoxy-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(difluoromethoxy)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropylpyridin-3-yl)-3-fluorophenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropyl-4-methylpyridin-3-yl)-3-fluorophenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(5-(cyclopropanesulfonamido)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(2-cyclopropylpyrimidin-5-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-methyl-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropyl-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyanopyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(1-hydroxyethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyano-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(3-methyl-1,2,4-oxadiazol-5-yl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(hydroxymethyl)-4-methoxypyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-((methylsulfonyl)methyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(difluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 5-(4-(1-(4-cyanobenzamido)cyclobutyl)phenyl)picolinic acid, 4-cyano-n-(1-(4-(6-(2,2,2-trifluoro-1-hydroxyethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(hydroxymethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-cyclopropyl-2-(hydroxymethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(5-cyclopropylpyrazin-2-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(5-(2-fluoroethoxy)pyrazin-2-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-isopropylpyridazin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-methoxy-4-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-methoxy-2-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide, n-(1-(4-(4,6-bis(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)-4-cyanobenzamide, 4-cyano-n-(1-(4-(6-(2-fluoroethoxy)pyridazin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-methoxy-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, cyano-n-(1-(4-(6-methoxy-5-(methylsulfonamido)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-methoxy-2,4-dimethylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-cyano-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(difluoromethoxy)-2,4-dimethylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(6-(difluoromethoxy)-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-formyl-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(4-(4-(difluoromethyl)-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide, 4-cyano-n-(1-(6′-cyclopropyl-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)benzamide, 3-cyano-n-(1-(6′-(difluoromethoxy)-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)bicyclo[1.1.1]-pentane-1-carboxamide, 3-cyano-n-(1-(6′-cyclopropyl-4′-methyl43,3′-bipyridin]-6-yl)cyclobutyl)bicyclo[1.1.1]pentane-1-carboxamide, 4-fluoro-n-(3-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)oxetan-3-yl)benzamide, 4-chloro-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide, n-(1-(4-(6-cyclopropoxy-4-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclopropyl)-4-fluorobenzamide, n-(1-(4-(6-cyclopropoxy-4-(hydroxymethyl)pyridin-3-yl)phenyl)cyclopropyl)-4-fluorobenzamide, 4-fluoro-n-(1-(4-(4-(hydroxymethyl)-6-isopropoxypyridin-3-yl)phenyl)cyclopropyl)benzamide, (s)-4-fluoro-n-(1-(4-(4-(1-hydroxyethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide, (r)-4-fluoro-n-(1-(4-(4-(1-hydroxyethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide, 2,2,2-trifluoroacetate salt, 4-fluoro-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide, and n-(1-(4-(6-cyclopropoxy-4-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclobutyl)-4-fluorobenzamide. 14. a composition which comprises an inert carrier and a compound of claim 1 or a pharmaceutically acceptable salt thereof.
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cross reference to related applications the present application is the 371 national phase application of international application no. pct/us2018/059979, filed nov. 9, 2018, which claims the benefit of u.s. provisional application no. 62/585,742, filed novmber 14, 2017, hereby incorporated by reference in their entirety. background of the invention tryptophan (trp) is an essential amino acid required for the biosynthesis of proteins, niacin and the neurotransmitter 5-hydroxytryptamine (serotonin). the enzyme indoleamine 2,3-dioxygenase (ido) catalyzes the first and rate limiting step in the degradation of l-tryptophan to n-formyl-kynurenine. in human cells, a depletion of trp resulting from ido activity is a prominent gamma interferon (efn-γ)-inducible antimicrobial effector mechanism. ifn-γ stimulation induces activation of ido, which leads to a depletion of trp, thereby arresting the growth of trp-dependent intracellular pathogens such as toxoplasma gondii and chlamydia trachomatis. ido activity also has an antiproliferative effect on many tumor cells, and ido induction has been observed in vivo during rejection of allogeneic tumors, indicating a possible role for this enzyme in the tumor rejection process (daubener, et al, 1999, adv. exp. med. biol, 467: 517-24; taylor, et al, 1991, faseb j., 5: 2516-22). it has been observed that hela cells co-cultured with peripheral blood lymphocytes (pbls) acquire an immuno-inhibitory phenotype through up-regulation of ido activity. a reduction in pbl proliferation upon treatment with interleukin-2 (il2) was believed to result from ido released by the tumor cells in response to ifn-γ secretion by the pbls. this effect was reversed by treatment with 1-methyl-tryptophan (imt), a specific ido inhibitor. it was proposed that ido activity in tumor cells may serve to impair antitumor responses (logan, et al, 2002, immunology, 105: 478-87). several lines of evidence suggest that ido is involved in induction of immune tolerance. studies of mammalian pregnancy, tumor resistance, chronic infections and autoimmune diseases have shown that cells expressing ido can suppress t-cell responses and promote tolerance. accelerated trp catabolism has been observed in diseases and disorders associated with cellular immune activation, such as infection, malignancy, autoimmune diseases and aids, as well as during pregnancy. for example, increased levels of ifns and elevated levels of urinary trp metabolites have been observed in autoimmune diseases; it has been postulated that systemic or local depletion of trp occurring in autoimmune diseases may relate to the degeneration and wasting symptoms of these diseases. in support of this hypothesis, high levels of ido were observed in cells isolated from the synovia of arthritic joints. ifns are also elevated in human immunodeficiency virus (hiv) patients and increasing ifn levels are associated with a worsening prognosis. thus, it was proposed that ido is induced chronically by hiv infection, and is further increased by opportunistic infections, and that the chronic loss of trp initiates mechanisms responsible for cachexia, dementia and diarrhea and possibly immunosuppression of aids patients (brown, et al., 1991, adv. exp. med. biol, 294: 425-35). to this end, it has recently been shown that ido inhibition can enhance the levels of virus-specific t cells and, concomitantly, reduce the number of virally-infected macrophages in a mouse model of hiv (portula et al., 2005, blood, 106: 2382-90). ido is believed to play a role in the immunosuppressive processes that prevent fetal rejection in utero. more than 40 years ago, it was observed that, during pregnancy, the genetically disparate mammalian conceptus survives in spite of what would be predicted by tissue transplantation immunology (medawar, 1953, symp. soc. exp. biol. 7: 320-38). anatomic separation of mother and fetus and antigenic immaturity of the fetus cannot fully explain fetal allograft survival. recent attention has focused on immunologic tolerance of the mother. because ido is expressed by human syncytiotrophoblast cells and systemic tryptophan concentration falls during normal pregnancy, it was hypothesized that ido expression at the maternal-fetal interface is necessary to prevent immunologic rejection of the fetal allografts. to test this hypothesis, pregnant mice (carrying syngeneic or allogeneic fetuses) were exposed to imt, and a rapid, t cell-induced rejection of all allogeneic conception was observed. thus, by catabolizing tryptophan, the mammalian conceptus appears to suppress t-cell activity and defends itself against rejection, and blocking tryptophan catabolism during murine pregnancy allows maternal t cells to provoke fetal allograft rejection (moan, et al., 1998, science, 281: 1191-3). further evidence for a tumoral immune resistance mechanism based on tryptophan degradation by ido comes from the observation that most human tumors constitutively express ido, and that expression of ido by immunogenic mouse tumor cells prevents their rejection by preimmunized mice. this effect is accompanied by a lack of accumulation of specific t cells at the tumor site and can be partly reverted by systemic treatment of mice with an inhibitor of ido, in the absence of noticeable toxicity. thus, it was suggested that the efficacy of therapeutic vaccination of cancer patients might be improved by concomitant administration of an ido inhibitor (uyttenhove et al., 2003, nature med., 9: 1269-74). it has also been shown that the ido inhibitor, 1-mt, can synergize with chemotherapeutic agents to reduce tumor growth in mice, suggesting that ido inhibition may also enhance the anti-tumor activity of conventional cytotoxic therapies (muller et al, 2005, nature med., 11: 312-9). one mechanism contributing to immunologic unresponsiveness toward tumors may be presentation of tumor antigens by tolerogenic host apcs. a subset of human ido-expressing antigen-presenting cells (apcs) that coexpressed cd 123 (il3ra) and ccr6 and inhibited t-cell proliferation have also been described. both mature and immature cd123-positive dendritic cells suppressed t-cell activity, and this ido suppressive activity was blocked by 1mt (munn, et al, 2002, science, 297: 1867-70). it has also been demonstrated that mouse tumor-draining lymph nodes (tdlns) contain a subset of plasmacytoid dendritic cells (pdcs) that constitutively express immunosuppressive levels of ido. despite comprising only 0.5% of lymph node cells, in vitro, these pdcs potently suppressed t cell responses to antigens presented by the pdcs themselves and also, in a dominant fashion, suppressed t cell responses to third-party antigens presented by nonsuppressive apcs. within the population of pdcs, the majority of the functional ido-mediated suppressor activity segregated with a novel subset of pdcs coexpressing the b-lineage marker cd19. thus, it was hypothesized that ido-mediated suppression by pdcs in tdlns creates a local microenvironment that is potently suppressive of host antitumor t cell responses (munn, et al., 2004, j. clin. invest, 114(2): 280-90). ido degrades the indole moiety of tryptophan, serotonin and melatonin, and initiates the production of neuroactive and immunoregulatory metabolites, collectively known as kynurenines. by locally depleting tryptophan and increasing proapoptotic kynurenines, ido expressed by dendritic cells (dcs) can greatly affect t-cell proliferation and survival. ido induction in dcs could be a common mechanism of deletional tolerance driven by regulatory t cells. because such tolerogenic responses can be expected to operate in a variety of physiopathological conditions, tryptophan metabolism and kynurenine production might represent a crucial interface between the immune and nervous systems (grohmann, et al, 2003, trends immunol, 24: 242-8). in states of persistent immune activation, availability of free serum trp is diminished and, as a consequence of reduced serotonin production, serotonergic functions may also be affected (wirleitner, et al., 2003, curr. med. chem., 10: 1581-91). in light of the potential role for ido in immunosuppression, tumor resistance and/or rejection, chronic infections, hiv-infection, aids (including its manifestations such as cachexia, dementia and diarrhea), autoimmune diseases or disorders (such as rheumatoid arthritis), and immunologic tolerance and prevention of fetal rejection in utero, therapeutic agents aimed at suppression of tryptophan degradation by inhibiting ido activity are desirable. inhibitors of ido can be used to activate t cells and therefore enhance t cell activation when the t cells are suppressed by pregnancy, malignancy or a virus such as hiv. inhibition of ido may also be an important treatment strategy for patients with neurological or neuropsychiatric diseases or disorders such as depression. compounds disclosed herein are useful in the potential treatment or prevention of ido-related diseases. summary of the invention disclosed herein are novel compounds of formula (i), which are inhibitors of the ido enzymes. also disclosed herein are uses of these compounds in the potential treatment or prevention of an ido-associated disease or disorder. also disclosed herein are compositions comprising one or more of the compounds. further disclosed herein are uses of these compositions in the potential prevention or treatment of an ido-associated disease or disorder. detailed description of the invention disclosed herein is a compound of formula (i), or a pharmaceutically acceptable salt thereof: wherein:n is selected from 1, 2 and 3;p is selected from 0, 1 and 2;each occurrence of a is independently selected from —ch═ and —n═, provided that at least one a is —c═;m is selected from —o—, —s— and —cr a r b —, each of r a and r b is independently selected from h, halogen, —oh, and —c 1-8 alkyl; or alternatively, r a and r b together with the carbon to which they are attached form a c 3-4 carbocyclic ring, optionally substituted with 1-2 substituents independently selected from halogen and c 1-4 alkyl;r 1 is selected from: (1) aryl, and(2) heterocyclyl;wherein each of the aryl of (1) and the heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl, optionally substituted with —oh,(c) —cn,(d) oxo,(e) —o—c 1-8 alkyl, optionally substituted with 1-5 halogens,(f) —o—c 3-8 cycloalkyl,(g) —c 1-8 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)r c , and —s(o) 2 —c 1-8 alkyl, wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl,(h) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl,(i) —c(o)—oh,(j) aryl, optionally substituted with 1-3 halogens and(k) heterocyclyl, optionally substituted with 1-3 substituents independently selected from halogen and —c 1-8 alkyl;r 2 is selected from: (1) c 1-8 alkyl,(2) —c 3-8 carbocyclyl,(3) aryl, and(4) heterocyclyl;wherein the c 1-8 alkyl of (1) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl,(c) —o—c 1-8 alkyl, and(d) heterocyclyl; andwherein each of the c 3-8 carbocyclyl of (2), the aryl of (3) and the heterocyclyl of (4) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl,(c) —cn,(d) —o—c 1-8 alkyl, optionally substituted with 1-3 halogens and(e) —c 1-8 alkyl, optionally substituted with 1-3 substituents independently selected from halogen, —oh, and —nh 2 ; andr 3 is selected from h, halogen and —c 1-8 alkyl. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1;p is 0 or 1;m is selected from —o— and —cr a r b —, each of r a and r b is independently selected from h, halogen, —oh and —c 1-6 alkyl;r 1 is selected from: (1) aryl, and(2) heterocyclyl;wherein each of the aryl of (1) and the heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl, optionally substituted with —oh,(c) —cn,(d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens,(e) —o—c 3-6 cycloalkyl,(f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)r c , and —s(o) 2 —c 1-6 alkyl, wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(h) —c(o)—oh, and(i) heterocyclyl, optionally substituted with 1-3 substituents independently selected from halogen and —c 1-6 alkyl;r 2 is selected from: (1) c 1-6 alkyl, optionally substituted with 1-3 halogens,(2) c 3-6 carbocyclyl,(3) aryl, and(4) heterocyclyl;wherein each of the c 3-6 carbocyclyl of (2), the aryl of (3) and the heterocyclyl of (4) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl,(c) —cn,(d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens, and(e) —c 1-6 alkyl, optionally substituted with 1-3 substituents independently selected from halogen, —oh, and —nh 2 ; andr 3 is selected from h and halogen. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1;p is 0 or 1;each a group is —ch═;or alternatively, one a group is —n═ and the three other a groups are each —ch═; andm is selected from —o—, —ch 2 —, —cf 2 —, and —ch(ch 3 )—. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof, r 3 is selected from h and halogen. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl, and(2) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s;wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl optionally substituted with —oh,(c) —cn,(d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens,(e) —o—c 3-6 cycloalkyl,(f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl,(g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(h) —c(o)—oh, and(i) a 5-6 membered monocyclic ring containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: r 1 is a 5-6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl, optionally substituted with —oh,(c) cyclobutyl, optionally substituted with —oh,(d) —cn,(e) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens,(f) —o-cyclopropyl,(g) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh and —s(o) 2 —c 1-4 alkyl,(h) —c(o)—oh, and(i) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: r 2 is selected from: (1) c 1-4 alkyl, optionally substituted with 1-3 halogens,(2) c 3-6 carbocyclyl, and(3) phenyl;wherein each of the c 3-6 carbocyclyl of (2) and the phenyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl,(c) —cn, and(d) —c 1-4 alkyl, optionally substituted with 1-3 substituents independently selected from halogen and —oh. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: r 2 is selected from: (1) 5-6 membered bridged bicyclic carbocyclyl, and(2) phenyl;wherein each of the 5-6 membered carbocyclyl of (1) and the phenyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn, and(c) —c 1-4 alkyl, optionally substituted with 1-3 halogens. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1;p is 0 or 1;each a group is —ch═;or alternatively, one a group is —n═ and the three other a groups are each —ch═;m is selected from —o—, —ch 2 —, —cf 2 —, and —ch(ch 3 )—;r 1 is selected from: (1) phenyl, and(2) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s;wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl, optionally substituted with —oh,(c) —cn,(d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens,(e) —o—c 3-6 cycloalkyl,(f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl,(g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(h) —c(o)—oh, and(i) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl;r 2 is selected from: (1) c 1-4 alkyl, optionally substituted with 1-3 halogens,(2) c 3-6 carbocyclyl, and(3) phenyl;wherein each of the c 3-6 carbocyclyl of (2) and the phenyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl,(c) —cn, and(d) —c 1-4 alkyl, optionally substituted with 1-3 substituents independently selected from halogen and —oh; andr 3 is selected from h and halogen. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1;p is 0 or 1;each a group is —ch═;or alternatively, one a group is —n═ and the three other a groups are each —ch═;m is selected from —o—, —ch 2 —, and —ch(ch 3 )—;r 1 is a 5-6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; each of which is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl, optionally substituted with —oh,(c) cyclobutyl, optionally substituted with —oh,(d) —cn,(e) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens,(f) —o-cyclopropyl,(g) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh and —s(o) 2 —c 1-4 alkyl,(h) —c(o)—oh, and(i) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl;r 2 is selected from: (1) a 5-6 membered bridged bicyclic carbocyclyl, and(2) phenyl;wherein each of the 5-6 membered carbocyclyl of (1) and the phenyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn, and(c) —c 1-4 alkyl, optionally substituted with 1-3 halogens; andr 3 is selected from h and halogen. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereofm the compound is of formula (ii): wherein:p is 0 or 1;r 1 is selected from: (1) phenyl, and(2) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s;wherein each of the phenyl of (1) and the mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl, optionally substituted with —oh,(c) —cn,(d) —o—c 1-6 alkyl, optionally substituted with 1-3 halogens,(e) —o—c 3-6 cycloalkyl,(f) —c 1-6 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-6 alkyl,(g) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(h) —c(o)—oh, and(i) a 5-6 membered monocyclic heterocyclyl containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl;r 3 is selected from h and halogen;r a is selected from (a) h and (b) c 1-4 alkyl; andr d is selected from: (a) h,(b) halogen, and(c) —cn. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: p is 0 or 1;r 1 is a 5-6 membered monocyclic heterocyclyl selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl; each of which is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl,(c) —cn,(d) —o—c 1-3 alkyl, optionally substituted with 1-3 halogens,(e) —o-cyclopropyl,(f) —c 1-4 alkyl, optionally substituted with 1-4 substituents independently selected from halogen, —oh, and —s(o) 2 —c 1-4 alkyl,(g) —nh—s(o) 2 —c 1-4 alkyl,(h) —nh—s(o) 2 -cyclopropyl,(i) —c(o)—oh, and(j) 1,2,4-oxadiazolyl, optionally substituted with —c 1-4 alkyl;r 3 is selected from h and halogen;r e is selected from (a) h and (b) —ch 3 ; andr d is selected from (a) halogen and (b) —cn. in one embodiment of the compound of formula (i), or a pharmaceutically acceptable salt thereof: n is selected from 1, 2 and 3;p is selected from 0, 1 and 2;each occurrence of a is independently selected from —ch═ and —n═;m is selected from —o—, —s— and —cr a r b —, each of r a and r b is independently selected from h, halogen, —oh and —c 1-8 alkyl; or alternatively, r a and r b together with the carbon to which they are attached form a c 3-4 carbocyclic ring, optionally substituted with 1-2 substituents independently selected from halogen and c 1-4 alkyl;r 1 is selected from: (1) aryl and(2) heterocyclyl;wherein each of the aryl of (1) and heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl optionally substituted with —oh,(c) —cn,(d) oxo,(e) —o—c 1-8 alkyl optionally substituted with 1-5 halogens,(f) —o—c 3-8 cycloalkyl,(g) —c 1-8 alkyl optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)r c and —s(o) 2 —c 1-8 alkyl, wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl,(h) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-8 alkyl and —c 3-8 cycloalkyl,(i) —c(o)—oh,(j) aryl optionally substituted with 1-3 halogens and(k) heterocyclyl optionally substituted with 1-3 substituents independently selected from halogen and —c 1-8 alkyl;r 2 is selected from: (1) c 1-8 alkyl,(2) c 3-8 carbocyclyl,(3) aryl and(4) heterocyclyl;wherein the c 1-8 alkyl of (1) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl,(c) —o—c 1-8 alkyl and(d) heterocyclyl; andwherein each of the c 3-8 carbocyclyl of (2), aryl of (3) and heterocyclyl of (4) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-8 cycloalkyl,(c) —cn,(d) —o—c 1-8 alkyl optionally substituted with 1-3 halogens and(e) —c 1-8 alkyl optionally substituted with 1-3 substituents independently selected from halogen, —oh and —nh 2 ; andr 3 is selected from h, halogen and —c 1-8 alkyl. in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl;(2) mono-cyclic heterocyclyl selected from a saturated, a partially unsaturated and an aromatic 4-7 membered ring containing one to four heteroatoms independently selected from n, o and s; and(3) a 6-12 membered fused bicyclic heterocyclyl containing one to three heteroatoms independently selected from n, o and s in either of the rings;wherein each of the phenyl of (1), mono-cyclic heterocyclyl of (2) and fused bicyclic heterocyclyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —c 3-6 cycloalkyl optionally substituted with —oh,(c) —cn,(d) oxo,(e) —o—c 1-6 alkyl optionally substituted with 1-5 halogens,(f) —o—c 3-6 cycloalkyl,(g) —c 1-6 alkyl optionally substituted with 1-4 substituents independently selected from halogen, —oh, —nh 2 , nhc(o)c 1-3 alkyl and —s(o) 2 —c 1-6 alkyl,(h) —nh—s(o) 2 —r c , wherein r c is selected from —c 1-6 alkyl and —c 3-6 cycloalkyl,(i) —c(o)—oh,(j) phenyl optionally substituted with 1-3 halogens and(k) an aromatic 4-7 membered monocyclic ring containing one to three heteroatoms independently selected from n, o, and s, optionally substituted with —c 1-6 alkyl. in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl; and(2) mono-cyclic heterocyclyl selected from isoxazolyl, isothiazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazolyl and 1,2,3-thiadiazolyl;wherein each of the phenyl of (1) and mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) cyclobutyl optionally substituted with —oh,(d) —o—c 1-3 alkyl optionally substituted with 1-5 halogens,(e) —o-cyclopropyl, and(f) —c 1-4 alkyl optionally substituted with 1-4 substituents independently selected from halogen, —oh and —nh 2 . in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: r 2 is selected from: (1) phenyl,(2) pyridinyl and(3) pyrimidinyl;wherein each of the phenyl of (1), pyridinyl of (2) and pyrimidinyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—c 1-4 alkyl optionally substituted with 1-3 halogens and(d) c 1-4 alkyl optionally substituted with 1-3 halogens. in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: r 2 is selected from: (1) phenyl,(2) pyridinyl andwherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—chf 2 ,(d) —o—cf 3 ,(e) —ch 3 ,(f) —ch 2 f,(g) —chf 2 , and(h) —cf 3 . in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1 or 2;p is 0 or 1;each a group is —ch═; or alternatively, one a group is —n═ and three other a groups are each —ch═;m is selected from —o—, —s—, —ch 2 —, —c(ch 3 ) 2 —, —c(ch 3 )f—, —chf—, —cf 2 — and r 1 is selected from: (1) phenyl,(2) pyridinyl, and(3) pyrimidinyl;wherein each of the phenyl of (1), pyridinyl of (2) and pyrimidinyl of (3) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) cyclobutyl optionally substituted with —oh,(d) —o—c 1-3 alkyl optionally substituted with 1-5 halogens,(e) —o-cyclopropyl, and(f) —c 1-4 alkyl optionally substituted with 1-4 substituents independently selected from halogen, —oh and —nh 2 ;r 2 is selected from: (1) phenyl, and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—c 1-4 alkyl optionally substituted with 1-3 halogens and(d) c 1-4 alkyl optionally substituted with 1-3 halogens; andr 3 is h. in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof: n is 1;p is 1;each a group is —ch═; or alternatively, one a group is —n═ and three other a groups are each —ch═;m is selected from —o—, —ch 2 —, —cf 2 — and r 1 is selected from: (1) phenyl and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) —o—ch 3 ,(d) —o—ch(ch 3 ) 2 ,(e) —o—cf 3 ,(f) —o—chf 2 ,(g) —chf 2 ,(h) —cf 3 ,(i) —ch 2 cf 3 ,(j) —ch 2 oh,(k) —ch 2 ch 3 ,(l) —ch(ch 3 )oh,(m) —ch 2 ch 2 oh,(n) —ch(chf 2 )oh,(o) —c(ch 3 ) 2 oh,(p) —ch(cf 3 )oh, and(q) —o-cyclopropyl;r 2 is selected from: (1) phenyl, and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn, and(c) —cf 3 ; andr 3 is h. in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof, the compound is of formula (ia) or (ib): in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof, the compound is of formula (ic) or (id): in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof, the compound is of formula (ie) or (if): in one embodiment of a compound of formula (i), or a pharmaceutically acceptable salt thereof, the compound is of formula (ig) or (ih): wherein q is 1 or 2; each a is independently —ch═ or —n═; and r c is h, halogen or c 1-3 alkyl. in one embodiment of a compound of formula (ia), (ib), (ic), (id), (ie), (if), (ig), or (ih), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl; and(2) mono-cyclic heterocyclyl selected from isoxazolyl, isothiazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazolyl and 1,2,3-thiadiazolyl;wherein each of the phenyl of (1) and mono-cyclic heterocyclyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) cyclobutyl optionally substituted with —oh,(d) —o—c 1-3 alkyl optionally substituted with 1-5 halogens,(e) —o-cyclopropyl, and(f) —c 1-4 alkyl optionally substituted with 1-4 substituents independently selected from halogen, —oh and —nh 2 ; andr 2 is selected from: (1) phenyl and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—c 1-3 alkyl optionally substituted with 1-3 halogens and(d) c 1-3 alkyl optionally substituted with 1-3 halogens. in one embodiment of a compound of formula (ia), (ib), (ic), (id), (ie), (if), (ig), or (ih), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) —o—ch 3 ,(d) —o—cf 3 ,(e) —o—chf 2 ,(f) —o—cf 2 cf 3 ,(g) —ch 3 ,(h) —ch 2 f,(i) —chf 2 ,(j) —cf 3 ,(k) —ch 2 cf 3 ,(l) —ch 2 oh,(m) —ch(ch 3 )oh,(n) —ch 2 ch 2 oh,(o) —ch(chf 2 )oh,(p) —c(ch 3 ) 2 oh,(q) —c(cf 3 ) 2 oh; andr 2 is selected from: (1) phenyl and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—chf 2 ,(d) —o—cf 3 ,(e) —ch 3 ,(f) —ch 2 f,(g) —chf 2 , and(h) —cf 3 . in one embodiment of a compound of formula (ia), (ib), (ic), (id), (ie), (if), (ig), or (ih), or a pharmaceutically acceptable salt thereof: r 1 is selected from: (1) phenyl and(2) pyridinyl;wherein each of the phenyl of (1) and pyridinyl of (2) is optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) cyclopropyl optionally substituted with —oh,(c) —o—ch 3 ,(d) —o—cf 3 ,(e) —o—chf 2 ,(f) —o—cf 2 cf 3 ,(g) —ch 3 ,(h) —ch 2 f,(i) —chf 2 ,(j) —cf 3 ,(k) —ch 2 cf 3 ,(l) —ch 2 oh,(m) —ch(ch 3 )oh,(n) —ch 2 ch 2 oh,(o) —ch(chf 2 )oh,(p) —c(ch 3 ) 2 oh,(q) —c(cf 3 ) 2 oh, andr 2 is phenyl, optionally substituted with 1-3 substituents independently selected from: (a) halogen,(b) —cn,(c) —o—chf 2 ,(d) —o—cf 3 ,(e) —ch 3 ,(f) —ch 2 f,(g) —chf 2 , and(h) —cf 3 . in one embodiment, a compound disclosed herein is selected from the group consisting of the compounds exemplified in examples 1 to 60; or a pharmaceutically acceptable salt, solvate or hydrate thereof. also disclosed herein is a pharmaceutical composition comprising a compound disclosed herein and at least one pharmaceutically acceptable carrier. also disclosed herein is a method of inhibiting activity of indoleamine 2,3-dioxygenase (ido) comprising contacting ido with a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. also disclosed herein is a method of inhibiting immunosuppression in a patient comprising administering to said patient an effective amount of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. also disclosed herein is a method of treating cancer, viral infection, depression, a neurodegenerative disorder, trauma, age-related cataracts, organ transplant rejection, or an autoimmune disease in a patient comprising administering to said patient an effective amount of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. also disclosed herein is a method of treating melanoma in a patient comprising administering to said patient an effective amount of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. further disclosed herein is a compound disclosed herein, or a pharmaceutically acceptable salt thereof, for use in therapy. in one embodiment, disclosed herein is the use of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, for the preparation of a medicament for use in therapy. “alkyl” refers to both branched- and straight-chain saturated aliphatic hydrocarbon groups of 1 to 18 carbon atoms, or more specifically, 1 to 12 carbon atoms. examples of such groups include, but are not limited to, methyl (me), ethyl (et), n-propyl (pr), n-butyl (bu), n-pentyl, n-hexyl, and the isomers thereof such as isopropyl (i-pr), isobutyl (i-bu), sec-butyl (s-bu), tert-butyl (t-bu), isopentyl, and isohexyl. alkyl groups may be optionally substituted with one or more substituents as defined herein. “c 1-6 alkyl” refers to an alkyl group as defined herein having 1 to 6 carbon atoms. “aryl” refers to an aromatic monocyclic or multicyclic ring moiety comprising 6 to 14 ring carbon atoms, or more specifically, 6 to 10 ring carbon atoms. monocyclic aryl rings include, but are not limited to, phenyl. multicyclic rings include, but are not limited to, naphthyl and bicyclic rings wherein phenyl is fused to a c 4-7 cycloalkyl or c 4-7 cycloalkenyl ring. aryl groups may be optionally substituted with one or more substituents as defined herein. bonding can be through any of the carbon atoms of any ring. “carbocyclyl” refers to a nonaromatic (i.e., saturated or partially unsaturated) monocyclic carbocyclic radical or a fused bicyclic, bridged bicyclic, or spirocyclic carbocyclic radical having the specified ring carbon atoms. for example, “c 3-8 carbocyclyl” refers to a nonaromatic 3 to 8-membered monocyclic carbocyclic radical or a nonaromatic 3 to 8-membered fused bicyclic, bridged bicyclic, or spirocyclic carbocyclic radical. the carbocycle may be attached by any atom of the cycle which results in the creation of a stable structure. non-limiting examples of 3 to 8-membered monocyclic carbocycles include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptanyl and cycloheptenyl. non-limiting examples of 6 to 8-membered fused bicyclic carbocyclic radicals include, but are not limited to, bicyclo[3.3.0]octane. non-limiting examples of 5 to 8-membered bridged bicyclic carbocyclic radicals include, but are not limited to, bicyclo[1.1.1]pentanyl, bicyclo[2.2.2]heptanyl, bicyclo[2.2.2]octanyl, and bicyclo[3.2.1]octanyl. non-limiting examples of 6 to 8-membered spirocyclic carbocyclic radicals include, but are not limited to, spiro[3,3]heptanyl and spiro[3,4]octanyl. in one embodiment, a carbocyclyl is a c 3-8 cycloalkyl. in one embodiment, a carbocyclyl is a 5-6 membered bridged bicyclic carbocyclyl. in another embodiment, a carbocyclyl is bicyclo[1.1.1]pentanyl. “cycloalkyl” refers to a monocyclic saturated carbocyclic ring having the specified number of ring carbon atoms. for example, c 3-8 cycloalkyl refers to a cycloalkyl group as defined herein having 3 to 8 carbon atoms. examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptanyl. cycloalkyl groups may be optionally substituted with one or more substituents as defined herein. “halo” or “halogen” refers to fluoro, chloro, bromo or iodo, unless otherwise noted. “heterocycle” or “heterocyclyl” refers to a saturated, partially unsaturated or aromatic ring moiety having at least one ring heteroatom and at least one ring carbon atom. in one embodiment, the heteroatom is oxygen, sulfur, or nitrogen. a heterocycle containing more than one heteroatom may contain different heteroatoms. heterocyclyl moieties include both monocyclic and multicyclic (e.g., bicyclic) ring moieties. bicyclic ring moieties include fused, spirocycle and bridged bicyclic rings and may comprise one or more heteroatoms in either of the rings. the ring attached to the remainder of the molecule may or may not contain a heteroatom. either ring of a bicyclic heterocycle may be saturated, partially unsaturated or aromatic. the heterocycle may be attached to the rest of the molecule via a ring carbon atom, a ring oxygen atom or a ring nitrogen atom. non-limiting examples of heterocycles are described below. in one embodiment, partially unsaturated and aromatic 4-7 membered monocyclic heterocyclyl moieties include, but are not limited to, 2,3-dihydro-1,4-dioxinyl, dihydropyranyl, dihydropyrazinyl, dihydropyridazinyl, dihydropyridinyl, dihydropyrimidinyl, dihydrotriazolyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, oxoimidazolidinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, tetrahydropyrazinyl, tetrahydropyridazinyl, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, thiophenyl, and triazolyl. in one embodiment, the heterocyclyl is selected from pyrazinyl, pyridazinyl, pyridinyl, and pyrimidinyl. in another embodiment, the heterocyclyl is pyridinyl. in one embodiment, the heterocyclyl is 1,2,4-oxadiazolyl. heterocyclic groups may be optionally substituted with one or more substituents as defined herein. “optionally substituted” refers to “unsubstituted or substituted,” and therefore, the generic structural formulas described herein encompass compounds containing the specified optional substituent(s) as well as compounds that do not contain the optional substituent(s). each substituent is independently defined each time it occurs within the generic structural formula definitions. polymorphism a compound disclosed herein, including a salt, solvate or hydrate thereof, may exist in crystalline form, non-crystalline form, or a mixture thereof. a compound or a salt or solvate thereof may also exhibit polymorphism, i.e. the capacity of occurring in different crystalline forms. these different crystalline forms are typically known as “polymorphs”. polymorphs have the same chemical composition but differ in packing, geometrical arrangement, and other descriptive properties of crystalline solid state. polymorphs, therefore, may have different physical properties such as shape, density, hardness, deformability, stability, and dissolution properties. polymorphs typically exhibit different melting points, ir spectra, and x-ray powder diffraction patterns, all of which may be used for identification. one of ordinary skill in the art will appreciate that different polymorphs may be produced, for example, by changing or adjusting the conditions used in crystallizing/recrystallizing a compound disclosed herein. optical isomers—diastereomers—geometric isomers—tautomers included herein are various isomers of the compounds disclosed herein. the term “isomers” refers to compounds that have the same composition and molecular weight but differ in physical and/or chemical properties. the structural difference may be in constitution (geometric isomers) or in the ability to rotate the plane of polarized light (stereoisomers). with regard to stereoisomers, a compound disclosed herein may have one or more asymmetric carbon atom and may occur as mixtures (such as a racemic mixture) or as individual enantiomers or diastereomers. all such isomeric forms are included herein, including mixtures thereof. if a compound disclosed herein contains a double bond, the substituent may be in the e or z configuration. if a compound disclosed herein contains a disubstituted cycloalkyl, the cycloalkyl substituent may have a cis- or trans-configuration. all tautomeric forms are also intended to be included. any asymmetric atom (e.g., carbon) of a compound disclosed herein, can be present in racemic mixture or enantiomerically enriched, for example the (r)-, (s)- or (r,s)-configuration. in certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (r)- or (s)-configuration. substituents at atoms with unsaturated double bonds may, if possible, be present in cis-(z)- or trans-(e)-form. a compound disclosed herein, can be in the form of one of the possible isomers, rotamers, atropisomers, tautomers or mixtures thereof, for example, as substantially pure geometric (cis or trans) isomers, diastereomers, optical isomers (antipodes), racemates or mixtures thereof. any resulting mixtures of isomers can be separated on the basis of the physicochemical differences of the constituents, into the pure or substantially pure geometric or optical isomers, diastereomers, racemates, for example, by chromatography and/or fractional crystallization. any resulting racemates of the final compounds of the examples or intermediates can be resolved into the optical antipodes by known methods, e.g., by separation of the diastereomeric salts thereof, obtained with an optically active acid or base, and liberating the optically active acidic or basic compound. in particular, a basic moiety may thus be employed to resolve the compounds of the present invention into their optical antipodes, e.g., by fractional crystallization of a salt formed with an optically active acid, e.g., tartaric acid, dibenzoyl tartaric acid, diacetyl tartaric acid, di-o,o′-p-toluoyl tartaric acid, mandelic acid, malic acid or camphor-10-sulfonic acid. racemic compounds can also be resolved by chiral chromatography, e.g., high pressure liquid chromatography (hplc) using a chiral adsorbent. some of the compounds described herein may exist with different points of attachment of hydrogen, referred to as tautomers. for example, compounds including carbonyl —ch 2 c(o)— groups (keto forms) may undergo tautomerism to form hydroxyl —ch═c(oh)— groups (enol forms). both keto and enol forms, individually as well as mixtures thereof, are included within the scope of the present invention. isotopic variations compounds disclosed herein, include unlabeled forms, as well as isotopically labeled forms. isotopically labeled compounds have structures depicted by the formulas given herein except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. examples of isotopes that can be incorporated into compounds disclosed herein include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, sulfur, fluorine, iodine and chlorine, such as 2 h (i.e., deuterium or “d”), 3 h, 11 c, 13 c, 14 c, 13 n, 15 n, 15 o, 17 o, 18 o, 32 p, 35 s, 18 f, 123 i, 125 i and 36 cl. the invention includes various isotopically labeled compounds as defined herein, for example those into which radioactive isotopes, such as 3 h and 14 c, or those into which non-radioactive isotopes, such as 2 h and 13 c are present. such isotopically labeled compounds are useful in metabolic studies (with 14 c), reaction kinetic studies (with, for example 2 h or 3 h), detection or imaging techniques, such as positron emission tomography (pet) or single-photon emission computed tomography (spect) including drug or substrate tissue distribution assays, or in radioactive treatment of patients. in particular, substitution with positron emitting isotopes, such as 11 c, 81 f, 15 o and 13 n may be particularly desirable for pet or spect studies. isotopically-labeled compounds disclosed herein, can generally be prepared by conventional techniques known to those skilled in the art. furthermore, substitution with heavier isotopes, particularly deuterium (i.e., 2 h or d) may afford certain therapeutic advantages resulting from greater metabolic stability, for example increased in vivo half-life or reduced dosage requirements or an improvement in therapeutic index. pharmaceutically acceptable salts the term “pharmaceutically acceptable salt” refers to a salt prepared from a pharmaceutically acceptable non-toxic base or acid, including inorganic or organic base and inorganic or organic acid. salts derived from inorganic bases include aluminum, ammonium, calcium, copper, ferric, ferrous, lithium, magnesium, manganic salts, manganous, potassium, sodium, zinc, and the like. particular embodiments include ammonium, calcium, magnesium, potassium, and sodium salts. salts in the solid form may exist in more than one crystal structure, and may also be in the form of hydrates. salts derived from pharmaceutically acceptable organic non-toxic bases include salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines, and basic ion exchange resins, such as arginine, betaine, caffeine, choline, n,n′-dibenzylethylene-diamine, diethylamine, 2-diethylaminoethanol, 2-dimethylaminoethanol, ethanolamine, ethylenediamine, n-ethyl-morpholine, n-ethylpiperidine, glucamine, glucosamine, histidine, hydrabamine, isopropylamine, lysine, methylglucamine, morpholine, piperazine, piperidine, polyamine resins, procaine, purines, theobromine, triethylamine, trimethylamine, tripropylamine, tromethamine, and the like. when a compound disclosed herein is basic, a salt may be prepared from a pharmaceutically acceptable non-toxic acid, including an inorganic and organic acid. such acids include acetic, benzenesulfonic, benzoic, camphorsulfonic, citric, ethanesulfonic, fumaric, gluconic, glutamic, hydrobromic, hydrochloric, isethionic, lactic, maleic, malic, mandelic, methanesulfonic, mucic, nitric, pamoic, pantothenic, phosphoric, succinic, sulfuric, tartaric, p-toluenesulfonic acid, trifluoroacetic acid (tfa) and the like. particular embodiments include the citric, hydrobromic, hydrochloric, maleic, phosphoric, sulfuric, fumaric, tartaric and trifluoroacetic acids. methods of use compounds disclosed herein can inhibit activity of the enzyme indoleamine-2,3-dioxygenase (ido). for example, the compounds disclosed herein can potentially be used to inhibit activity of ido in cell or in an individual in need of modulation of the enzyme by administering an effective amount of a compound. further disclosed herein are methods of inhibiting the degradation of tryptophan in a system containing cells expressing ido such as a tissue, living organism, or cell culture. in some embodiments, the present invention provides methods of altering (e.g., increasing) extracellular tryptophan levels in a mammal by administering an effective amount of a compound or composition provided herein. methods of measuring tryptophan levels and tryptophan degradation are routine in the art. also disclosed herein are methods of inhibiting immunosuppression such as ido-mediated immunosuppression in a patient by administering to the patient an effective amount of a compound or composition recited herein. ido-mediated immunosuppression has been associated with, for example, cancers, tumor growth, metastasis, viral infection, viral replication, etc. also disclosed herein are methods of treating diseases associated with activity or expression, including abnormal activity and/or overexpression, of ido in an individual (e.g., patient) by administering to the individual in need of such treatment an effective amount or dose of a compound disclosed herein or a pharmaceutical composition thereof. example diseases can include any disease, disorder or condition that may be directly or indirectly linked to expression or activity of the ido enzyme, such as over expression or abnormal activity. an ido-associated disease can also include any disease, disorder or condition that may be prevented, ameliorated, or cured by modulating enzyme activity. examples of ido-associated diseases include cancer, viral infection such as hiv and hcv, depression, neurodegenerative disorders such as alzheimer's disease and huntington's disease, trauma, age-related cataracts, organ transplantation (e.g., organ transplant rejection), and autoimmune diseases including asthma, rheumatoid arthritis, multiple sclerosis, allergic inflammation, inflammatory bowel disease, psoriasis and systemic lupus erythematosusor. example cancers potentially treatable by the methods herein include cancer of the colon, pancreas, breast, prostate, lung, brain, ovary, cervix, testes, renal, head and neck, lymphoma, leukemia, melanoma, and the like. the compounds of the invention may also be useful in the treatment of obesity and ischemia. as used herein, the term “cell” is meant to refer to a cell that is in vitro, ex vivo or in vivo. in some embodiments, an ex vivo cell can be part of a tissue sample excised from an organism such as a mammal. in some embodiments, an in vitro cell can be a cell in a cell culture. in some embodiments, an in vivo cell is a cell living in an organism such as a mammal. as used herein, the term “contacting” refers to the bringing together of indicated moieties in an in vitro system or an in vivo system. for example, “contacting” the ido enzyme with a compound disclosed herein includes the administration of a compound of the present invention to an individual or patient, such as a human, as well as, for example, introducing a compound of the invention into a sample containing a cellular or purified preparation containing the ido enzyme. a subject administered with a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, is generally a mammal, such as a human being, male or female. a subject also refers to cows, sheep, goats, horses, dogs, cats, rabbits, rats, mice, fish, and birds. in one embodiment, the subject is a human. as used herein, the terms “treatment” and “treating” refer to all processes wherein there may be a slowing, interrupting, arresting, controlling, or stopping of the progression of a disease or disorder that may be associated with ido enzyme activity. the terms do not necessarily indicate a total elimination of all disease or disorder symptoms. the terms also include the potential prophylactic therapy of the mentioned conditions, particularly in a subject that is predisposed to such disease or disorder. the terms “administration of” and or “administering a” compound should be understood to include providing a compound described herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, and compositions of the foregoing to a subject. the amount of a compound administered to a subject is an amount sufficient to inhibit ido enzyme activity in the subject. in an embodiment, the amount of a compound can be an “effective amount”, wherein the subject compound is administered in an amount that will elicit a biological or medical response of a tissue, system, animal or human that is being sought by a researcher, veterinarian, medical doctor or other clinician. an effective amount does not necessarily include considerations of toxicity and safety related to the administration of a compound. it is recognized that one skilled in the art may affect physiological disorders associated with an ido enzyme activity by treating a subject presently afflicted with the disorders, or by prophylactically treating a subject likely to be afflicted with the disorders, with an effective amount of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. an effective amount of a compound will vary with the particular compound chosen (e.g. considering the potency, efficacy, and/or half-life of the compound); the route of administration chosen; the condition being treated; the severity of the condition being treated; the age, size, weight, and physical condition of the subject being treated; the medical history of the subject being treated; the duration of the treatment; the nature of a concurrent therapy; the desired therapeutic effect; and like factors and can be routinely determined by the skilled artisan. the compounds disclosed herein may be administered by any suitable route including oral and parenteral administration. parenteral administration is typically by injection or infusion and includes intravenous, intramuscular, and subcutaneous injection or infusion. the compounds disclosed herein may be administered once or according to a dosing regimen wherein a number of doses are administered at varying intervals of time for a given period of time. for example, doses may be administered one, two, three, or four times per day. doses may be administered until the desired therapeutic effect is achieved or indefinitely to maintain the desired therapeutic effect. suitable dosing regimens for a compound disclosed herein depend on the pharmacokinetic properties of that compound, such as absorption, distribution and half-life which can be determined by a skilled artisan. in addition, suitable dosing regimens, including the duration such regimens are administered, for a compound disclosed herein depend on the disease or condition being treated, the severity of the disease or condition, the age and physical condition of the subject being treated, the medical history of the subject being treated, the nature of concurrent therapy, the desired therapeutic effect, and like factors within the knowledge and expertise of the skilled artisan. it will be further understood by such skilled artisans that suitable dosing regimens may require adjustment given an individual subject's response to the dosing regimen or over time as the individual subject needs change. typical daily dosages may vary depending upon the particular route of administration chosen. typical daily dosages for oral administration, to a human weighing approximately 70 kg would range from about 0.1 mg to about 2 grams, or more specifically, 0.1 mg to 500 mg, or even more specifically, 0.2 mg to 100 mg, of a compound disclosed herein. one embodiment of the present invention provides for a method of treating a disease or disorder associated with ido enzyme activity comprising administration of an effective amount of a compound disclosed herein to a subject in need of treatment thereof. in one embodiment, the disease or disorder associated with an ido enzyme is a cell proliferation disorder. in one embodiment, disclosed herein is the use of a compound disclosed herein in a therapy. the compound may be useful in a method of inhibiting ido enzyme activity in a subject, such as a mammal in need of such inhibition, comprising administering an effective amount of the compound to the subject. in one embodiment, disclosed herein is a pharmaceutical composition comprising a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, for use in potential treatment of a disorder or disease related to ido enzyme activity. compositions the term “composition” as used herein is intended to encompass a dosage form comprising a specified compound in a specified amount, as well as any dosage form which results, directly or indirectly, from a combination of a specified compound in a specified amount. such term is intended to encompass a dosage form comprising a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, and one or more pharmaceutically acceptable carriers or excipients. accordingly, the compositions of the present invention encompass any composition made by admixing a compound of the present invention and one or more pharmaceutically acceptable carrier or excipients. by “pharmaceutically acceptable” it is meant the carriers or excipients are compatible with the compound disclosed herein and with other ingredients of the composition. in one embodiment, disclosed herein is a composition comprising a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof, and one or more pharmaceutically acceptable carriers or excipients. the composition may be prepared and packaged in bulk form wherein an effective amount of a compound of the invention can be extracted and then given to a subject, such as with powders or syrups. alternatively, the composition may be prepared and packaged in unit dosage form wherein each physically discrete unit contains an effective amount of a compound disclosed herein. when prepared in unit dosage form, the composition of the invention typically contains from about 0.1 mg to 2 grams, or more specifically, 0.1 mg to 500 mg, or even more specifically, 0.2 mg to 100 mg, of a compound disclosed herein, or a pharmaceutically acceptable salt, solvate or hydrate thereof. a compound disclosed herein and a pharmaceutically acceptable carrier or excipient(s) will typically be formulated into a dosage form adapted for administration to a subject by a desired route of administration. for example, dosage forms include those adapted for (1) oral administration, such as tablets, capsules, caplets, pills, troches, powders, syrups, elixirs, suspensions, solutions, emulsions, sachets, and cachets; and (2) parenteral administration, such as sterile solutions, suspensions, and powders for reconstitution. suitable pharmaceutically acceptable carriers or excipients will vary depending upon the particular dosage form chosen. in addition, suitable pharmaceutically acceptable carriers or excipients may be chosen for a particular function that they may serve in the composition. for example, certain pharmaceutically acceptable carriers or excipients may be chosen for their ability to facilitate the production of uniform dosage forms. certain pharmaceutically acceptable carriers or excipients may be chosen for their ability to facilitate the production of stable dosage forms. certain pharmaceutically acceptable carriers or excipients may be chosen for their ability to facilitate the carrying or transporting of a compound disclosed herein, once administered to the subject, from one organ or portion of the body to another organ or another portion of the body. certain pharmaceutically acceptable carriers or excipients may be chosen for their ability to enhance patient compliance. suitable pharmaceutically acceptable excipients include the following types of excipients: diluents, lubricants, binders, disintegrants, fillers, glidants, granulating agents, coating agents, wetting agents, solvents, co-solvents, suspending agents, emulsifiers, sweeteners, flavoring agents, flavor masking agents, coloring agents, anti-caking agents, hemectants, chelating agents, plasticizers, viscosity increasing agents, antioxidants, preservatives, stabilizers, surfactants, and buffering agents. a skilled artisan possesses the knowledge and skill in the art to select suitable pharmaceutically acceptable carriers and excipients in appropriate amounts for the use in the invention. in addition, there are a number of resources available to the skilled artisan, which describe pharmaceutically acceptable carriers and excipients and may be useful in selecting suitable pharmaceutically acceptable carriers and excipients. examples include remington's pharmaceutical sciences (mack publishing company), the handbook of pharmaceutical additives (gower publishing limited), and the handbook of pharmaceutical excipients (the american pharmaceutical association and the pharmaceutical press). the compositions of the invention are prepared using techniques and methods known to those skilled in the art. some methods commonly used in the art are described in remington's pharmaceutical sciences (mack publishing company). in one embodiment, the invention is directed to a solid oral dosage form such as a tablet or capsule comprising an effective amount of a compound of the invention and a diluent or filler. suitable diluents and fillers include lactose, sucrose, dextrose, mannitol, sorbitol, starch (e.g. corn starch, potato starch, and pre-gelatinized starch), cellulose and its derivatives, (e.g. microcrystalline cellulose), calcium sulfate, and dibasic calcium phosphate. the oral solid dosage form may further comprise a binder. suitable binders include starch (e.g. corn starch, potato starch, and pre-gelatinized starch) gelatin, acacia, sodium alginate, alginic acid, tragacanth, guar gum, povidone, and cellulose and its derivatives (e.g. microcrystalline cellulose). the oral solid dosage form may further comprise a disintegrant. suitable disintegrants include crospovidone, sodium starch glycolate, croscarmelose, alginic acid, and sodium carboxymethyl cellulose. the oral solid dosage form may further comprise a lubricant. suitable lubricants include stearic acid, magnesium stearate, calcium stearate, and talc. where appropriate, dosage unit formulations for oral administration can be microencapsulated. the composition can also be prepared to prolong or sustain the release as, for example, by coating or embedding particulate material in polymers, wax, or the like. the compounds disclosed herein may also be coupled with soluble polymers as targetable drug carriers. such polymers can include polyvinylpyrrolidone, pyrancopolymer, polyhydroxypropylmethacrylamidephenol, polyhydroxyethylaspartamidephenol, or polyethyleneoxidepolylysine substituted with palmitoyl residues. furthermore, the compounds of the invention may be coupled to a class of biodegradable polymers useful in achieving controlled release of a drug, for example polylactic acid, polepsilon caprolactone, polyhydroxy butyric acid, polyorthoesters, polyacetals, polydihydropyrans, polycyanacrylates and cross-linked or amphipathic block copolymers of hydrogels. in one embodiment, the invention is directed to a liquid oral dosage form. oral liquids such as solution, syrups and elixirs can be prepared in dosage unit form so that a given quantity contains a predetermined amount of a compound disclosed herein. syrups can be prepared by dissolving the compound of the invention in a suitably flavored aqueous solution; while elixirs are prepared through the use of a non-toxic alcoholic vehicle. suspensions can be formulated by dispersing a compound disclosed herein in a non-toxic vehicle. solubilizers and emulsifiers such as ethoxylated isostearyl alcohols and polyoxy ethylene sorbitol ethers, preservatives, flavor additives such as peppermint oil or other natural sweeteners or saccharin or other artificial sweeteners and the like can also be added. in one embodiment, the invention is directed to compositions for parenteral administration. compositions adapted for parenteral administration include aqueous and non-aqueous sterile injection solutions which may contain anti-oxidants, buffers, bacteriostats and solutes which render the formulation isotonic with the blood of the intended recipient; and aqueous and non-aqueous sterile suspensions which may include suspending agents and thickening agents. the compositions may be presented in unit-dose or multi-dose containers, for example sealed ampoules and vials, and may be stored in a freeze dried (lyophilized) condition requiring only the addition of the sterile liquid carrier, for example water for injections, immediately prior to use. extemporaneous injection solutions and suspensions may be prepared from sterile powders, granules and tablets. combinations a compound disclosed herein may be used in combination with one or more other active agents, including but not limited to, other anti-cancer agents, that are used in the prevention, treatment, control, amelioration, or reduction of risk of a particular disease or condition (e.g., cell proliferation disorders). in one embodiment, a compound disclosed herein is combined with one or more other anti-cancer agents for use in the prevention, treatment, control amelioration, or reduction of risk of a particular disease or condition for which the compounds disclosed herein are useful. such other active agents may be administered, by a route and in an amount commonly used therefor, contemporaneously or sequentially with a compound of the present invention. when a compound disclosed herein is used contemporaneously with one or more other active agents, a composition containing such other active agents in addition to the compound disclosed herein is contemplated. accordingly, the compositions of the present invention include those that also contain one or more other active ingredients, in addition to a compound disclosed herein. a compound disclosed herein may be administered either simultaneously with, or before or after, one or more other therapeutic agent(s). a compound disclosed herein may be administered separately, by the same or different route of administration, or together in the same pharmaceutical composition as the other agent(s). products provided as a combined preparation include a composition comprising a compound disclosed herein and one or more other active agent(s) together in the same pharmaceutical composition, or a compound disclosed herein, and one or more other therapeutic agent(s) in separate form, e.g. in the form of a kit. the weight ratio of a compound disclosed herein to a second active agent may be varied and will depend upon the effective dose of each agent. generally, an effective dose of each will be used. thus, for example, when a compound disclosed herein is combined with another agent, the weight ratio of the compound disclosed herein to the other agent will generally range from about 1000:1 to about 1:1000, such as about 200:1 to about 1:200. combinations of a compound disclosed herein and other active agents will generally also be within the aforementioned range, but in each case, an effective dose of each active agent should be used. in such combinations, the compound disclosed herein and other active agents may be administered separately or in conjunction. in addition, the administration of one element may be prior to, concurrent to, or subsequent to the administration of other agent(s). in one embodiment, the invention provides a composition comprising a compound disclosed herein, and at least one other therapeutic agent as a combined preparation for simultaneous, separate or sequential use in therapy. in one embodiment, the therapy is the treatment of a disease or disorder associated with ido enzyme activity. in one embodiment, the invention provides a kit comprising two or more separate pharmaceutical compositions, at least one of which contains a compound disclosed herein. in one embodiment, the kit comprises means for separately retaining said compositions, such as a container, divided bottle, or divided foil packet. an example of such a kit is a blister pack, as typically used for the packaging of tablets, capsules and the like. a kit disclosed herein may be used for administering different dosage forms, for example, oral and parenteral, for administering the separate compositions at different dosage intervals, or for titrating the separate compositions against one another. to assist with compliance, a kit of the invention typically comprises directions for administration. disclosed herein is a use of a compound disclosed herein, for treating a disease or disorder associated with ido enzyme activity, wherein the medicament is prepared for administration with another active agent. the invention also provides the use of another active agent for treating a disease or disorder associated with an ido enzyme, wherein the medicament is administered with a compound disclosed herein. the invention also provides the use of a compound disclosed herein for treating a disease or disorder associated with ido enzyme activity, wherein the patient has previously (e.g. within 24 hours) been treated with another active agent. the invention also provides the use of another therapeutic agent for treating a disease or disorder associated with ido enzyme activity, wherein the patient has previously (e.g. within 24 hours) been treated with a compound disclosed herein. the second agent may be applied a week, several weeks, a month, or several months after the administration of a compound disclosed herein. in one embodiment, the other active agent is selected from the group consisting of vascular endothelial growth factor (vegf) receptor inhibitors, topoisomerase ii inhibitors, smoothen inhibitors, alkylating agents, anti-tumor antibiotics, anti-metabolites, retinoids, immunomodulatory agents including but not limited to anti-cancer vaccines, ctla-4, lag-3 and pd-1 antagonists. examples of vascular endothelial growth factor (vegf) receptor inhibitors include, but are not limited to, bevacizumab (sold under the trademark avastin by genentech/roche), axitinib, (n-methyl-2-[[3-[([pound])-2-pyridin-2-ylethenyl]-1h-indazol-6-yl]sulfanyl]benzamide, also known as ag013736, and described in pct publication no. wo 01/002369), brivanib alaninate ((s)-((r)-1-(4-(4-fluoro-2-methyl-1h-indol-5-yloxy)-5-methylpyrrolo[2,1-f][1,2,4]triazin-6-yloxy)propan-2-yl)2-aminopropanoate, also known as bms-582664), motesanib (n-(2,3-dihydro-3,3-dimethyl-1h-indoi-6-yl)-2-[(4-pyridinyimethyj)amino]-3-pyfidinecarboxamide. and described in pct publication no. wo 02/068470), pasireotide (also known as so 230, and described in pct publication no. wo 02/010192), and sorafenib (sold under the tradename nexavar). examples of topoisomerase ii inhibitors, include but are not limited to, etoposide (also known as vp-16 and etoposide phosphate, sold under the tradenames toposar, vepesid and etopophos), and teniposide (also known as vm-26, sold under the tradename vumon). examples of alkylating agents, include but are not limited to, 5-azacytidine (sold under the trade name vidaza), decitabine (sold under the trade name of decogen), temozolomide (sold under the trade names temodar and temodal by schering-plough/merck), dactinomycin (also known as actinomycin-d and sold under the tradename cosmegen), melphalan (also known as l-pam, l-sarcolysin, and phenylalanine mustard, sold under the tradename alkeran), altretamine (also known as hexamethylmelamine (hmm), sold under the tradename hexalen), carmustine (sold under the tradename bcnu), bendamustine (sold under the tradename treanda), busulfan (sold under the tradenames busulfex and myleran), carboplatin (sold under the tradename paraplatin), lomustine (also known as ccnu, sold under the tradename ceenu), cisplatin (also known as cddp, sold under the tradenames platinol and platinol-aq), chlorambucil (sold under the tradename leukeran), cyclophosphamide (sold under the tradenames cytoxan and neosar), dacarbazine (also known as dtic, dic and imidazole carboxamide, sold under the tradename dtic-dome), altretamine (also known as hexamethylmelamine (hmm) sold under the tradename hexalen), ifosfamide (sold under the tradename ifex), procarbazine (sold under the tradename matulane), mechlorethamine (also known as nitrogen mustard, mustine and mechloroethamine hydrochloride, sold under the tradename mustargen), streptozocin (sold under the tradename zanosar), thiotepa (also known as thiophosphoamide, tespa and tspa, and sold under the tradename thioplex). examples of anti-tumor antibiotics include, but are not limited to, doxorubicin (sold under the tradenames adriamycin and rubex), bleomycin (sold under the tradename lenoxane), daunorubicin (also known as dauorubicin hydrochloride, daunomycin, and rubidomycin hydrochloride, sold under the tradename cerubidine), daunorubicin liposomal (daunorubicin citrate liposome, sold under the tradename daunoxome), mitoxantrone (also known as dhad, sold under the tradename novantrone), epirubicin (sold under the tradename ellence), idarubicin (sold under the tradenames idamycin, idamycin pfs), and mitomycin c (sold under the tradename mutamycin). examples of anti-metabolites include, but are not limited to, claribine (2-chlorodeoxyadenosine, sold under the tradename leustatin), 5-fluorouracil (sold under the tradename adrucil), 6-thioguanine (sold under the tradename purinethol), pemetrexed (sold under the tradename alimta), cytarabine (also known as arabinosylcytosine (ara-c), sold under the tradename cytosar-u), cytarabine liposomal (also known as liposomal ara-c, sold under the tradename depocyt), decitabine (sold under the tradename dacogen), hydroxyurea (sold under the tradenames hydrea, droxia and mylocel), fludarabine (sold under the tradename fludara), floxuridine (sold under the tradename fudr), cladribine (also known as 2-chlorodeoxyadenosine (2-cda) sold under the tradename leustatin), methotrexate (also known as amethopterin, methotrexate sodium (mtx), sold under the tradenames rheumatrex and trexall), and pentostatin (sold under the tradename nipent). examples of retinoids include, but are not limited to, alitretinoin (sold under the tradename panretin), tretinoin (all-trans retinoic acid, also known as atra, sold under the tradename vesanoid), isotretinoin (13-c/s-retinoic acid, sold under the tradenames accutane, amnesteem, claravis, clarus, decutan, isotane, izotech, oratane, isotret, and sotret), and bexarotene (sold under the tradename targretin). “pd-1 antagonist” means any chemical compound or biological molecule that blocks binding of pd-l1 expressed on a cancer cell to pd-1 expressed on an immune cell (t cell, b cell or nkt cell) and preferably also blocks binding of pd-l2 expressed on a cancer cell to the immune-cell expressed pd-1. alternative names or synonyms for pd-1 and its ligands include: pdcd1, pd1, cd279 and sleb2 for pd-1; pdcd1l1, pdl1, b7h1, b7-4, cd274 and b7-h for pd-l1; and pdcd1l2, pdl2, b7-dc, btdc and cd273 for pd-l2. in any of the treatment method, medicaments and uses of the present invention in which a human individual is being treated, the pd-1 antagonist blocks binding of human pd-l1 to human pd-1, and preferably blocks binding of both human pd-l1 and pd-l2 to human pd-1. human pd-1 amino acid sequences can be found in ncbi locus no.: np_005009. human pd-l1 and pd-l2 amino acid sequences can be found in ncbi locus no.: np_054862 and np_079515, respectively. pd-1 antagonists useful in any of the treatment method, medicaments and uses of the present invention include a monoclonal antibody (mab), or antigen binding fragment thereof, which specifically binds to pd-1 or pd-l1, and preferably specifically binds to human pd-1 or human pd-l1. the mab may be a human antibody, a humanized antibody or a chimeric antibody, and may include a human constant region. in some embodiments the human constant region is selected from the group consisting of igg1, igg2, igg3 and igg4 constant regions, and in preferred embodiments, the human constant region is an igg1 or igg4 constant region. in some embodiments, the antigen binding fragment is selected from the group consisting of fab, fab′-sh, f(ab′) 2 , scfv and fv fragments. examples of pd-1 antagonists include, but are not limited to, pembrolizumab (sold under the tradename keytruda) and nivolumab (sold under the tradename opdivo). examples of mabs that bind to human pd-1, and useful in the treatment method, medicaments and uses of the present invention, are described in u.s. pat. nos. 7,488,802, 7,521,051, 8,008,449, 8,354,509, 8,168,757, wo2004/004771, wo2004/072286, wo2004/056875, and us2011/0271358. examples of mabs that bind to human pd-l1, and useful in the treatment method, medicaments and uses of the present invention, are described in wo2013/019906, wo2010/077634 a1 and u.s. pat. no. 8,383,796. specific anti-human pd-l1 mabs useful as the pd-1 antagonist in the treatment method, medicaments and uses of the present invention include mpdl3280a, bms-936559, medi4736, msb0010718c and an antibody which comprises the heavy chain and light chain variable regions of seq id no:24 and seq id no:21, respectively, of wo2013/019906. other pd-1 antagonists useful in any of the treatment method, medicaments and uses of the present invention include an immunoadhesin that specifically binds to pd-1 or pd-l1, and preferably specifically binds to human pd-1 or human pd-l1, e.g., a fusion protein containing the extracellular or pd-1 binding portion of pd-l1 or pd-l2 fused to a constant region such as an fc region of an immunoglobulin molecule. examples of immunoadhesion molecules that specifically bind to pd-1 are described in wo2010/027827 and wo2011/066342. specific fusion proteins useful as the pd-1 antagonist in the treatment method, medicaments and uses of the present invention include amp-224 (also known as b7-dcig), which is a pd-l2-fc fusion protein and binds to human pd-1. examples of other cytotoxic agents include, but are not limited to, arsenic trioxide (sold under the tradename trisenox), asparaginase (also known as l-asparaginase, and erwinia l-asparaginase, sold under the tradenames elspar and kidrolase). experimental the following synthetic schemes and examples are intended to be illustrative only and not limiting in any way. abbreviations used are those conventional in the art or the following. acn acetonitrileaq. aqueousboc tert-butyloxycarbonylboc 2 o di-tert-butyl dicarbonatecalc'd calculatedcu(i)i copper(i) iodidecv column volume° c. degree celsiuscelite diatomaceous earth used as a filtration mediumdast (dimethylamino)sulfur trifluoridedcm dichloromethanediea n,n-diisopropylethylaminedma dimethylaminedmf n,n-dimethylformamidedmso dimethylsulfoxidedppf 1,1′-bis(diphenylphosphino)ferroceneedc n-(3-dimethylaminopropyl)-n′-ethylcarbodiimide hydrochlorideei electron ionizationemem eagle's minimal essential mediumet ethylet 2 o diethyl etheret 3 n triethylamineetoac ethyl acetateetoh ethanolg gramh hour(s)hatu 1-[bis(dimethylamino)methylene]-1h-1,2,3-triazolo[4,5-b]pyridinium 3-oxid-hexafluorophosphatehcl hydrochloric acidhplc high pressure liquid chromatographyk 3 po 4 potassium phosphate tribasickg kilogramko′bu potassium tert-butoxidel literlc liquid chromatographylcms liquid chromatography and mass spectrometrylda lithium diisopropylamidelihmds lithium bis(trimethylsilyl)amidelioh lithium hydroxidem molarme methylmeoh methanolmg miligrammmol milimolems mass spectrometrymtbe methyl tert-butyl ethermin minute(s)ml milliliter(s)m/z mass to charge rationm nanometernm nanomolarn normaln 2 nitrogenna 2 so 4 sodium sulfatenah sodium hydridenahco 3 sodium bicarbonatenahmds sodium bis(trimethylsilyl)amidenan 3 sodium azidenaoh sodium hydroxidenh 4 cl ammonium chlorideotf trifluoromethanesulfonatepd 2 (dba) 3 tris(dibenzylideneacetone)dipalladium(0)pd(dppf) 2 cl 2 [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(ii)pd(dtbpf)cl 2 [1,1′-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(ii)pe petroleum etherpg protecting grouppmp p-methoxyphenylpocl 3 phosphorus oxychlorideps polystyrenerpmi roswell park memorial institutert or rt room temperaturesat. saturatedt 3 p propylphosphonic anhydride solutiont-buoh tert-butanoltbaf tetrabutylammonium fluoridetea triethyl aminetfa trifluoroacetic acidthf tetrahydrofurantlc thin layer chromatographyul microliter(s)xphos pd g2 chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(ii) general synthetic schemes the compounds of formula (i) may be prepared by methods known in the art of organic synthesis as set forth in part by the following synthetic schemes and synthetic procedures and conditions for the illustrative intermediates and examples. in the schemes described below, it is well understood that protecting groups for sensitive or reactive groups are employed where necessary in accordance with general principles of chemistry. protecting groups are manipulated according to standard methods of organic synthesis (t. w. greene and p. g. m. wuts, “protective groups in organic synthesis”, third edition, wiley, new york 1999). these groups are removed at a convenient stage of the compound synthesis using methods that are readily apparent to those skilled in the art. the compounds of formula i can be prepared by scheme 1. an appropriate amine of general structure gen-4 is coupled with an appropriate carboxylic acid r 2 —cooh or acid chloride r 2 —cocl under standard amide coupling conditions to give amide intermediate gen-5. gen-5 then reacts with an appropriate boronic acid, boronic acid pinacol ester, silicon containing agent, zincate, stannane or appropriate metallic agents under the suzuki, negishi, stille, or other coupling conditions to give compounds of formula i. alternatively, gen-5 is converted to the corresponding boronic acid pinacol ester gen-6 by reacting with bis(pinacolato)diboron (b2pin2) under pd-catalyzed cross-coupling conditions. reaction of gen-6 with an appropriate halide, triflate, etc. under the suzuki coupling conditions affords the compounds of formula i. the compounds described herein may be made from commercially available starting materials or synthesized using known organic, inorganic, and/or enzymatic processes. 1 h nmr spectra were obtained on a bruker ultra shield spectrometer at 600 mhz or a varian 500 spectrometer at 499 mhz with tetramethylsilane used as an internal reference. lc/ms spectra were obtained on agilent 6120 quadrupole lc/ms spectrometers using electrospray ionization. examples example 1: 4-cyano-n-(1-(4-(6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide step 1: synthesis of n-(1-(4-bromophenyl)cyclobutyl)-4-cyanobenzamide (i-86) to a 40 ml vial was charged with 4-cyanobenzoic acid (1952 mg, 13.27 mmol) in dmf (10.0 ml) and hatu (6054 mg, 15.92 mmol) with stirring and the reaction mixture was stirred for a few minutes. to it was added 1-(4-bromophenyl) cyclobutanamine (3000.0 mg, 13.27 mmol) and diea (6.95 ml, 39.8 mmol) and the reaction mixture was stirred for 12 h at rt. the reaction mixture was diluted with etoac and washed with 1n aq. hcl (3×), water, brine and aq. nahco 3 . the organic layer was dried over na 2 so 4 , filtered and the filtrate was concentrated. the residue was purified by chromatography (isco combiflash system, using 80 g redisep silica gel gold column, and 0-20% meoh/dcm as eluent) to afford compound i-86. ms (esi) [m+h] + : m/z 355. step 2: 4-cyano-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)benzamide (i-87) to a dry round bottom flask was charged with i-86 (1500.0 mg, 4.22 mmol), bis(pinacolato)diboron (2788 mg, 10.98 mmol), potassium acetate (1227 mg, 12.50 mmol) and pdcl 2 (dppf) (345 mg, 0.422 mmol) in dioxane (15.0 ml). the mixture was then evacuated and back filled with nitrogen (3×). the mixture was heated to 80° c. for 4 h, and was then cooled to rt and filtered through a celite pad. the filtrate was concentrated in vacuo to give a residue which was dissolved in dichloromethane. after washing with water (3×) and brine (3×), the dichloromethane layer was dried over anhydrous na 2 so 4 and concentrated in vacuo to give a crude product which was purified by column chromatography (silica gel, etoac/hexane, 12 to 100%) to afford compound i-87. ms (esi) [m+h] + : m/z 403. step 3: 4-cyano-n-(1-(4-(6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide 5-bromo-2-isopropoxypyridine (48.3 mg, 0.224 mmol), compound i-87 (30.0 mg, 0.075 mmol) and 1,1′-bis(di-tert-butylphosphino)-ferrocene palladium dichloride (4.86 mg, 7.46 μmol) were dissolved in 1,4-dioxane (2.0 ml) in a 20 ml round bottom flask, and sodium carbonate (0.075 ml, 0.149 mmol) was added. the reaction mixture was evacuated and refilled with nitrogen 3 times and heated at 80° c. for 4 h. the reaction mixture was cooled to rt and filtered through a celite pad and concentrated. the crude material was purified by mass-directed reversed phase chromatography (acn/water gradient with 0.1% tfa modifier) to afford the title compound. ms (esi) [m+h] + : m/z 412. 1 h nmr (499 mhz, dmso-d 6 ) δ 9.34 (s, 1h), 8.44 (d, j=1.9 hz, 1h), 8.03 (d, j=8.2 hz, 2h), 7.96 (d, j=8.4 hz, 2h), 7.60 (d, j=8.2 hz, 2h), 7.55 (d, j=8.2 hz, 2h), 6.82 (d, j=8.6 hz, 2h), 5.28 (dt, j=12.3, 6.1 hz, 1h), 2.60 (dt, j=19.4, 6.8 hz, 2h), 2.05 (dd, j=12.2, 8.4 hz, 2h), 1.93-1.81 (m, 2h), 1.31 (d, j=6.1 hz, 6h). hereinafter, the reaction conditions in this step are referred to as the standard suzuki cross-coupling conditions. example 2: n-(1-(4-(2-chloro-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)-4-cyanobenzamide the title compound was prepared in a manner analogous to the synthesis of example 1 except 3-bromo-2-chloro-6-isopropoxypyridine was used. ms (esi) [m+h] + : m/z 446. 1 h nmr (499 mhz, dmso-d6) δ 9.35 (s, 1h), 8.05 (d, j=8.2 hz, 2h), 7.97 (d, j=8.2 hz, 2h), 7.76 (d, j=8.3 hz, 1h), 7.55 (d, j=8.2 hz, 2h), 7.41 (d, j=8.1 hz, 2h), 6.85 (d, j=8.3 hz, 1h), 5.20 (dt, j=12.3, 6.1 hz, 1h), 2.63 (td, j=17.8, 16.1, 10.1 hz, 2h), 2.15-1.98 (m, 2h), 1.96-1.78 (m, 2h), 1.33 (s, 3h), 1.31 (s, 3h). example 3: 4-cyano-n-(1-(4-(6-methoxy-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide 4-cyano-n-(1-(4-(6-methoxy-4-methylpyridin-3-yl)phenyl)cyclobutyl)benzamide was prepared in a manner analogous to the synthesis of example 1 except 5-bromo-2-methoxy-4-methylpyridine was used. ms (esi) [m+h] + : m/z 398. 1 h nmr (499 mhz, dmso-d6) δ 9.33 (s, 1h), 8.05 (d, j=8.2 hz, 2h), 8.00-7.94 (m, 3h), 7.55 (d, j=8.1 hz, 2h), 7.33 (d, j=8.0 hz, 2h), 6.78 (s, 1h), 3.86 (s, 3h), 2.62 (dt, j=23.3, 6.9 hz, 2h), 2.23 (s, 3h), 2.11-1.84 (m, 2h), 1.20 (dd, j=28.4, 12.8 hz, 2h). example 4: 4-cyano-n-(1-(4-(6-(difluoromethoxy)pyridin-3-yl)phenyl)cyclobutyl)benzamide the title compound was prepared in a manner analogous to the synthesis of example 1. ms (esi) [m+h] + : m/z 420. 1 h nmr (499 mhz, dmso-d6) δ 9.36 (s, 1h), 8.64-8.49 (m, 1h), 8.20 (dd, j=8.5, 2.2 hz, 1h), 8.03 (d, j=8.2 hz, 2h), 7.96 (d, j=8.2 hz, 2h), 7.66 (d, j=8.2 hz, 2h), 7.59 (d, j=8.4 hz, 2h), 7.18 (d, j=8.5 hz, 1h), 2.61 (dt, j=18.2, 6.8 hz, 2h), 2.06 (dd, j=10.4, 6.6 hz, 2h), 1.96-1.78 (m, 2h). example 5: 4-cyano-n-(1-(4-(6-cyclopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide the title compound was prepared in a manner analogous to the synthesis of example 1 except 5-bromo-2-cyclopropoxypyridine was used. ms (esi) [m+h] + : m/z 410. 1 h nmr (499 mhz, dmso-d6) δ 9.35 (s, 1h), 8.49 (s, 1h), 8.07-7.99 (m, 2h), 7.96 (d, j=8.2 hz, 2h), 7.68-7.52 (m, 4h), 6.94 (d, j=8.6 hz, 2h), 4.23 (dd, j=5.9, 3.1 hz, 1h), 2.91-2.53 (m, 4h), 1.97 (ddd, j=94.0, 16.3, 10.0 hz, 2h), 0.98-0.55 (m, 4h). example 6: 4-cyano-n-(1-(4-(6-cyclopropylpyridin-3-yl)-3-fluorophenyl)cyclobutyl)benzamide step 1: synthesis of n-(1-(4-bromo-3-fluorophenyl)cyclobutyl)-4-cyanobenzamide (93) to a 20 ml vial charged with 4-cyanobenzoic acid (275.0 mg, 1.869 mmol) in dmf (5.0 ml) was added with stirring hatu (853 mg, 2.243 mmol), and the reaction mixture was stirred for a few minutes at rt. to it was added 1-(4-bromo-3-fluorophenyl)cyclobutanamine-hcl (524 mg, 1.869 mmol), diea (1.959 ml, 11.21 mmol), and the reaction mixture was stirred for 4 h at rt. the reaction was diluted with etoac and washed with 1n aq. hcl (3×), water, brine and saturated aqueous nahco 3 . the organic layer was dried over na 2 so 4 , filtered, and concentrated. the residue was purified by chromatography (isco combiflash system, using 24 g redisep silica gel gold column, and 0-20% meoh/dcm as eluent) to afford compound i-93. ms (esi) [m+h] + : m/z 373. step 2: 4-cyano-n-(1-(4-(6-cyclopropylpyridin-3-yl)-3-fluorophenyl)cyclobutyl)benzamide compound i-93 (76 mg, 0.204 mmol) and 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (11.96 mg, 0.018 mmol) were dissolved in 1,4-dioxane (2.0 ml) in a 20 ml round bottom flask. sodium carbonate (0.204 ml, 0.408 mmol) was added and the reaction mixture was evacuated and refilled with nitrogen three times and heated at 80° c. for 4 h. the reaction mixture was cooled down, filtered through a celite pad and concentrated. the crude material was purified by mass-directed reversed phase chromatography (acn/water gradient with 0.1% tfa modifier) to afford the title compound. ms (esi) [m+h] + : m/z 412. 1 h nmr (499 mhz, dmso-d6) δ 9.40 (s, 1h), 8.66 (s, 1h), 8.04 (d, j=8.1 hz, 3h), 7.97 (d, j=8.1 hz, 2h), 7.56 (t, j=8.2 hz, 1h), 7.49 (d, j=8.2 hz, 1h), 7.42 (t, j=9.6 hz, 2h), 2.61 (dt, j=13.2, 7.7 hz, 3h), 2.13-1.98 (m, 2h), 1.96-1.82 (m, 2h), 1.09 (d, j=7.5 hz, 2h), 1.03 (s, 2h). example 7: 4-cyano-n-(1-(4-(6-cyclopropyl-4-methylpyridin-3-yl)-3-fluorophenyl)cyclobutyl)benzamide the title compound was prepared in an analogous manner to example 6 except 2-cyclopropyl-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine was used. ms (esi) [m+h] + : m/z 426. 1 h nmr (499 mhz, dmso-d6) δ 9.39 (s, 1h), 8.45 (s, 1h), 8.06 (d, j=8.2 hz, 2h), 7.98 (d, j=8.2 hz, 2h), 7.49 (s, 1h), 7.44 (t, j=8.7 hz, 2h), 7.38 (t, j=7.9 hz, 1h), 2.61 (dq, j=18.1, 11.7, 9.7 hz, 3h), 2.23 (d, j=9.8 hz, 3h), 2.12-1.97 (m, 2h), 1.97-1.86 (m, 2h), 1.16 (dd, j=22.9, 5.4 hz, 2h), 1.09 (s, 2h). examples 8-39 were prepared in a similar fashion as example 6 by using bromo intermediate i-86 and the respective boronates. ex. #structurechemical namemass [m + h]+84-cyano-n-(1-(4-(5- (cyclopropanesulfonamido) pyridin-3- yl)phenyl)cyclobutyl)benzamide47394-cyano-n-(1-(4-(2- cyclopropylpyrimidin-5- yl)phenyl)cyclobutyl)benzamide394104-cyano-n-(1-(4-(6-(2- hydroxypropan-2-yl)pyridin-3- yl)phenyl)cyclobutyl)benzamide412114-cyano-n-(1-(4-(4-methyl-6- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide436124-cyano-n-(1-(4-(6-cyclopropyl- 4-methylpyridin-3- yl)phenyl)cyclobutyl)benzamide408134-cyano-n-(1-(4-(6- cyclopropylpyridin-3- yl)phenyl)cyclobutyl)benzamide394144-cyano-n-(1-(4-(6- cyanopyridin-3- yl)phenyl)cyclobutyl)benzamide378154-cyano-n-(1-(4-(6-(1- hydroxyethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide398164-cyano-n-(1-(4-(6-cyano-4- methylpyridin-3- yl)phenyl)cyclobutyl)benzamide393174-cyano-n-(1-(4-(6-(3-methyl- 1,2,4-oxadiazol-5-yl)pyridin-3- yl)phenyl)cyclobutyl)benzamide436184-cyano-n-(1-(4-(6- (hydroxymethyl)-4- methoxypyridin-3- yl)phenyl)cyclobutyl)benzamide414194-cyano-n-(1-(4-(6- ((methylsulfonyl)methyl) pyridin-3- yl)phenyl)cyclobutyl)benzamide446204-cyano-n-(1-(4-(6- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide422214-cyano-n-(1-(4-(6- (difluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide404225-(4-(1-(4- cyanobenzamido)cyclobutyl) phenyl)picolinic acid398234-cyano-n-(1-(4-(6-(2,2,2- trifluoro-1- hydroxyethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide452244-cyano-n-(1-(4-(6- (hydroxymethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide384254-cyano-n-(1-(4-(6-cyclopropyl- 2-(hydroxymethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide424264-cyano-n-(1-(4-(5- cyclopropylpyrazin-2- yl)phenyl)cyclobutyl)benzamide395274-cyano-n-(1-(4-(5-(2- fluoroethoxy)pyrazin-2- yl)phenyl)cyclobutyl)benzamide417284-cyano-n-(1-(4-(6- isopropylpyridazin-3- yl)phenyl)cyclobutyl)benzamide397294-cyano-n-(1-(4-(6-methoxy-4- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide452304-cyano-n-(1-(4-(6-methoxy-2- methylpyridin-3- yl)phenyl)cyclobutyl)benzamide39831n-(1-(4-(4,6- bis(trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)-4- cyanobenzamide490324-cyano-n-(1-(4-(6-(2- fluoroethoxy)pyridazin-3- yl)phenyl)cyclobutyl)benzamide417334-cyano-n-(1-(4-(4-methoxy-6- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide45234cyano-n-(1-(4-(6-methoxy-5- (methylsulfonamido)pyridin-3- yl)phenyl)cyclobutyl)benzamide477354-cyano-n-(1-(4-(4- (hydroxymethyl)-6- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide452364-cyano-n-(1-(4-(6-methoxy- 2,4-dimethylpyridin-3- yl)phenyl)cyclobutyl)benzamide412374-cyano-n-(1-(4-(4-cyano-6- (trifluoromethyl)pyridin-3- yl)phenyl)cyclobutyl)benzamide447384-cyano-n-(1-(4-(6- (difluoromethoxy)-2,4- dimethylpyridin-3- yl)phenyl)cyclobutyl)benzamide448394-cyano-n-(1-(4-(6- (difluoromethoxy)-4- methylpyridin-3- yl)phenyl)cyclobutyl)benzamide434 examples 40-41 were prepared by the following scheme: example 40: 4-cyano-n-(1-(4-(4-formyl-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide to a 25-ml flask containing 5-bromo-2-isopropoxyisonicotinaldehyde (152 mg, 0.621 mmol), 4-cyano-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)benzamide (200.0 mg, 0.497 mmol), tetrakis(triphenylphosphine)palladium(0) (57.4 mg, 0.050 mmol) and k 2 co 3 (206 mg, 1.491 mmol) was added 1,4-dioxane (8.0 ml) and water (2.000 ml). the reaction mixture was evacuated and refilled with nitrogen three times and the mixture was heated under nitrogen at 90° c. for 24 h. the solvents were removed under vacuum. the resulting residue was suspended in etoac/dcm, filtered through a celite pad which was washed with etoac/dcm. the combined filtrates were concentrated to afford the title compound. ms (esi) [m+h] + : m/z 440. example 41: 4-cyano-n-(1-(4-(4-(difluoromethyl)-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide to a stirred solution of 4-cyano-n-(1-(4-(4-formyl-6-isopropoxypyridin-3-yl)phenyl)cyclobutyl)benzamide (65 mg, 0.148 mmol) in dcm (1.5 ml) at 0° c. was added dropwise bis(2-methoxyethyl)aminosulfur trifluoride (0.104 ml, 0.562 mmol). the reaction mixture was stirred at 0° c. for 2 h, quenched with sat. aq. sodium bicarbonate and extracted with ch 2 cl 2 (2×). the combined organics were washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. the crude material was purified by mass-directed reversed phase chromatography (acn/water gradient with 0.1% tfa modifier) to afford the title compound. ms (esi) [m+h] + : m/z 462. 1 h nmr (499 mhz, dmso-d6) δ 9.34 (s, 1h), 8.20 (s, 1h), 8.05 (d, j=8.2 hz, 2h), 7.97 (d, j=8.2 hz, 2h), 7.58 (d, j=8.1 hz, 2h), 7.36 (d, j=8.1 hz, 2h), 6.99 (d, j=8.3 hz, 1h), 5.32 (dd, j=12.2, 6.1 hz, 1h), 2.62 (dt, j=24.6, 6.8 hz, 2h), 2.15-1.82 (m, 2h), 1.34 (s, 3h), 1.32 (s, 3h), 1.25 (dd, j=16.6, 5.9 hz, 2h). example 42: 4-cyano-n-(1-(6′-cyclopropyl-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)benzamide step 1: synthesis of n-(1-(5-bromopyridin-2-yl)cyclobutyl)-4-cyanobenzamide (i-130) to a 40 ml vial charged with 4-isocyanobenzoic acid (324 mg, 2.202 mmol) in dmf (5 ml) was added with stirring hatu (1005 mg, 2.64 mmol) and the reaction was stirred for a few minutes. 1-(5-bromopyridin-2-yl)cyclobutanamine (500.0 mg, 2.202 mmol) was added followed by diea (1.154 ml, 6.60 mmol), and the reaction mixture was stirred for 12 h at rt. the reaction was diluted with etoac and washed with 1n aq. hcl (3×), water (2×), brine and sat. aq. nahco 3 . the organic extracts were then dried over na 2 so 4 , filtered, and concentrated. the residue was purified by chromatography (isco combiflash system, using 48 g redisep silica gel gold column, 0-20% meoh/dcm as eluent) to afford compound 1-130. ms (esi) [m+h] + : m/z 356. step 2: 4-cyano-n-(1-(6′-cyclopropyl-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)benzamide 2-cyclopropyl-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (43.7 mg, 0.168 mmol), compound i-130 (60.0 mg, 0.168 mmol) and 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (9.88 mg, 0.015 mmol) were dissolved in 1,4-dioxane (2.0 ml) in a 20 ml round bottom flask, and sodium carbonate (0.168 ml, 0.337 mmol) was added. the reaction mixture was subjected to the standard suzuki coupling conditions and the crude product was purified by mass-directed reverse phase chromatography (acn/water gradient with 0.1% tfa modifier) to afford the title compound. ms (esi) [m+h] + : m/z 409. 1 h nmr (499 mhz, dmso-d6) δ 9.47 (s, 1h), 8.68 (s, 1h), 8.53 (s, 1h), 8.09 (t, j=9.2 hz, 2h), 8.03-7.96 (m, 2h), 7.90-7.84 (m, 1h), 7.53 (d, j=5.9 hz, 2h), 2.85-2.71 (m, 2h), 2.58 (q, j=9.2 hz, 2h), 2.38 (s, 3h), 2.34-2.20 (m, 1h), 2.05 (ddd, j=23.6, 12.6, 5.4 hz, 2h), 1.26-1.19 (m, 2h), 1.13 (s, 2h). example 43: 3-cyano-n-(1-(6′-(difluoromethoxy)-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)bicyclo[1.1.1]-pentane-1-carboxamide step 1: n-(1-(5-bromopyridin-2-yl)cyclobutyl)-3-cyanobicyclo[1.1.1]pentane-1-carboxamide (i-132) n-(1-(5-bromopyridin-2-yl)cyclobutyl)-3-cyanobicyclo[1.1.1]pentane-1-carboxamide (i-132) was prepared in a manner analogous to the synthesis of intermediate i-130 except 3-cyanobicyclo[1.1.1]pentane-1-carboxylic acid was used. ms (esi) [m+h] + : m/z 346. step 2: 3-cyano-n-(1-(6′-(difluoromethoxy)-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)bicyclo[1.1.1]pentane-1-carboxamide the title compound was prepared with intermediate i-132 and 2-(difluoromethoxy)-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine under the standard suzuki coupling conditions. ms (esi) [m+h] + : m/z 425. 1 h nmr (499 mhz, dmso-d6) δ 8.69 (s, 1h), 8.60 (s, 1h), 8.13 (s, 1h), 7.91-7.81 (m, 1h), 7.74 (s, 1h), 7.34 (d, j=8.2 hz, 1h), 7.12 (s, 1h), 2.66 (dt, j=15.2, 8.8 hz, 2h), 2.48 (s, 4h), 2.40 (dd, j=18.8, 9.1 hz, 2h), 2.30 (s, 3h), 2.08-1.90 (m, 4h). example 44: 3-cyano-n-(1-(6′-cyclopropyl-4′-methyl-[3,3′-bipyridin]-6-yl)cyclobutyl)bicyclo[1.1.1]pentane-1-carboxamide this compound was prepared in a similar fashion as example 43 except 2-cyclopropyl-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine was used. ms (esi) [m+h] + : m/z 399. 1 h nmr (499 mhz, dmso-d6) δ 8.71 (s, 1h), 8.64 (s, 1h), 8.51 (s, 1h), 7.96-7.75 (m, 1h), 7.52 (s, 1h), 7.35 (d, j=8.2 hz, 1h), 2.65 (dt, j=15.3, 8.9 hz, 2h), 2.48 (s, 3h), 2.44-2.39 (m, 2h), 2.37 (s, 2h), 2.25 (dd, j=10.3, 5.6 hz, 2h), 1.97 (dd, j=14.6, 7.3 hz, 4h), 1.26-1.18 (m, 2h), 1.12 (s, 3h). example 45: 4-fluoro-n-(3-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yflphenyl)oxetan-3-yl)benzamide step 1: n-(3-(4-bromophenyl)oxetan-3-yl)-4-fluorobenzamide (i-160) to a vial equipped with a stir bar was added commercially available 3-(4-bromophenyl)oxetan-3-amine hydrochloride (300.00 mg, 1.134 mmol), dcm (2.00 ml) and diea (0.990 ml, 5.67 mmol). to this stirred solution at 0° c. was then added 4-fluorobenzoyl chloride (0.161 ml, 1.361 mmol) and the reaction mixture was allowed to stir for 2 h. the reaction mixture was partitioned into excess dcm, washed with sat. nahco 3 , and the organic layers was separated, washed with water and brine, dried over mgso 4 , filtered and the filtrates were concentrated under reduced pressure. the oil obtained was purified on a silica gel column using (0-60%) hex-3:1 etoac-ethanol to give compound i-160 as a solid. ms (esi) [m+h] + : m/z 352. step 2: n-(3-(4-(4-(((tert-butyldimethylsilyl)oxy)methyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)oxetan-3-yl)-4-fluorobenzamide (i-161) to a vial were added 4-(((tert-butyldimethylsilyl)oxy)methyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethyl)pyridine (179 mg, 0.428 mmol), compound i-160 (100 mg, 0.286 mmol), 1,1′-bis(di-tert-butylphosphino)palladium dichloride (27.9 mg, 0.043 mmol), and 2 m aq. solution of sodium carbonate (286 μl, 0.571 mmol) and 1,4-dioxane (1904 μl). the vial was evacuated and purged with nitrogen thrice and the mixture was heated under nitrogen and then subjected to microwave irradiation at 110° c. for 40 min. the reaction mixture was cooled, diluted with water, and extracted with etoac. the organic layers were separated, washed with brine, dried over mgso 4 , and concentrated. the residue was purified on a silica gel column using 0-70% hex-etoac/ethanol (3:1 mixture) to give compound i-161 as a solid. ms (esi) [m+h] + : m/z 561. step 3: 4-fluoro-n-(3-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)oxetan-3-yl)benzamide to a stirred solution of compound i-161 (155.40 mg, 0.277 mmol) in thf (0.5 ml) in a vial, was added tbaf (1.109 ml, 1.109 mmol) and the reaction mixture was allowed to stir for 2 h. the reaction was diluted with sat. nahco 3 solution and excess etoac. the organic layer was separated, washed with water and brine, dried over mgso 4 , filtered and the solvents were removed under reduced pressure. the oil obtained was purified on a silica gel column using (0-60%) hex-3:1 etoac-ethanol mixture to give the title compound as a solid. ms esi [m+h] + : m/z 447. 1 h nmr (600 mhz, dmso-d6) δ 9.61 (s, 1h), 8.62 (s, 1h), 8.18-7.94 (m, 3h), 7.69 (d, j=8.4 hz, 2h), 7.52 (d, j=8.4 hz, 2h), 7.37 (t, j=8.8 hz, 2h), 5.67 (t, j=5.5 hz, 1h), 5.06 (d, j=7.0 hz, 2h), 4.84 (s, 1h), 4.57 (d, j=5.4 hz, 2h). example 46: 4-chloro-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide step 1: n-(1-(4-bromophenyl)cyclopropyl)-4-chlorobenzamide to a stirred solution of 1-(4-bromophenyl)cyclopropanamine (200 mg, 0.943 mmol) in ch 2 cl 2 (10 ml) were added 4-chlorobenzoic acid (221 mg, 1.415 mmol), tea (0.4 ml, 2.87 mmol) and hatu (538 mg, 1.415 mmol) at rt and the reaction was stirred at rt for 15 h. the solvent was concentrated and the residue was diluted with water (20 ml) and extracted with etoac (30 ml×2). the organic layers were collected, washed with brine (20 ml), dried over na 2 so 4 , filtered, and the filtrate was concentrated in vacuo. the residue was first purified by silica gel chromatography followed by additional purification using reversed phase hplc on a gilson 281 instrument fitted with a waters xbridge prep obd c18 column (100×19 mm×5 um) using water (0.225% formic acid)-acn as eluents. the title compound was obtained as a solid after concentration of the desired fractions. ms (esi) m/z: 349.9 [m+h + ]. step 2: n-(1-(4-(4-(((tert-butyldimethylsilyl)oxy)methyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)-4-chlorobenzamide to a stirred solution of n-(1-(4-bromophenyl)cyclopropyl)-4-chlorobenzamide (50 mg, 0.143 mmol) in 1,4-dioxane (2.5 ml) and water (0.5 ml) were added pd(dppf)cl 2 (10 mg, 0.014 mmol) and k 3 po 4 (91 mg, 0.428 mmol) at rt and the reaction was heated to 100° c. with stirring for 5 h. after cooled to rt, the solvent was concentrated, and the residue was diluted with water (20 ml) and extracted by etoac (30 ml×2). the organic layers were collected, washed with brine (20 ml), dried over na 2 so 4 , filtered, and the filtrate was concentrated in vacuo. the residue was purified by silica gel chromatography to afford the title compound as a solid. 1 h nmr (400 mhz, cdcl 3 ) δ 8.5 (s, 1 h), 8.0 (s, 1 h), 7.7-7.8 (m, 2 h), 7.4 (d, 2 h), 7.4 (d, 2 h), 7.2 (d, 2 h), 6.9 (br s, 1 h), 4.7 (s, 2 h), 1.3 (br s, 2 h), 0.9 (s, 9 h), 0.8-0.9 (m, 2 h), 0.0 (s, 6 h). step 3: 4-chloro-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide to a stirred solution of n-(1-(4-(4-(((tert-butyldimethylsilyl)oxy)methyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)-4-chlorobenzamide (106 mg, 0.189 mmol) in thf (10 ml) was added tbaf (0.4 ml, 0.400 mmol) at rt and the mixture was stirred at rt for 15 h. the solvent was removed in vacuo, the residue was quenched with water (30 ml) and extracted with etoac (30 ml×2). the organic layers were collected, washed with brine (20 ml), dried over na 2 so 4 , filtered, and the filtrate was concentrated in vacuo. the residue was purified by reversed phase hplc on a gilson 281 instrument fitted with a waters xbridge prep obd c18 column (100×19 mm×5 um) using water (0.225% formic acid)-acn as mobile phases to afford the title compound as a solid. 1 h nmr (400 mhz, cdcl 3 ) δ 8.54 (s, 1 h), 8.02 (s, 1 h), 7.75-7.79 (m, 2 h), 7.42-7.46 (m, 2 h), 7.37-7.40 (m, 2 h), 7.23-7.26 (m, 2 h), 4.72 (s, 2 h), 1.46 (s, 4 h). ms (esi) m/z: 447.1 [m+h + ]. example 47: n-(1-(4-(6-cyclopropoxy-4-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclopropyl)-4-fluorobenzamide step 1: n-(1-(4-bromophenyl)cyclopropyl)-4-fluorobenzamide to a stirred solution of 4-fluorobenzoic acid (290 mg, 2.070 mmol) in dmf (8 ml) were added hatu (905 mg, 2.380 mmol), 1-(4-bromophenyl)cyclopropanamine (505 mg, 2.380 mmol) and tea (0.87 ml, 6.24 mmol) at rt and the reaction was stirred rt for 16 h. then the mixture was diluted with water (50 ml), extracted with etoac (30 ml×3), and the organic layers were collected, washed with brine, dried over na 2 so 4 , and filtered. after filtration, the filtrate was concentrated in vacuo. the residue was purified by flash silica gel chromatography to afford the title compound as a solid. ms (esi) m/z: 333.9 [m+h + ]. step 2: 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropyl)benzamide to a stirred solution of n-(1-(4-bromophenyl)cyclopropyl)-4-fluorobenzamide (280 mg, 0.838 mmol) in 1,4-dioxane (10 ml) were added 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (255 mg, 1.005 mmol), potassium acetate (247 mg, 2.51 mmol) and pd(dppf)cl 2 (62 mg, 0.085 mmol) at rt and the reaction was subjected to the typical suzuki coupling conditions. the crude product was purified by flash silica gel chromatography to afford the title compound as a solid. ms (esi) m/z: 382.1 [m+h + ]. step 3: n-(1-(4-(6-cyclopropoxy-4-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclopropyl)-4-fluorobenzamide to a solution of 2-(5-bromo-2-cyclopropoxypyridin-4-yl)propan-2-ol (40 mg, 0.147 mmol) and 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropyl)benzamide (56 mg, 0.147 mmol) in dioxane (5 ml) and water (1 ml) were added pd(dtbpf)cl 2 (9 mg, 0.014 mmol) and k 3 po 4 (94 mg, 0.441 mmol) at rt and the reaction mixture was stirred at 100° c. under nitrogen for 16 h. then the mixture was cooled to rt, filtered through a pad of celite, and the filtrate was concentrated under reduced pressure to give a residue, which was purified by reversed phase hplc on a gilson 281 instrument fitted with a waters xselect c18 column (150×30 mm×5 um) using water (0.1% tfa) and acn as eluents followed by freeze drying to afford the title compound as a solid. 1 h nmr (400 mhz, cd 3 od) δ 7.93 (dd, 2 h), 7.78 (s, 1 h), 7.63 (br s, 1 h), 7.28-7.34 (m, 2 h), 7.15-7.24 (m, 4 h), 4.20 (br s, 1 h), 1.40 (s, 4 h), 1.31 (s, 6 h), 0.89 (br d, 2 h), 0.82 (br s, 2 h). ms (esi) m/z: 447.2 [m+h + ]. example 48: n-(1-(4-(6-cyclopropoxy-4-(hydroxymethyl)pyridin-3-yl)phenyl)cyclopropyl)-4-fluorobenzamide the title compound was prepared using intermediate 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropyl)benzamide and 5-bromo-2-cyclopropoxypyridin-4-yl)methanol in a similar fashion as example 47. 1 h nmr (400 mhz, cd 3 od) δ 8.00 (s, 1 h), 7.93 (dd, 2 h), 7.55 (br s, 1 h), 7.34-7.40 (m, 2 h), 7.25-7.30 (m, 2 h), 7.21 (t, 2 h), 4.59 (s, 2 h), 4.26 (br s, 1 h), 1.41 (s, 4 h), 0.93 (br d, 2 h), 0.87 (br s, 2 h). ms (esi) m/z: 419.2 [m+h + ]. example 49: 4-fluoro-n-(1-(4-(4-(hydroxymethyl)-6-isopropoxypyridin-3-yl)phenyl)cyclopropyl)benzamide step 1: 5-bromo-2-isopropoxyisonicotinaldehyde to a solution of 5-bromo-2-isopropoxypyridine (500 mg, 2.314 mmol) in thf (8 ml) was added lda (1.4 ml, 2.80 mmol) (2m in thf) at −78° c. and the mixture was stirred at −78° c. for 1 h. then dmf (300 mg, 4.10 mmol) was added at −78° c. and the reaction was gradually warmed to rt and stirred for 16 h. the mixture was quenched with water (10 ml), extracted with etoac (10 ml×2), the organic layers were collected, washed with brine, dried over na 2 so 4 , and filtered. after filtration, the filtrate was concentrated in vacuo. the residue was purified by flash silica gel chromatography to afford the title compound. 1 h nmr (400 mhz, cd 3 od) δ 8.05-8.22 (m, 1 h), 6.94 (s, 1 h), 5.19 (spt, 1 h), 1.30 (d, 6 h). step 2: (5-bromo-2-isopropoxypyridin-4-yl)methanol to a solution of 5-bromo-2-isopropoxyisonicotinaldehyde (120 mg, 0.492 mmol) in meoh (5 ml) was added nabh 4 (23 mg, 0.608 mmol) at 0° c., and the mixture was stirred at 0° c. for 30 min and quenched with water (10 ml). the meoh was removed in vacuo and the aq. residue was extracted with etoac (10 ml×3). the organic layers were collected, washed with brine, dried over na 2 so 4 , and filtered. after filtration, the filtrate was concentrated in vacuo to afford the title compound as an oil, which was used directly in the next step without further purification. ms (esi) m/z: 246.0 [m+h + ]. step 3: 4-fluoro-n-(1-(4-(4-(hydroxymethyl)-6-isopropoxypyridin-3-l)phenyl)cyclopropyl)benzamide the title compound was prepared in a similar fashion to example 47 using (5-bromo-2-isopropoxypyridin-4-yl)methanol and 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropyl)benzamide as suzuki coupling partners and the crude was purified by reversed phase hplc on a gilson 281 instrument fitted with a agela asb c18 column (150×25 mm×5 um) using water (0.225% formic acid) and acn. 1 h nmr (400 mhz, cd 3 od) δ 7.97-8.01 (m, 1 h), 7.93 (dd, 2 h), 7.32-7.41 (m, 3 h), 7.25-7.30 (m, 2 h), 7.20 (t, 2 h), 5.22 (dt, 1 h), 4.58 (s, 2 h), 1.43-1.47 (m, 6 h), 1.41 (s, 4 h). ms (esi) m/z: 421.2 [m+h + ]. example 50: (s)-4-fluoro-n-(1-(4-(4-(1-hydroxyethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide the title compound was prepared in a similar fashion as example 49 using (s)-1-(5-bromo-2-(trifluoromethyl)pyridin-4-yl)ethanol as the coupling partner. 1 h nmr (499 mhz, dmso-d6) δ 9.26 (s, 1h), 8.51 (s, 1h), 8.11-7.92 (m, 3h), 7.41-7.26 (m, 6h), 4.92-4.77 (m, 1h), 1.43-1.30 (m, 4h), 1.24-1.14 (m, 4h). ms (esi) m/z: 445.1 [m+1] + . example 51: (r)-4-fluoro-n-(1-(4-(4-(1-hydroxyethyl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclopropyl)benzamide, 2,2,2-trifluoroacetate salt the title compound was prepared in a similar fashion as example 49 using (r)-1-(5-bromo-2-(trifluoromethyl)pyridin-4-yl)ethanol the coupling partner. 1 h nmr (499 mhz, dmso-d 6 ) δ 9.26 (s, 1h), 8.51 (s, 1h), 8.10-7.93 (m, 3h), 7.43-7.26 (m, 6h), 4.97-4.73 (m, 2h), 1.41-1.31 (m, 4h), 1.23-1.15 (m, 3h). ms (esi) m/z: 445.1 [m+h] + . example 52: n-(3-bromo-4-fluorophenyl)-4-((2-(sulfamoylamino)ethyl)amino)-1,2,5-oxadiazole-3-carboximidamide step 1: n-(1-(4-bromophenyl)cyclobutyl)-4-fluorobenzamide to a stirred solution of 1-(4-bromophenyl)cyclobutanamine (300 mg, 1.327 mmol) in dmf (10 ml) were added 4-fluorobenzoic acid (223 mg, 1.592 mmol), et 3 n (0.56 ml, 4.02 mmol) and hatu (605 mg, 1.592 mmol) at rt and the reaction was stirred at rt for 15 h. the solvent was concentrated and water (20 ml) was added to the mixture which was extracted with etoac (30 ml×2). the organic layers were collected, washed with brine (20 ml), dried over na 2 so 4 , filtered, and the filtrate was concentrated in vacuo. the residue was purified by silica gel chromatography to give the title compound as a solid. ms (esi) m/z: 347.9 [m+h + ]. step 2: 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)benzamide to a stirred solution of n-(1-(4-bromophenyl)cyclobutyl)-4-fluorobenzamide (146 mg, 0.419 mmol) in 1,4-dioxane (10 ml) were added 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (128 mg, 0.503 mmol), potassium acetate (123 mg, 1.258 mmol) and pd(dppf)cl 2 (31 mg, 0.042 mmol) at rt and the mixture was subjected to the usual suzuki coupling and workup conditions. the crude was purified by silica gel chromatography to give the title compound as a solid. ms (esi) m/z: 396.1 [m+h + ]. step 3: 4-fluoro-n-(1-(4-(4-(2-hydroxypropan-2-yl)-6-(trifluoromethyl)pyridin-3-yl)phenyl)cyclobutyl)benzamide to a stirred solution of 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)benzamide (50 mg, 0.126 mmol) in 1,4-dioxane (2.5 ml) and water (0.5 ml) were added pd(dtbpf)cl 2 (10 mg, 0.015 mmol), 2-(5-bromo-2-(trifluoromethyl)pyridin-4-yl)propan-2-ol (40 mg, 0.141 mmol) and k 3 po 4 (81 mg, 0.379 mmol) at rt and the mixture was subjected to the usual suzuki coupling and workup conditions. the crude was purified by reversed phase hplc on a gilson 281 instrument fitted with a waters xbridge prep obd c18 column (100×19 mm×5 um) using water (0.225% formic acid)-acn as mobile phases to afford the title compound as a solid. 1 h nmr (400 mhz, cd 3 od) δ 9.1 (s, 1 h), 8.3 (s, 1 h), 8.3 (s, 1 h), 7.9 (dd, 2 h), 7.6 (d, 2 h), 7.3 (d, 2 h), 7.2 (t, 2 h), 2.7 (t, 4 h), 2.1-2.2 (m, 1 h), 2.0-2.1 (m, 1 h), 1.3 (s, 6 h). ms (esi) m/z: 473.2 [m+h + ]. example 53: 4-fluoro-n-(1-(4-(4-(hydroxymethyl)-6-(trifluoromethyl)pyridin-3-yflphenyl)cyclobutyl)benzamide the title compound was prepared in a similar fashion as example 52. 1 h nmr (500 mhz, cdcl 3 ) δ 8.57 (s, 1 h), 8.02 (s, 1 h), 7.81 (dd, 2 h), 7.62 (d, 2 h), 7.30 (d, 2 h), 7.12 (t, 2 h), 6.67 (s, 1 h), 4.74 (s, 2 h), 2.66-2.80 (m, 4 h), 2.18-2.26 (m, 1 h), 2.02-2.06 (m, 1 h). ms (esi) m/z: 445.1 [m+h + ]. example 54: n-(1-(4-(6-cyclopropoxy-4-(2-hydroxypropan-2-yl)pyridin-3-yl)phenyl)cyclobutyl)-4-fluorobenzamide the title compound was prepared from 4-fluoro-n-(1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)benzamide and 2-(5-bromo-2-cyclopropoxypyridin-4-yl)propan-2-ol in a similar manner as example 52. 1 h nmr (400 mhz, cd3od) δ 7.89 (dd, 2 h), 7.77 (s, 1 h), 7.75-7.79 (m, 1 h), 7.58 (d, 2 h), 7.46 (s, 1 h), 7.26 (d, 2 h), 7.18 (t, 2 h), 4.11-4.18 (m, 1 h), 2.71 (t, 4 h), 2.11-2.21 (m, 1 h), 1.95-2.07 (m, 1 h), 1.31 (s, 6 h), 0.82-0.90 (m, 2 h), 0.74-0.81 (m, 2 h). ms (esi) m/z: 461.2 [m+h + ]. examples 55-60: 4-fluoro-n-(1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide step 1: 1-(6-chloropyridin-3-yl)-2-methylcyclopropanamine to a flask that was thoroughly purged with nitrogen and vacuumed three times was added a solution of 6-chloronicotinonitrile (200.00 mg, 1.443 mmol) in thf (4.00 ml). the mixture was cooled to −78° c. and titanium isopropoxide (0.893 ml, 3.02 mmol) was added and the mixture was stirred for 15 min. to this stirred solution was added propylmagnesium chloride (1.941 ml, 3.88 mmol) and the mixture was allowed to warm to rt and stirred overnight. the reaction mixture was quenched with aq. 1n naoh and then extracted with etoac. the organic layer was collected, dried over anhydrous mgso 4 , filtered and the filtrate was concentrated under reduced pressure. the title compound was obtained as an oil and used in the next step directly. ms (esi) m/z: 183.1 [m+h] + . step 2: n-(1-(6-chloropyridin-3-yl)-2-methylcyclopropyl)-4-fluorobenzamide to a solution of 1-(6-chloropyridin-3-yl)-2-methylcyclopropanamine (262.00 mg, 1.434 mmol) in dcm (3.00 ml) at 0° c. were added diea (0.752 ml, 4.30 mmol) and 4-fluorobenzoyl chloride (0.085 ml, 0.717 mmol). the mixture was stirred at 0° c. for 1 h, diluted with sat. nahco 3 , and extracted with etoac. the organic layer was separated, washed with brine, dried over anhydrous mgso 4 , filtered and concentrated. the residue was purified by flash chromatography (0-50% etoac/hexanes) to give the title compound as a solid. ms (esi) m/z: 305.1 [m+h] + . step 3: (5-(1-(4-fluorobenzamido)-2-methylcyclopropyl)pyridin-2-yl)boronic acid to a vial were added n-(1-(6-chloropyridin-3-yl)-2-methylcyclopropyl)-4-fluorobenzamide (124.00 mg, 0.407 mmol), bis(pinacolato)diboron (155 mg, 0.610 mmol), 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (39.8 mg, 0.061 mmol) and potassium acetate (120 mg, 1.221 mmol). the vial was purged with nitrogen and then dioxane (2 ml) was added. the vial was again thoroughly purged with nitrogen and then allowed to stir at 75° c. for 6 h. the reaction mixture was filtered and the filtrate was concentrated. the residue was co-evaporated with hexane (2×) and vacuum dried to afford the title compound which was used in the next step without further purification. ms (esi) m/z: 315.1[m+h] + . step 4: 4-fluoro-n-(1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide to a vial equipped with a stir bar were added (5-(1-((tert-butoxycarbonyl)amino)cyclopropyl)pyridin-2-yl)boronic acid, 2-(5-bromo-2-(trifluoromethyl)pyridin-4-yl)propan-2-ol (116 mg, 0.407 mmol), 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (39.8 mg, 0.061 mmol), sodium carbonate (0.611 ml, 1.222 mmol) and dioxane (2 ml). the vial was thoroughly flushed with nitrogen and then subjected to microwave irradiation at 130° c. the reaction mixture was cooled, diluted with etoac and washed with sat. nahco 3 . the organic layer was separated, washed with water and brine, dried over mgso 4 , filtered and the filtrate was concentrated under reduced pressure. the oil obtained was first purified on a silica gel column to give a crude material which was further purified by reversed phase hplc using acn/water (0.1% tfa) as eluents. peak 1 was assigned as the trans-isomer and peak 2 as the cis-isomer. absolute stereochemistry was not determined. peak 1 (ex. 55) and peak 2 (ex. 56) were then separately resolved by sfc purification to give peak a-trans and peak b-trans, and peak c-cis and peak d-cis. p1-a (trans) (ex. 57): 4-fluoro-n-((1s,2s)-1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide.ms (esi) m/z: 474.1 [m+h] + .1 h nmr (499 mhz, dmso-d 6 ) δ 9.11 (s, 1h), 8.48 (d, 2h), 8.17 (s, 1h), 8.07-7.95 (m, 2h), 7.68 (d, 1h), 7.49 (d, 1h), 7.34 (t, 2h), 1.80-1.64 (m, 1h), 1.58-1.39 (m, 2h), 1.28 (s, 3h), 1.23 (d, 7h), 1.13 (d, 1h).p1-b (trans) (ex. 58): 4-fluoro-n-((1r,2r)-1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide.ms (esi) m/z: 474.1 [m+h] + .1 h nmr (499 mhz, dmso-d 6 ) δ 9.12 (s, 1h), 8.48 (d, 2h), 8.18 (s, 1h), 8.02 (d, 2h), 7.69 (d, 1h), 7.49 (d, 1h), 7.34 (t, 2h), 1.81-1.65 (m, 1h), 1.54-1.44 (m, 1h), 1.28 (d, 6h), 1.23 (s, 3h), 1.17-1.12 (m, 2h).p2-c (cis) (ex. 59): 4-fluoro-n-((1r,2s)-1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide.ms (esi) m/z: 474.1 [m+h] + .1 h nmr (499 mhz, dmso-d 6 ) δ 9.38 (s, 1h), 8.73 (s, 1h), 8.54 (s, 1h), 8.19 (s, 1h), 7.96 (d, 3h), 7.56 (s, 1h), 7.31 (d, 3h), 1.41 (d, 3h), 1.25 (d, 6h), 0.86 (d, 3h).p2-d (cis) (ex. 60): 4-fluoro-n-((1s,2r)-1-(4′-(2-hydroxypropan-2-yl)-6′-(trifluoromethyl)-[2,3′-bipyridin]-5-yl)-2-methylcyclopropyl)benzamide.ms (esi) m/z: 474.1 [m+h] + .1 h nmr (499 mhz, dmso-d 6 ) δ 9.40 (s, 1h), 8.73 (s, 1h), 8.54 (s, 1h), 8.19 (s, 1h), 8.10-7.96 (m, 1h), 7.96-7.84 (m, 2h), 7.55 (d, 1h), 7.36-7.24 (m, 2h), 5.83-5.66 (m, 1h), 1.71-1.53 (m, 1h), 1.43 (s, 1h), 1.25 (s, 7h), 0.87 (s, 3h). biological assays ido1 cellular assay in hela cells stimulated with ifnγ hela cells were cultured in complete hela culture medium (90% emem, 10% heat-inactivated fetal bovine serum) and expanded to about 1×10 9 cells. the cells were then collected and frozen down at 1×10 7 cells/vial in 1 ml frozen medium (90% complete hela culture medium, 10% dmso). compounds to be tested were serially diluted in ten 3-fold steps in dmso starting from 10 mm dmso stocks in echo low volume plate(s). compound dilutions or dmso alone were then dispensed from the dilution plate(s) into greiner black 384-well assay plate(s) (catalog #781086, 50 nl/well) using an echo 550 acoustic liquid handler (labcyte). frozen hela cells were thawed and transferred into hela assay medium (99% complete hela culture medium, 1% pen/strep) with 20 ml medium/vial of cells. the cells were spun down at 250 g in a table top centrifuge for 5 min and suspended in same volume of hela assay medium. the cells were then counted and adjusted to a density of 2×10 5 cells/ml in hela assay medium. sterile l-tryptophan were added to the cells with final concentration of 300 um l-tryptophan. a small aliquot (2 ml/plate) of hela cells were set aside and were not treated with ifnγ, to serve as the max-e control. the rest of hela cells were added with sterile ifnγ (cat #285-if, r & d systems) with a final concentration of 100 ng/ml. hela cells with and without ifnγ were dispensed to the respective wells of 384-well assay plates containing the compounds. the plates were incubated for about 48 hours at a 37° c., 5% co 2 incubator. afterwards, 12 μl of 0.5 m methyl isonipecotate in dimethyl sulfoxide were added into each well and the plates were sealed and incubated at 37° c. without co 2 overnight. the plates were centrifuged for 1 min at 200×g. the resulting fluorescence was measured in a spectramax plate reader (molecular devices) with a 400 nm excitation filter and a 510 nm emission filter. the fluorescence intensity of each well was corrected for the background observed in wells with non-ifnγ-treated cells and was expressed as a fraction of the intensity observed in wells of ifnγ-treated cells and dmso only. potencies were calculated by linear least squares fit to the four parameter logistic ic 50 equation. the biological activity data using the ido1 cellular assay described above are summarized in the table below. compounds disclosed herein generally have ic 50 of about 0.1 nm to about 10,000 nm, or more specifically, about 1 nm to about 10,000 nm, or more specifically, about 2 nm to about 5,000 nm, or more specifically, about 5 nm to about 1,000 nm, or still more specifically, about 10 nm to about 500 nm. specific ic 50 activity data for the exemplified compounds disclosed herein is provided in the following table. ido1 human whole blood assay compounds to be tested were serially diluted in ten 3-fold steps in dmso starting from 10 mm. 3 μl of compound dilutions or dmso alone were then dispensed from the dilution plate into a polypropylene 96-well assay plate containing 97 μl of rpmi using an echo 555 acoustic liquid handler (labcyte). lps and ifnγ was prepared in in rpmi to a 10× of final conc. (1000 ng/ml), final concentration is 100 ng/ml. human whole blood was drawn in sodium heparin coated tubes from healthy internal donors. 240 μl of blood was transferred to each of the wells of a v-bottom 96 well plate. 30 μl of compound was transferred from intermediate dilution plate, and incubated for 15 min. 30 μl from stimulants was then transferred to blood and mixed thoroughly. plate was covered with breathable membrane and incubated at 37° c. for overnight (18 h). on day 2 isotope labeled standard of kynurenine and tryptophan was made in water at 10× concentration and 30 μl was added to the blood at 3 μm final concentration. the assay plates were centrifuged at 300×g for 10 min with no brake to separate plasma from red blood cells. 60 μl of plasma samples was removed without disturbing red blood cells. plasma was diluted with rpmi in 1:1 ratio and proteins were precipitated out with two volume of acetonitrile. the plates were centrifuged at 4000×g for 60 min. 20 μl of supernatant was carefully transferred to a 384 well plate contain 40 μl of 0.1% formic acid in water and analyzed by lc/ms/ms. lc/ms/ms analyses were performed using thermo fisher's lx4-tsq quantum ultra system. this system consists of four agilent binary high-performance liquid chromatography (hplc) pumps and a tsq quantum ultra triple quadrupole ms/ms instrument. for each sample, 5 μl were injected onto an atlantis t3 column (2.1 mm×150 mm, 3 μm particle size) from waters. the mobile phase gradient pumped at 0.8 ml/min was used to elute the analytes from the column at 25° c. the elution started at 0% b increasing linearly to 25% b at 6.5 min, holding at 25% for 1 min, re-equilibrating to 10 min. mobile phase a consisted of 0.1% formic acid in water. mobile phase b consisted of 0.1% of formic acid in acetonitrile. data was acquired in positive mode using a hesi interface. the operational parameters for the tsq quantum ultra instrument were a spray voltage of 4000 v, capillary temperature of 380° c., vaporizer temperature 400° c., shealth gas 60 arbitrary units, aux gas 20 arbitrary units, tube lens 85 and collision gas 1.2 mtorr. srm chromatograms of kynurenine (q1: 209.2>q3:94.0) and internal standard (q1: 215.3>q3:98.2) were collected for 90 sec. the peak area was integrated by xcalibur quan software. the ratios between the kynurenine generated in the reaction and 2d6-kynurenine spiked-in internal standard were used to generate percentage inhibition and ic 50 values. compounds were titrated and ic 50 's were calculated by 4 parameter sigmoidal curve fitting formula. the biological activity data of selective compounds using the ido1 human whole blood assay described above are summarized in the table below. hela cell potency,human whole blood potency,ex. #ic 50 (nm)ic 50 (nm)13.823.735.247.1518.2636.674.439882,825919.110445.1113.0122.12461314.61467.715318.61617.117153.018197.51910,0002018.52130.22210,00023116.224316.2259.95872645.52795.22831.72928.5304.43115.131136.1338.934295.8358.21066361.930837120.3386.13912.640nd418.4424.939243524.044308.3451.5462.1703.3472.1126.7484.2922.1492.7578.5501.5185.9512.3233.2522.2151.9534.31000542.2336.15526.5568.3361.15741.7589.9284.1594.9171603.8210.5 while the invention has been described and illustrated with reference to certain particular embodiments thereof, those skilled in the art will appreciate that various adaptations, changes, modifications, substitutions, deletions, or additions of procedures and protocols may be made without departing from the spirit and scope of the invention.
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063-442-713-390-541
|
US
|
[
"JP",
"US"
] |
B65H7/06,G03G15/00
| 2008-03-06T00:00:00 |
2008
|
[
"B65",
"G03"
] |
image forming apparatus, sheet state determination method, and sheet state determination program
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<p>problem to be solved: to provide a technique to prevent damage to a sheet due to drawing out operation of a drawable unit in an image forming apparatus with a part of a sheet conveying passage reversing both sides of the sheet unitized to be drawable to the outside of the device. <p>solution: in this image forming apparatus, the sheet conveyed in a first conveying direction leading to a predetermined discharge tray is made to switchback in a second conveying direction leading into a reverse conveyance pass to thereby reverse both sides. when the sheet is detected simultaneously by both a first sensor detecting the sheet existing in an intermediate conveyance unit and a second sensor detecting the sheet existing in the other sheet conveyance unit located adjacently to the upstream side of the second conveying direction of the intermediate conveyance unit, it is determined that the sheet extends over a boundary between the intermediate conveyance unit and the other sheet conveyance unit. <p>copyright: (c)2009,jpo&inpit
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1 . an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus comprising: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to an outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit; and a determining unit that determines, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. 2 . the apparatus according to claim 1 , wherein the conveyance guide is integrally formed with an upper or lower cover of the discharge tray. 3 . the apparatus according to claim 2 , wherein the discharge tray is provided to project to an outer side in a horizontal direction in the apparatus, and the conveyance guide is integrally formed with the lower cover of the discharge tray that opens downward. 4 . the apparatus according to claim 1 , wherein the conveyance guide is openable around a predetermined rotation axis, and the second sensor is located further on the upstream side than the predetermined rotation axis in the second conveying direction. 5 . the apparatus according to claim 1 , further comprising a notification control unit that causes, if the determining unit determines that the sheet is present across the boundary between the intermediate conveying unit and the other sheet conveying unit, a display unit to perform notification for urging a user to open the conveyance guide before extracting the intermediate conveying unit. 6 . the apparatus according to claim 5 , wherein the conveyance guide is integrally formed with a lower cover that opens downward to below the discharge tray provided to project to an outer side in a horizontal direction in the apparatus, a processing unit that performs predetermined processing is detachably attachable to a side of the apparatus below the discharge tray, the apparatus further includes a unit identifying unit that identifies the processing unit mounted on the apparatus, and the notification control unit causes, when the processing unit identified by the unit identifying unit prevents the opening of the conveyance guide, the display unit to notify to the effect that, before the conveyance guide is opened, the processing unit should be retracted to a position where the processing unit does not prevent the opening of the conveyance guide. 7 . a sheet state determining method in an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus including: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to an outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; and a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit, the method comprising determining, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. 8 . the method according to claim 7 , wherein the conveyance guide is integrally formed with an upper or lower cover of the discharge tray. 9 . the method according to claim 8 , wherein the discharge tray is provided to project to an outer side in a horizontal direction in the apparatus, and the conveyance guide is integrally formed with the lower cover of the discharge tray that opens downward. 10 . the method according to claim 7 , wherein the conveyance guide is openable around a predetermined rotation axis, and the second sensor is located further on the upstream side than the predetermined rotation axis in the second conveying direction. 11 . the method according to claim 7 , further comprising causing, if it is determined that the sheet is present across the boundary between the intermediate conveying unit and the other sheet conveying unit, a display unit to perform notification for urging a user to open the conveyance guide before extracting the intermediate conveying unit. 12 . the method according to claim 11 , wherein the conveyance guide is integrally formed with a lower cover that opens downward to below the discharge tray provided to project to an outer side in a horizontal direction in the apparatus, a processing unit that performs predetermined processing is detachably attachable to a side of the apparatus below the discharge tray, and the method further including: identifying the processing unit mounted on the apparatus; and causing, when the processing unit identified by the unit identifying unit prevents the opening of the conveyance guide, the display unit to notify to the effect that, before the conveyance guide is opened, the processing unit should be retracted to a position where the processing unit does not prevent the opening of the conveyance guide. 13 . a sheet state determining program in an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus including: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to the outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; and a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit, the program causing a computer to execute processing for determining, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. 14 . the program according to claim 13 , wherein the conveyance guide is integrally formed with an upper or lower cover of the discharge tray. 15 . the program according to claim 14 , wherein the discharge tray is provided to project to an outer side in a horizontal direction in the apparatus, and the conveyance guide is integrally formed with the lower cover of the discharge tray that opens downward. 16 . the program according to claim 13 , wherein the conveyance guide is openable around a predetermined rotation axis, and the second sensor is located further on the upstream side than the predetermined rotation axis in the second conveying direction. 17 . the program according to claim 13 , further causing the computer to execute processing for causing, if the determining unit determines that the sheet is present across the boundary between the intermediate conveying unit and the other sheet conveying unit, a display unit to perform notification for urging a user to open the conveyance guide before extracting the intermediate conveying unit. 18 . the program according to claim 17 , wherein the conveyance guide is integrally formed with a lower cover that opens downward to below the discharge tray provided to project to an outer side in a horizontal direction in the apparatus, a processing unit that performs predetermined processing is detachably attachable to a side of the apparatus below the discharge tray, and the program further causing the computer to execute processing for: identifying the processing unit mounted on the apparatus, and causing, when the processing unit identified by the unit identifying unit prevents the opening of the conveyance guide, the display unit to notify to the effect that, before the conveyance guide is opened, the processing unit should be retracted to a position where the processing unit does not prevent the opening of the conveyance guide.
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cross-reference to related application this application is based upon and claims the benefit of priority from u.s. provisional application 61/034,397 filed on mar. 6, 2008, the entire contents of which are incorporated herein by reference. technical field the present invention relates to determination of a sheet conveying state in an image forming apparatus, and, more particularly to a technique for determining a sheet conveying state in a conveying path through which a sheet is passed to be reversed. background in the past, there is known an image forming apparatus that reverses print target surfaces of a sheet, which is conveyed in a direction toward a predetermined discharge tray, by switching back the sheet using different sheet conveying paths. as the image forming apparatus in the past, there is an image forming apparatus in which, in order to allow a user to remove a sheet from a sheet conveying path when sheet clogging (so-called sheet jam) occurs in the sheet conveying path, a part of the sheet conveying path is formed as a unit to be extractable to the outside of the apparatus. in the image forming apparatus in the past in which a part of the sheet conveying path is formed as the unit extractable to the outside of the apparatus as explained above, when sheet conveyance is stopped by some cause such as a sheet jam, a sheet could be present in both the extractable unit and a sheet conveying path adjacent to the unit and continuous to the sheet conveying path in the unit. in such a state, if the user attempts to extract the unit to the outside of the apparatus in order to remove the jammed sheet, force in a direction of keeping the sheet in the apparatus acts on the sheet. therefore, it is likely that the sheet is damaged. summary it is an object of an embodiment of the present invention to provide, in an image forming apparatus in which a part of a sheet conveying path for reversing a sheet is formed as a unit to be extractable to the outside of the apparatus, a technique for preventing damage to the sheet involved in extracting operation for the extractable unit. in order to solve the problem, according to an aspect of the present invention, there is provided an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus including: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to the outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit; and a determining unit that determines, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. according to another aspect of the present invention, there is provided a sheet state determining method in an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus including: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to the outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; and a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit, the method including determining, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. according to still another aspect of the present invention, there is provided a sheet state determining program in an image forming apparatus that reverses a sheet conveyed in a first conveying direction for leading the sheet to a predetermined discharge tray side by switching back the sheet in a second conveying direction for leading the sheet into a reversing and conveying path, the apparatus including: an intermediate conveying unit that is located further on an upstream side than the reversing and conveying path in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during switchback conveyance and is extracted to the outside of the apparatus together with a part of the sheet conveying path; a conveyance guide that forms at least a part of a sheet conveying path in another sheet conveying unit adjacent to the upstream side in the second conveying direction of the intermediate conveying unit and is openable; a first sensor that detects a sheet present in the sheet conveying path in the intermediate conveying unit; and a second sensor that detects a sheet present in the sheet conveying path in the other sheet conveying unit, the program causing a computer to execute processing for determining, if a sheet is simultaneously detected by both the first and second sensors, that the sheet is present across a boundary between the intermediate conveying unit and the other sheet conveying unit. description of the drawings fig. 1 is a schematic diagram for explaining an overall configuration of an image processing system including an image forming apparatus 1 according to an embodiment of the present invention; fig. 2 is a longitudinal sectional view for explaining an overall configuration of the image forming apparatus 1 according to the embodiment; fig. 3 is an enlarged longitudinal sectional view of a section near a relay reversing unit 2 and a reversing and conveying path 3 for reversal processing for a sheet in the image forming apparatus 1 according to the embodiment; fig. 4 is a diagram for explaining a first conveying direction; fig. 5 is a diagram for explaining a second conveying direction; fig. 6 is a diagram of a state in which entering length into a reversing and retracting path 9 a of a sheet is equal to or larger than predetermined length; fig. 7 is a diagram of a state in which entering length into the reversing and retracting path 9 a of the sheet is smaller than the predetermined length; fig. 8 is a diagram of a state in which a lower conveyance guide 9 c is opened; fig. 9 is a functional block diagram of the image forming apparatus according to the embodiment; and fig. 10 is a flowchart of a flow of jam processing in the image forming apparatus according to the embodiment. detailed description an embodiment of the present invention is explained below with reference to the accompanying drawings. fig. 1 is a schematic diagram for explaining an overall configuration of an image processing system (mfp: multi function peripheral) including an image forming apparatus 1 according to the embodiment. fig. 2 is a longitudinal sectional view for explaining an overall configuration of the image forming apparatus 1 according to the embodiment. first, a schematic configuration of the image processing system including the image forming apparatus 1 according to this embodiment is explained. as shown in fig. 1 , the image processing system according to this embodiment includes an image scanning unit r, an image forming unit p, a large-capacity paper feeding apparatus d, a post-processing apparatus f, a display unit 102 a , and an operation input unit 102 b. the large-capacity paper feeding apparatus d can feed a large number of (e.g., several thousand) sheets as recording media to the image forming unit p. the post-processing apparatus f is mounted on a side of the image forming apparatus 1 below a paper discharge tray 7 b (see fig. 2 ) and applies predetermined post-processing to sheets subjected to image formation processing by the image forming unit p. specifically, the post-processing apparatus f applies so-called “post processing (finishing)” such as stapling, folding, punching, and bookbinding to the sheets subjected to predetermined image formation processing by the image forming unit p and discharges the sheets subjected to the post processing onto a discharge tray ft. the display unit 102 a can be, for example, an lcd (liquid crystal display), an el (electronic luminescence), a pdp (plasma display panel), or a crt (cathode ray tube). the operation input unit 102 b can be, for example, a keyboard, a mouse, a touch panel, a touchpad, or a graphics tablet. functions of the display unit 102 a and the operation input unit 102 b can be realized by a so-called touch panel display. a configuration of the image forming apparatus 1 according to this embodiment is explained. the image forming apparatus 1 shown in fig. 2 includes the image forming unit p and the image scanning unit r. the image forming unit p performs processing for forming images on sheets as recording media such as paper and an ohp sheet. the image scanning unit r performs processing for scanning an image on an original document when copy or scan processing is performed. the image forming unit p includes a relay reversing unit 2 (an intermediate conveying unit) indicated by being surrounded by a dotted line in fig. 2 , a reversing and conveying path 3 indicated by being surrounded by an alternate long and short dash line, a transfer roller 5 and an intermediate transfer belt 5 a, a fixing device 6 , a paper discharge tray 7 b, a first paper discharge port 7 , a second paper discharge port 8 , a reversing and retracting unit 9 (another sheet conveying unit), a cpu 10 , a memory 12 , and a sheet feeding unit 14 . the cpu 10 has a role of performing various kinds of processing in the image forming apparatus 1 and also has a role of realizing various functions by executing a computer program stored in the memory 12 . the memory 12 can be, for example, a ram (random access memory), a rom (read only memory), a dram (dynamic random access memory), an sram (static random access memory), or a vram (video ram). the memory 12 has a role of storing various kinds of information and computer programs used in the image forming apparatus 1 . a flow of image formation processing in the image forming apparatus 1 according to this embodiment is explained. when an image is formed only on one side of a sheet by the image forming unit p, first, a sheet is fed from the sheet feeding unit 14 and a developer image formed on the intermediate transfer belt 5 a is transferred onto the sheet by the transfer roller 5 (so-called secondary transfer). the developer image on the sheet is heated and fixed thereon by the fixing device 6 . the sheet having the image formed thereon is conveyed, through the relay reversing unit 2 , to the first paper discharge port 7 for discharging the sheet onto the paper discharge tray 7 b or to the second paper discharge port 8 for conveying the sheet to the post-processing apparatus f and discharged to the outside of the image forming apparatus 1 . the paper discharge tray 7 b is provided to project to an outer side substantially in the horizontal direction (in fig. 2 , to the left side) in the image forming apparatus 1 . on the other hand, when images are formed on both sides of a sheet, after an image is formed on a first side, reversal processing for reversing a side of the sheet opposed to the intermediate transfer belt 5 a is performed, then, the sheet is conveyed to a secondary transfer position again, and an image is formed on a second side. the reversal processing is performed by switching back the sheet on which the developer image heated and fixed by the fixing device 6 to change a conveying direction using a conveying path for reversal and retraction of the relay reversing unit 2 explained later and the reversing and retracting unit 9 and conveying the sheet to the reversing and conveying path 3 such that an end as the trailing end of the sheet during the image formation on the first side is changed to the leading end. when the reversal processing is performed, if the cpu 10 of the image forming apparatus 1 determines, on the basis of a detection result of a sensor provided in the reversing and conveying path 3 explained later, that the sheet cannot be conveyed to the reversing and conveying path 3 because another sheet is already present in the reversing and conveying path 3 , the cpu 10 performs processing for putting the sheet on standby in a predetermined standby position until it becomes possible to convey the sheet. when it becomes possible to convey the sheet to the reversing and conveying path 3 , the sheet is conveyed to the reversing and conveying path 3 and reversed. an image is formed on the second side by the intermediate transfer belt 5 a and the fixing device 6 . components related to the reversal processing for a sheet in the image forming apparatus 1 according to this embodiment are explained in detail below. fig. 3 is an enlarged longitudinal sectional view of a section near the relay reversing unit 2 and the reversing and conveying path 3 for the reversal processing for a sheet in the image forming apparatus 1 according to this embodiment. the relay reversing unit 2 is a section surrounded by a dotted line in fig. 3 . the reversing and conveying path 3 is a section surrounded by an alternate long and short dash line in fig. 3 . the relay reversing unit 2 conveys a sheet having an image formed thereon to the first paper discharge port 7 or the second paper discharge port 8 . in order to perform duplex printing, after once conveying the sheet to the reversing and retracting unit 9 (a first conveying direction shown in fig. 4 ), the relay reversing unit 2 switches back the sheet to change a conveying direction of the sheet from the first conveying direction to a second conveying direction (a direction toward the reversing and conveying path 3 shown in fig. 5 ) and conveys the sheet to the reversing and conveying path 3 . the relay reversing unit 2 is located between the reversing and conveying path 3 and the reversing and retracting unit 9 (further on the upstream side than the reversing and conveying path 3 in the second conveying direction and in the middle of a sheet conveying path through which the sheet passes during the switchback conveyance). the relay reversing unit 2 is extractable in a y axis direction (see, for example, fig. 3 ) from the image forming apparatus 1 together with a part of the sheet conveying path by slide rails 701 and 702 . consequently, for example, when a sheet jam occurs, it is possible to extract the relay reversing unit 2 and remove a sheet held up in the relay reversing unit 2 . the relay reversing unit 2 includes a first conveying path 2 a and a second conveying path 2 b . the first conveying path 2 a includes a paper discharge conveying path 2 a 1 that leads a sheet to the first paper discharge port 7 and a retracting path 2 a 2 through which the sheet is conveyed when the sheet is switched back. a first sensor s 1 (an actuator-type sensor) that can detect a sheet present in the retracting path 2 a 2 is arranged in the retracting path 2 a 2 . when the sheet is discharged from the first paper discharge port 7 , the sheet is conveyed to the paper discharge conveying path 2 a 1 . when the sheet is conveyed to the reversing and conveying path 3 in order to reverse the sheet, the sheet is conveyed to the retracting path 2 a 2 . when the sheet is conveyed to the reversing and conveying path 3 after the switchback of the sheet, the sheet is conveyed to the reversing and conveying path 3 through the reversing path 2 a 3 . the second conveying path 2 b is a conveying path for conveying the sheet to the second paper discharge port 8 when the sheet is discharged from the second paper discharge port 8 and conveyed to, for example, the post processing apparatus f. roller pairs 201 , 204 , 206 , 208 , and 209 for conveying the sheets in the conveying paths are provided in the respective conveying paths. the relay reversing unit 2 includes a first flapper 202 that selectively switches conveyance of the sheet to the first conveying path 2 a or the second conveying path 2 b and a second flapper 205 that selectively switches conveyance of the sheet to the paper discharge conveying path 2 a 1 or the retracting path 2 a 2 . an optical reversal sensor 203 that detects, for switchback, an end of the sheet is provided on the reversing and conveying path 3 side of the roller pair 204 in a sheet conveying direction in the first conveying path 2 a . the reversal sensor 203 is arranged further on a downstream side than a reversal mylar 207 , which is arranged above the first flapper 202 , in the first conveying direction of the first conveying path 2 a . the reversal mylar 207 has a function of passing the leading end of a sheet conveyed from the fixing device 6 side to the first conveying path 2 a but preventing the leading end of the sheet from entering the fixing device 6 from the first conveying path 2 a . therefore, the reversal sensor 203 is arranged further on the downstream side than the reversal mylar 207 in the first conveying direction as explained above. consequently, the sheet is switched back further on the downstream side in the first conveying direction than the reversal mylar 207 and the switched-back sheet is surely conveyed to the reversing path 2 a 3 . operations of the conveying rollers and the flappers in the relay reversing unit 2 are controlled by the cpu 10 . a paper discharge roller pair 7 a and a paper discharge tray 7 b are provided near the first paper discharge port 7 . the sheet conveyed through the paper discharge conveying path 2 a 1 of the relay reversing unit 2 is discharged onto the paper discharge tray 7 b by the paper discharge roller pair 7 a. the reversing and retracting unit 9 is provided to temporarily retract, when the sheet is switched back and conveyed, a portion near the end in the downstream side in the first conveying direction of the sheet until the end on the upstream side in the first conveying direction of the sheet passes the reversal sensor 203 and is switched back. in the image forming apparatus 1 according to this embodiment, the reversing and retracting unit 9 is integrally formed with the paper discharge tray 7 b of the first paper discharge port 7 under the paper discharge tray 7 b. the reversing and retracting unit 9 includes a reversing and retracting path 9 a connected to the retracting path 2 a 2 of the relay reversing unit 2 and an optical standby position sensor s 2 (equivalent to the second sensor) that detects the passage of the end on the upstream side in the second conveying direction of the sheet during the switchback. the standby position sensor s 2 is arranged in a position where, for example, when standby processing is performed until the sheet becomes capable of entering the reversing and conveying path 3 after the switchback of the sheet, it is possible to put the sheet on standby in a predetermined standby position for preventing the end on the upstream side in the second conveying direction of the sheet from entering the reversing and retracting path 9 a by length equal to or larger than predetermined length l 1 . in this embodiment, as shown in fig. 3 , the standby position sensor s 2 is arranged in a position at the predetermined length l 1 on the first conveying direction side from the end on the relay reversing unit 2 side of the reversing and retracting path 9 a. therefore, after the switchback, the conveyance of the sheet is stopped when the standby position sensor s 2 detects the passage of the end of the sheet. this makes it possible to put the sheet on standby in the position where the end of the sheet does not enter the reversing and retracting path 9 a by a length equal to or larger than the predetermined length. the “predetermined length” means shortest entering length among entering lengths of the sheet into the reversing and retracting path 9 a that cause damage in a portion of the sheet entering the reversing and retracting path 9 a when the relay reversing unit 2 is extracted from the image forming apparatus 1 in the y axis direction in fig. 2 . the damage is caused because the end of the sheet enters the reversing and retracting path 9 a in a state in which the sheet is put on standby until it becomes possible to convey the sheet to the reversing and conveying path 3 . therefore, for example, if entering length of the sheet into the reversing and retracting path 9 a is equal to or larger than the predetermined length in the standby state of the sheet (see fig. 6 ), when the relay reversing unit 2 is extracted, a portion of the sheet entering the reversing and retracting path 9 a is caught by the reversing and retracting path 9 a and damage to the sheet occurs, for example, the sheet is torn or bent. on the other hand, if entering length of the sheet into the reversing and retracting path 9 a is smaller than the predetermined length in the standby state of the sheet (see fig. 7 ), no damage to the end of the sheet occurs even if the relay reversing unit 2 is extracted. the entering length of the sheet into the reversing and retracting path 9 a is smaller than the predetermined length not only when the sheet enters the reversing and retracting path 9 a by length smaller than the predetermined length but also when the end of the sheet is present in the relay reversing unit 2 and does not enter the reversing and retracting path 9 a at all. in this embodiment, as explained above, for example, as shown in fig. 3 , the “predetermined length” is set to l 1 . specific “predetermined length” changes according to the structure of the image forming apparatus 1 . in a general image forming apparatus, usually, the predetermined length is in a range of length larger than 0 mm and equal to or smaller than 20 mm. for example, when the predetermined length l 1 of the image forming apparatus 1 according to this embodiment is 15 mm, the sheet is put on standby in a position where entering length of the sheet into the reversing and retracting path 9 a is smaller than 15 mm. consequently, the sheet is not damaged even if the relay reversing unit 2 is extracted. “length” in the “predetermined length” means length from a position on the most upstream side in the first conveying direction to a position of the leading end on the downstream side in the first conveying direction in a side end of the sheet that comes into contact with an inner wall of the reversing and retracting path 9 a when the relay reversing unit 2 is extracted. a lower conveyance guide 9 c forming a bottom surface of the inner wall of the reversing and retracting path 9 a in the reversing and retracting unit 9 (at least a part of the sheet conveying path) is integrally formed with a cover on the lower side of the paper discharge tray 7 b. the lower conveyance guide 9 c is openable downward around a rotation axis 9 d (a predetermined rotation axis). fig. 8 is a diagram of a state in which the lower conveyance guide 9 c is opened. it is preferable that the standby position sensor s 2 is arranged further on the upstream side of the reversing and retracting path 9 a in the second conveying direction than the rotation axis 9 d. since the position of the standby position sensor s 2 is set further on the upstream side in the second conveying direction than the rotation axis 9 d in this way, when the lower conveyance guide 9 c is opened to eliminate a sheet jam or the like, the standby position sensor s 2 portion is integrally opened. therefore, there is an effect that it is possible to minimize damage to the standby position sensor s 2 when the sheet is removed. the reversing and conveying path 3 is a path for reversing a switch-backed sheet. when the sheet having an image formed on the first side is conveyed through the reversing and conveying path 3 with the end on the downstream side in the second conveying direction set as the leading end, the reversing and conveying path 3 reverses the sheet to make it possible to form an image on the second side of the sheet. when the sheet reversed by being conveyed through the reversing and conveying path 3 is conveyed to the secondary transfer position 5 b again, the image is formed on the second side of the sheet. the reversing and conveying path 3 includes roller pairs 301 to 304 , a switch-type sensor 305 that detects entrance of a sheet into the reversing and conveying path 3 , and a switch-type sensor 306 that detects conveyance of the sheet near an outlet of the reversing and conveying path 3 . the cpu 10 determines, according to presence or absence of a sheet detected by the switch-type sensor 305 and the switch-type sensor 306 , whether the sheet can enter the reversing and conveying path 3 . if the cpu 10 determines, on the basis of detection results of the sensors 305 and 306 , that the sheet cannot enter the reversing and conveying path 3 , the cpu 10 puts the sheet on standby in the standby position. on the other hand, if the cpu 10 determines that the sheet can enter the reversing and conveying path 3 , the cpu 10 performs processing for conveying the switched-back sheet or the sheet put on standby in the standby position to the reversing and conveying path 3 . as an example of a state in which the sheet cannot enter the reversing and conveying path 3 , a sheet is already present in the reversing and conveying path 3 and both the switch-type sensors 305 and 306 detect conveyance of the sheet. as another example, a sheet is present on the upstream side of the reversing and conveying path 3 and only the switch-type sensor 305 detects the sheet. on the other hand, as an example of a state in which the sheet can enter the reversing and conveying path 3 , there is no sheet in the reversing and conveying path 3 and both the switch-type sensors 305 and 306 do not detect conveyance of a sheet. as another example, a sheet being conveyed is already present in the reversing and conveying path 3 but the sheet is short and only the switch-type sensor 306 detects the sheet and, even if the next sheet is conveyed to the reversing and conveying path 3 , the next sheet can be stored in the reversing and conveying path 3 without overlapping the sheet already being conveyed. a flow of an operation of reversal processing involving standby processing for a sheet performed by the image forming apparatus 1 according to this embodiment having the above configuration is explained below. as explained above, a developer image formed on the intermediate transfer belt 5 a is transferred onto a sheet fed from the sheet feeding unit 14 and the developer image is heated and fixed on the sheet by the fixing device 6 , whereby an image is formed on the first side of the sheet. the sheet having the image formed on the first side is conveyed from the fixing device 6 in the first conveying direction by the roller pair 201 . when duplex printing is applied to the sheet, the sheet conveyed in the first conveying direction is switched back to be conveyed in the second conveying direction and is conveyed to the reversing and conveying path 3 to be subjected to the reversal processing. in the reversal processing, first, in order to lead the sheet to the first conveying path 2 a and the retracting path 2 a 2 , the cpu 10 controls the first flapper 202 to be lowered and controls the second flapper 205 to be lifted in advance as shown in fig. 4 . in this state, the sheet conveyed from the fixing device 6 is conveyed in the first conveying direction until the end on the upstream side in the first conveying direction of the sheet (i.e., the trailing end in the first conveying direction of the sheet) passes the reversal sensor 203 . the end on the downstream side in the first conveying direction of the sheet (i.e., the leading end in the first conveying direction of the sheet) is conveyed to the first conveying path 2 a and the retracting path 2 a 2 (the paper discharge tray side) by the roller pair 204 and the like. the sheet conveyed through the retracting path 2 a 2 enters the reversing and retracting path 9 a in the reversing and retracting unit 9 as another unit adjacent to the relay reversing unit 2 . in a state in which the leading end side of the sheet is retracted by using the first conveying path 2 a , the retracting path 2 a 2 , and the reversing and retracting path 9 a of the reversing and retracting unit 9 as explained above, when the reversal sensor 203 detects the passage of the trailing end of the sheet, the cpu 10 starts switchback of the sheet. specifically, when the reversal sensor 203 detects the passage of the end of the sheet, the cpu 10 performs control to stop the conveyance of the sheet in the first conveying direction by the roller pair 204 and convey the sheet in the second conveying direction. in the example shown in fig. 6 , at a point when the trailing end of the sheet passes the reversal sensor 203 and is switched back in a switchback position 1001 a , the leading end of the sheet is retracted into the retracting path 2 a 2 and the reversing and retracting path 9 a and reaches a switchback position 1002 a. after the switchback, another sheet is already held up in the reversing and conveying path 3 and the cpu 10 determines, on the basis of detection results of the sensors 305 and 306 in the reversing and conveying path 3 , that the sheet having the image formed on the first side cannot be conveyed to the reversing and conveying path 3 . in this case, the image forming apparatus 1 according to this embodiment conveys the sheet in the second conveying direction from the switchback position to the predetermined standby position and puts the sheet on standby in the predetermined standby position. in the state shown in fig. 6 , at the start of the switchback, the end on the upstream side in the second conveying direction of the sheet (i.e., the trailing end in the second conveying direction of the sheet) is present in the switchback position 1002 a . the end on the upstream side enters the reversing and retracting path 9 a by length equal to or larger than the predetermined length l 1 . if the relay reversing unit 2 is extracted in this state, it is likely that the sheet entering the reversing and retracting path 9 a is damaged. therefore, the cpu 10 drives the roller pairs to convey the sheet in the second conveying direction until the entering length of the sheet into the reversing and retracting path 9 a is reduced to be smaller than the predetermined length l 1 and puts the sheet on standby. specifically, after switching back the sheet in the switchback position 1002 a , the cpu 10 conveys the sheet in the second conveying direction until it is detected that the end on the upstream side in the second direction of the sheet passes the standby position sensor s 2 . when the passage of the end on the upstream side of the sheet is detected by the standby position sensor s 2 , the cpu 10 stops the driving of the roller pair 204 and puts the sheet on standby. in the case of the sheet in the state shown in fig. 6 , the end of the sheet in the reversing and retracting path 9 a moves from the switchback position 1002 a to the standby position 1002 b , the end of the sheet on the reversing and conveying path 3 side moves from the switchback position 1001 a to the standby position 1001 b , and the sheet is put on standby. according to the standby processing after the switchback explained above, the image forming apparatus 1 can put the sheet on standby in a state in which the end of the sheet does not enter the reversing and retracting path 9 a of the reversing and retracting unit 9 adjacent to the relay reversing unit 2 by length equal to or larger than the predetermined length l 1 . therefore, there is an effect that, even if a sheet jam or the like occurs in this standby state and the relay reversing unit 2 is extracted from the image forming apparatus 1 , a portion of the sheet on the reversing and retracting unit 9 side is not damaged. consequently, it is possible to prevent waste of sheets due to damage to the sheets and prevent deficiencies in the image forming apparatus 1 caused by a part of a torn sheet remaining in the image forming apparatus 1 . determination of jam processing time in the image forming apparatus 1 according to this embodiment is explained below. fig. 9 is a functional block diagram of the image forming apparatus 1 according to this embodiment. as shown in fig. 9 , the image forming apparatus 1 according to this embodiment includes a determining unit 101 , a notification control unit 102 , and a unit identifying unit 103 . functions of the determining unit 101 , the notification control unit 102 , and the unit identifying unit 103 are realized by causing the cpu 10 to execute a sheet state determining program stored in the memory 12 or a storage area provided in the image forming apparatus 1 . if a sheet is simultaneously detected by both the first sensor s 1 and the standby position sensor s 2 , the determining unit 101 determines that the sheet is present across a boundary between the relay reversing unit 2 and the reversing and retracting unit 9 . if the determining unit 101 determines that the sheet is present across the boundary between the relay reversing unit 2 and the reversing and retracting unit 9 , the notification control unit 102 causes the display unit 102 a to perform notification for urging the user to open the lower conveyance guide 9 c before extracting the relay reversing unit 2 . the unit identifying unit 103 identifies a processing unit to be mounted on the image forming apparatus 1 . if the processing unit identified by the unit identifying unit 103 prevents the opening of the lower conveyance guide 9 c, the notification control unit 102 causes the display unit 102 a to notify to the effect that, before the lower conveyance guide 9 c is opened, the processing unit should be retracted to a position where the processing unit does not prevent the opening of the lower conveyance guide 9 c. a flow of processing performed when a sheet jam occurs in the image forming apparatus 1 according to this embodiment is explained. fig. 10 is a flowchart of a flow of jam processing in the image forming apparatus 1 according to this embodiment. if the cpu 10 determines, on the basis of, for example, a sheet detection result in any one of the first sensor s 1 , the standby position sensor s 2 , and the reversal sensor 203 , that a sheet jam occurs in the relay reversal unit 2 (act 101 , yes), the determining unit 101 determines whether the sheet is simultaneously detected by both the first sensor s 1 and the standby position sensor s 2 (act 102 ). if the sheet is not simultaneously detected by the first sensor s 1 and the standby position sensor s 2 (act 102 , no), the determining unit 101 determines that a sheet across the boundary between the relay reversing unit 2 and the reversing and retracting unit 9 is not present. in this case, the notification control unit 102 causes the display unit 102 a to notify to the effect that the sheet jam should be eliminated by opening the lower conveyance guide 9 c (act 103 ). on the other hand, if a sheet is simultaneously detected by both the first sensor s 1 and the standby position sensor s 2 (act 102 , yes), the determining unit 101 determines that the sheet across the boundary between the relay reversing unit 2 and the reversing and retracting unit 9 is present. subsequently, the unit identifying unit 103 identifies a processing unit mounted on the image forming apparatus 1 (act 104 ). if the processing unit identified by the unit identifying unit 103 prevents the opening of the lower conveyance guide 9 c (e.g., when the post-processing unit f is mounted right below the paper discharge tray 7 b as a processing unit), the notification control unit 102 causes the display unit 102 a to notify to the effect that, before the lower conveyance guide 9 c is opened, the processing unit should be retracted to a position where the processing unit does not prevent the opening of the lower conveyance guide 9 c (e.g., the processing unit is removed from the image forming apparatus 1 ) (act 105 ). on the other hand, if the processing unit identified by the unit identifying unit 103 does not prevent the opening of the lower conveyance guide 9 c, the notification control unit 102 causes the display unit 102 a to notify to the effect that the lower conveyance guide 9 c should be opened to attempt sheet removal before the relay reversing unit 2 is extracted (act 106 ). if a sheet is detected only by the first sensor s 1 in act 102 , there is no sheet projecting from the sheet conveying path of the relay reversing unit 2 to the reversing and retracting path 9 . therefore, it is unnecessary to open the lower conveyance guide 9 c when the sheet jam is eliminated. in other words, work for opening the lower conveyance guide 9 c and checking presence or absence of a sheet in the reversing and retracting path 9 a is omitted from a work procedure for eliminating the sheet jam. as explained above, according to this embodiment, it is necessary to operate the lower conveyance guide 9 c of the paper discharge tray 7 b forming the lower left of the reversing and retracting path 9 a only when a sheet is simultaneously detected by the first sensor s 1 and the standby position sensor s 2 . therefore, it is possible to clearly display, only when necessary, a message for urging operation of the lower conveyance guide 9 c to the user to omit the operation for opening the lower conveyance guide 9 c from the normal sheet jam eliminating work. this contributes to a substantial reduction in work load when a sheet jam occurs. in the image forming apparatus 1 according to this embodiment, it is possible to remove a sheet jammed in the apparatus according to any one of procedures (1) to (3) below or a combination of these procedures. (1) remove a sheet entering the relay reversing unit 2 specifically, a jammed sheet is removed from the fixing device side. a sheet jammed near an inlet to the reversing and conveying path 3 after reversal is removed. (2) remove a sheet being discharged from the relay reversing unit 2 specifically, a jammed sheet is removed from the paper discharge tray 7 b side. (2b) when there is a sheet put on standby for reversal and length of the leading end of the sheet extending out to the area of the relay reversing unit 2 is equal to or larger than fixed length, open the lower conveyance guide 9 c to remove the sheet from the outside(3) extract the relay reversing unit 2 to the outside of the apparatus and remove a sheet jammed in the relay reversing unit 2 with the image forming apparatus 1 according to this embodiment, since the lower conveyance guide 9 c is openable, it is possible to perform the operation ( 2 b ) after the procedures (1) and (2a). however, work for checking a state of a sheet jam by opening the lower conveyance guide 9 c is not work that always needs to be performed when a sheet jam occurs but is rather operation that is very rarely necessary. with the image forming apparatus 1 according to this embodiment, since the image forming apparatus 1 notifies the user that that the user should open the lower conveyance guide 9 c only when it is necessary to open the lower conveyance guide 9 c, it is possible to prevent the user from performing an unnecessary check. the operations in the processing in the image forming apparatus 1 are realized by causing the cpu 10 to execute the sheet state determining program stored in the memory 12 . a computer program that causes a computer configuring the image forming apparatus to execute the operations can be provided as the sheet state determining program. in the example explained in this embodiment, the computer program for realizing the functions for carrying out the present invention is recorded in advance in the storage area provided in the apparatus. however, present invention is not limited to this. the same computer program may be downloaded from a network to the apparatus or the same computer program stored in a computer-readable recording medium may be installed in the apparatus. a form of the recording medium may be any form as long as the recording medium can store the computer program and can be read by the computer. specifically, examples of the recording medium include internal storage devices implemented in the computer such as a rom and a ram, portable storage media such as a cd-rom, a flexible disk, a dvd disk, a magneto-optical disk, and an ic card, a database that stores a computer program, other computers and databases for the computers, and a transmission medium on a line. functions obtained by the installation and the download in this way may realize the functions in cooperation with an os (operating system) in the apparatus. the computer program in this embodiment includes a computer program for dynamically generating an execution module. in the example explained in the embodiment, the first sensor s 1 is the actuator-type sensor, the reversal sensor 203 and the standby position sensor s 2 are the optical sensors, and the switch-type sensor 305 and the switch-type sensor 306 in the reversing and conveying path 3 are the sensors of the switch type. however, the present invention is not limited to this. any sensor may be adopted as long as the sensor can detect the passage of a sheet such as a reflective sensor and a transmissive sensor. the arrangement of the first sensor s 1 and the standby position sensor s 2 is not always limited to the positions explained in the embodiment. it goes without saying that the first sensor s 1 and the standby position sensor s 2 may be arranged in other positions as long as the sensors can detect a sheet present in the reversing and retracting path 9 and the relay reversing unit 2 . in the example explained in the embodiment, it is determined on the basis of sheet detection results in the two sensors whether a sheet across the boundary between the relay reversing unit 2 and the reversing and retracting unit 9 is present. however, the present invention is not always limited to this. it goes without saying that, for example, it is also possible to perform the determination using sheet detection results of two or more sensors arranged in each of the relay reversing unit 2 and the reversing and retracting unit 9 . in the example of the procedure explained with reference to the flowchart shown in fig. 10 , after determining whether the sheet is simultaneously detected by both the first and second sensors (act 102 ), the determining unit 101 determines whether a processing unit that prevents the opening of the lower conveyance guide 9 c is mounted on the main body of the image forming apparatus (act 104 ). however, a processing procedure in the sheet state determining method is not always limited to this procedure by the present invention. for example, the processing in act 104 may be performed prior to the processing in act 102 . the processing in act 102 and the processing in act 104 can be simultaneously performed. in other words, results obtained by the determination processing in act 102 and act 104 only have to be acquired at timing when the determination processing for determining contents of notification by the notification control unit 102 is executed. in the example explained in the embodiment, the notification processing by the notification control unit 102 is realized by screen display on the display unit 102 a . however, the present invention is not limited to this. for example, the notification can be realized by processing such as sound notification by a speaker incorporated in the image forming apparatus 1 or flashing of a lamp provided in the image forming apparatus 1 . the present invention is explained in detail above with reference to the specific embodiment. however, it would be apparent to those skilled in the art that various modifications and alterations can be made without departing from the spirit and the scope of the present invention. as explained above in detail, it is possible to provide, in an image forming apparatus in which a part of a sheet conveying path for reversing a sheet is formed as a unit to be extractable to the outside of the apparatus, a technique for preventing damage to the sheet involved in extracting operation for the extractable unit.
|
067-189-245-071-775
|
GB
|
[
"US",
"GB",
"EP"
] |
E04G21/18,G01C15/00,G01C15/10
| 1999-12-16T00:00:00 |
1999
|
[
"E04",
"G01"
] |
apparatus for and a method of providing a reference point or line
|
a level apparatus is disclosed that includes a body mounted on an elongate member. the body typically includes a laser that is capable of rotation about horizontal and/or vertical axes. the elongate member can be braced between, for example, a floor and a ceiling and the body is typically capable of longitudinal movement along an axis that is substantially parallel to a longitudinal axis of the elongate member. movement of the body and other functions of the apparatus can be remote controlled.
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1 . apparatus for providing a reference point or line, the apparatus comprising a body and an elongate member having a longitudinal axis, the body having a laser and being capable of movement substantially parallel to the longitudinal axis of the elongate member. 2 . apparatus according to claim 1 , wherein the elongate member is adapted to be fixed to a support. 3 . apparatus according to claim 1 , wherein the elongate member is provided with a first bracket for engaging a first supporting structure. 4 . apparatus according to claim 3 , wherein the elongate member is provided with a second bracket for engaging a second supporting surface. 5 . apparatus according to claim 1 , wherein the elongate member is provided with adjustment means to facilitate adjustment of the length of the elongate member. 6 . apparatus according to claim 5 , wherein the adjustment means comprises a telescopic or sliding portion of the elongate member. 7 . apparatus according to claim 5 , wherein the adjustment means includes a locking means. 8 . apparatus according to claim 7 , wherein the locking means comprises a locking collar and a tightening sleeve. 9 . apparatus according to claim 1 , wherein the elongate member is adapted to be held using one or more guy ropes attached to the member. 10 . apparatus according to claim 1 , wherein the elongate member comprises two or more portions that are coupled together. 11 . apparatus according to claim 10 , wherein the portions are of different lengths. 12 . apparatus according to claim 1 , wherein the elongate member has a counterweight attached thereto. 13 . apparatus according to claim 12 , wherein the counterweight is suspended from a plumb line. 14 . apparatus according to claim 13 , wherein the plumb line is attached at a first end thereof to the body, and at a second end thereof to the counterweight. 15 . apparatus according to claim 13 , wherein the plumb line passes through a pulley provided at an end of the elongate member. 16 . apparatus according to claim 13 , wherein the plumb line passes over a pulley provided at an end of the elongate member. 17 . apparatus according to claim 13 , wherein the body can be moved substantially parallel to the elongate member by varying the length of the plumb line. 18 . apparatus according to claim 13 , wherein the elongate member is provided with a bore in which the plumb line and the counterweight can be located. 19 . apparatus according to claim 12 , wherein the counterweight engages a portion of the elongate member. 20 . apparatus according to claim 1 , wherein the movement of the body substantially parallel to the longitudinal axis of the elongate member can be remotely controlled. 21 . apparatus according to claim 1 , wherein the body is provided with a motor and gear assembly to move the body substantially parallel to the longitudinal axis of the elongate member. 22 . apparatus according to claim 21 , wherein the elongate member is provided with engagement means for engagement with the motor and gear assembly provided on the body. 23 . apparatus according to claim 1 , wherein the laser is capable of rotation about a first axis that is substantially parallel to the longitudinal axis of the elongate member. 24 . apparatus according to claim 23 , wherein the laser can rotate through 360 about the first axis. 25 . apparatus according to claim 1 , wherein the laser is capable of rotation about a second axis that is substantially perpendicular to the longitudinal axis of the elongate member. 26 . apparatus according to claim 25 , wherein the laser can rotate through 360 about the second axis. 27 . apparatus according to claim 1 , wherein the laser is interchangeable so that a number of different lasers can be used for different functions. 28 . apparatus according to claim 1 , wherein the laser is mounted to the body using a swivel. 29 . apparatus according to claim 28 , wherein the laser is mounted to the swivel using a mounting plate, the mounting plate being capable of rotation about an axis that is substantially perpendicular to the longitudinal axis of the elongate member 30 . apparatus according to claim 29 , wherein the mounting plate is capable of 360 rotation about the axis. 31 . apparatus according to claim 29 , wherein the mounting plate is provided with indication means. 32 . apparatus according to claim 31 , wherein the indication means comprises a plurality of lines indicating angular positions of the laser relative to one of the pole and the mounting plate. 33 . apparatus according to claim 29 , wherein one of the mounting plate and the body is provided with a locking means to lock the laser at a certain angle. 34 . a method of providing a reference point or line, the method comprising the steps of providing a body and an elongate member having a longitudinal axis, the body having a laser and being capable of movement substantially parallel to the longitudinal axis of the elongate member; securing the elongate member in a substantially vertical orientation; positioning the laser at a pre-selected position on the elongated member; and actuating the laser. 35 . a method according to claim 34 , wherein the elongate member is secured in a substantially vertical orientation by bracing it between first and second surfaces. 36 . a method according to claim 35 , wherein the first surface comprises a ceiling. 37 . a method according to claim 35 , wherein the second surface comprises a floor.
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the present invention relates to apparatus for and a method of providing a reference point or line, and more particularly, but not exclusively, to apparatus and a method that incorporates a laser. description of the related art it is known to incorporate lasers into apparatus that can provide reference points (e.g. levels, plumb lines etc) such as plumb levels. plumb levels are used particularly in the building trade to establish straight lines for brickwork, plumb points for wall corners and various other functions. the design and configuration of conventional apparatus incorporating lasers varies, but generally they require some form of tripod stand for support or alternatively some surface on which they are placed. once placed on the surface or on the tripod, the apparatus requires to be levelled either manually or automatically using various adjustment mechanisms. the operation of conventional apparatus is limited due to the limitations of a tripod stand or other surface upon which the apparatus rests. it is often required to provide levels at various heights, and the conventional mounting of the apparatus cannot always be used as its height variability is limited. where tripod stands are used, the tripods are limited by their size and extension capabilities and generally do not have the capability of being extended to allow the apparatus to be positioned at or near a ceiling, particularly in rooms with high ceilings. additionally, where the apparatus merely rests on a surface, height adjustment is dependent on having a suitable surface at the correct height, which is not always possible. additionally, conventional apparatus requires a user to adjust the height either by manually moving the apparatus to a different surface, or by manually adjusting the height of the tripod or other stand. this can be a time-consuming process particularly where the user is working up a ladder or on scaffolding for example, and has to climb down before manually adjusting the apparatus, and then climb up again. furthermore, conventional apparatus typically does not provide for a full range of motion i.e. they normally allow for 360 rotation about a vertical axis, but do not provide for 360 rotation about a horizontal axis. brief summary of the invention according to a first aspect of the present invention, there is provided apparatus for providing a reference point or line, the apparatus comprising a body and an elongate member having a longitudinal axis, the body having a laser and being capable of movement substantially parallel to the longitudinal axis of the elongate member. according to a second aspect of the present invention, there is provided a method of providing a reference point or line, the method comprising the steps of providing a body and an elongate member having a longitudinal axis, the body having a laser and being capable of movement substantially parallel to the longitudinal axis of the elongate member; securing the elongate member in a substantially vertical orientation; positioning the laser at a pre-selected position on the elongated member; and actuating the laser. the elongate member is typically adapted to be fixed to a support. the elongate member is typically provided with a first bracket for engaging a first supporting surface or structure. the elongate member is typically also provided with a second bracket for engaging a second supporting surface or structure. the elongate member is typically provided with adjustment means to facilitate adjustment of the length of the elongate member. the adjustment means typically comprises a telescopic or sliding portion of the elongate member. the adjustment means typically includes a locking means. the locking means typically comprises a locking collar and a tightening sleeve. optionally, the elongate member can be adapted to be held using one or more guy ropes attached to the member. the elongate member preferably comprises two or more portions that are coupled together. the portions are typically of different lengths. thus, different portions having different lengths can be coupled together so that the elongate member can be braced between the first and second surfaces or structures the length of the elongate member can be adjustable in use, and this can be achieved by providing a second telescopic portion or sliding pole portions either side by side or concentrically. the elongate member preferably has a counterweight attached thereto. the counterweight is typically suspended from a plumb line. the plumb line is typically attached at a first end thereof to the body, and at a second end thereof to the counterweight. the plumb line typically passes through or over a pulley provided at an end of the elongate member. the body can optionally be moved substantially parallel to the elongate member by varying the length of the plumb line. the counterweight is typically used to ensure that the elongate member is plumb before and/or during use. the elongate member is typically provided with a bore in which the plumb line and/or the counterweight can be located. the counterweight can engage a portion of the elongate member. the body can move relative to the elongate member itself, or can be fixed in relation to one of the portions of the elongate member and can be moved along the axis of the elongate member by moving the location of the portion within the member. the movement of the body substantially parallel to the longitudinal axis of the elongate member can be remotely controlled. the body is optionally provided with a motor and gear assembly to move the body substantially parallel to the longitudinal axis of the elongate member. the elongate member is optionally provided with engagement means for engagement with the motor and gear assembly provided on the body. the laser is typically capable of rotation about a first axis that is substantially parallel to the longitudinal axis of the elongate member. the laser is typically also capable of rotation about a second axis that is substantially perpendicular to the longitudinal axis of the elongate member. the laser can preferably rotate through 360 about the first and/or second axis thus, a light beam emitted by the laser can be directed in substantially any direction. optionally, rotation of the laser about the first and/or second axis can be remotely controlled. the laser can be interchangeable so that a number of different lasers can be used for different functions. alternatively, two or more different lasers can be provided that are capable of being operated independently of one another. optionally, the or each laser can be remotely controlled so that they can be remotely interchanged or operated. the laser is typically mounted to the body using a swivel. the laser is typically mounted to the swivel using a mounting plate, the mounting plate being capable of rotation about an axis that is substantially perpendicular to the longitudinal axis of the elongate member. the mounting plate is typically capable of 360 rotation about the axis. optionally, the mounting plate is provided with indication means. the indication means typically comprises a plurality of lines indicating angular positions of the laser relative to the pole or plate. the mounting plate and/or the body are typically provided with a locking means to lock the laser at a certain angle. the elongate member is typically secured in a substantially vertical orientation by bracing it between first and second surfaces or structures. the first surface typically comprises a ceiling, and the second surface typically comprises a floor the method typically includes the additional step of adjusting the adjustment means so that the elongate member is braced between the first and second surfaces or structures. the method optionally includes the additional steps of providing one or more guy ropes and attaching these to the elongate member to secure the elongate member in a substantially vertical orientation. the method typically includes the additional steps of coupling the portions together to form the elongate member. the method typically includes the additional step of attaching the plumb line at a first end thereof to the body, and at a second end thereof to the counterweight. the method typically includes the additional step of adjusting the orientation of the elongate member so that it is plumb by using the counterweight as a reference. the method optionally includes the additional step of varying the length of the plumb line to move the body substantially parallel to the elongate member to set the laser at a pre-selected height. the method typically includes the additional steps to rotating the laser about the first and/or second axis to direct the laser at a pre-selected angle. the method optionally includes the additional steps of removing the laser from the body and replacing with another laser. brief description of the several views of the drawings embodiments of the present invention shall now be described, by way of example only, with reference to the accompanying drawings, in which: fig. 1 is a cross sectional elevation of apparatus according to the present invention; fig. 2 is an enlarged view of part of the apparatus of fig. 1 ; fig. 3 is a further enlarged view of part of the apparatus of fig. 1 ; fig. 4 is a side elevation of the apparatus of figs. 1 to 3 ; fig. 5 is a side elevation of a second embodiment of apparatus; and fig. 6 is a plurality of cross-sectional views of the apparatus of fig. 5 wherein a) shows a body at a lower end of a pole; b) shows the body at an intermediate position on the pole; and c) shows the body at the top of the pole. detailed description of the invention referring to the drawings, figs. 1 and 4 show a first embodiment of apparatus for providing a reference point or line, generally designated 10 , according to the present invention. fig. 1 shows a cross-sectional elevation and fig. 4 shows a side elevation of the apparatus 10 . apparatus 10 includes an elongate member (e.g. a pole 12 ) that advantageously comprises a plurality of portions 12 p. portions 12 p are coupled together, typically by screw threads at junctions 12 j. different lengths of portions 12 p can be used so that the overall length of pole 12 can thus be varied. this allows the pole 12 to be positioned (and thus supported) between a floor 14 and a ceiling 16 , for example. it should be noted that the pole 12 may be supported using any conventional means the pole portions 12 p can be fixed together in a particular embodiment for use at a particular height, but it is preferred that the length of a pole 12 can be varied by using different lengths of individual portions 12 p. alternatively, the length of pole 12 p may be adjusted by collapsing or extending pole portions 12 p relative to one another. thus, the pole 12 can be disassembled for more compact storage and easier transportation and can then be assembled to any length, depending upon the lengths of portions 12 p. it should be noted that the portions 12 p may be coupled using any conventional means, such as a pin provided on one end of a portion 12 p that engages in an aperture on the end of a successive portion 12 p. the portions 12 p may also be telescopically coupled together apparatus 10 includes a body 20 that is attachable to the pole 12 and can move substantially parallel to the longitudinal axis of the pole 12 . for example, body 20 may be provided with a central aperture 22 through which the pole 12 may pass, thus allowing the body 20 to slide longitudinally along the pole 12 . in the embodiment shown in figs. 1 and 4 , the body 20 is provided with a motor and gear assembly (not shown in detail) that engages the pole 12 , typically using a track 42 ( fig. 2 ). the motor and gear assembly can be remotely controlled so that the body 20 can be moved up and down the pole 12 using the motor and gear assembly. the motor and gear assembly may be activated using a remote controller (not shown) that may be hard-wired to the body 20 , or preferably communicates with the body 20 using infra-red or the like. alternatively, a drive mechanism can be provided on the pole 12 (such as a belt or chain with a pulley arrangement at the pole ends) so that the body 20 can be pulled along the pole axis. activating the motor and gear assembly allows the vertical displacement of the body 20 to be adjusted to different heights without any manual adjustment. this is advantageous where the user is located up a ladder or on scaffolding for example. a counterweight 24 (or plumb bob) is used to balance the weight of the body 20 and is attached thereto using a plumb line 26 . line 26 is tied at a first end to the counterweight 24 and at a second end to the body 20 . the line 26 is located in a bore 12 b extending through the portions 12 p (i.e. it is located within the pole 12 ) and also passes around a pulley 20 located at or near the upper end 12 u of the pole 12 . the upper and lower ends 12 u, 12 l of the pole 12 may each be provided with a bracket 18 u at the upper end 12 u and a bracket 18 l at the lower end 12 l of the pole 12 , the brackets 18 u, 18 l facilitating engagement with the ceiling 16 and floor 14 , respectively. referring to fig. 3 , there is shown an enlarged view of the lower portion 12 l of the pole 12 . the bracket 18 l includes a viewing slot 18 s that allows a user to see the counterweight 24 (shown in dotted outline in fig. 3 ). the pole 12 should be plumb when the counterweight 24 is located in an aperture 18 a within bracket 18 l. it will be appreciated that bore 12 b through each portion of pole 12 is typically a throughbore, but it will also be appreciated that the bore 12 b at the ends 12 u, 12 l of the pole 12 will be blind bores. that is, the bores 12 b at the ends 12 u, 12 l will be closed at these ends because of brackets 18 u, 18 l. bracket 18 l is further provided with a telescopic portion 18 t that facilitates adjustment of the height of the bracket 18 so that the pole 12 can extend between the floor 14 and the ceiling 16 . it will be appreciated that a portion of the pole 12 can be provided with a telescopic portion in addition or in the alternative to portion 18 t on the bracket 18 l. also, a telescopic portion may alternatively or additionally be provided on the upper bracket 18 u. thus, the telescopic portion 18 t facilitates fine adjustment of the height of pole 12 so that pole 12 fits securely between the floor 14 and ceiling 16 . bracket 18 l includes a locking collar 18 c that is slidably engaged with the lower portion 12 l of the pole 12 , and is used to lock the height of the telescopic portion 18 t. the locking collar 18 c is typically held in place using, for example, a locking bolt and nut, generally designated 19 . a tightening sleeve 21 is threadedly attached to the lower portion 12 l of pole 12 , and abuts against the locking collar 18 c to prevent axial movement thereof. in use, the tightening sleeve 21 is slackened by rotating it in a first direction. the locking bolt and nut 19 is then slackened to allow for movement of the telescopic portion 18 t. the telescopic portion 18 t is then set to the required height and the locking nut and bolt 19 tightened. the tightening sleeve 21 is then brought into abutment with the locking collar 18 c and rotated in a second direction, typically opposite to the first direction, to prevent axial movement of the locking collar 18 c. in use, the portions 12 p are coupled together to provide a pole 12 that typically extends between the floor 14 and ceiling 16 . the body 20 is located on the pole 12 before the pole 12 is braced between the floor 14 and ceiling 16 . where the apparatus 10 is being used outdoors, or where the pole 12 cannot be braced between a floor and ceiling, guy ropes (not shown) may be used, attached at or near the upper end 12 p of the pole 12 , to stabilise the pole 12 during use. it will be appreciated that the pole 12 can be braced between any two spaced-apart surfaces that are generally parallel to one another (that is, it need not be braced between the floor and the ceiling). also, guy ropes may be used and coupled to the pole 12 even when the pole 12 is braced between the floor 14 and the ceiling 16 . the plumb line 26 is tied to the body 12 and the counterweight 24 (plumb bob) is positioned at or near the lower end 12 l of the pole 12 , thus allowing the pole 12 to be adjusted so that it is plumb. as shown in fig. 3 , the counterweight 24 is located within the lower portion 12 l of the pole 12 and is aligned with the aperture 18 a in the bracket 18 in use. the slot 18 s in the bracket 18 l allows the user to check that the apparatus is plumb (i.e. that the counterweight 24 is engaged in the aperture 18 a ). the counterweight 24 is suspended on the plumb line 26 so that the lower portion 24 l of the counterweight 24 is loosely engaged in the aperture 18 a. once the apparatus 10 has been set plumb, the counterweight 24 remains in the aperture 18 a in the bracket 18 so that it can be checked for accuracy during use. use of a plumb line 26 that extends the axial length of the pole 12 gives the apparatus 10 the potential to be more accurate as it is plumbed over a longer distance (e.g. 8 to 10 feet or 2.4 to 3 meters) than conventional apparatus. referring now to fig. 6 , there are shown views of the apparatus 10 with the body 20 a) at the bottom of the pole 12 ; b) in an intermediate position on the pole 12 ; and c) at an upper end of the pole 12 . once the apparatus 10 has been set plumb as described above, the counterweight 24 is used to balance the weight of the body 20 . the counterweight 24 is pulled up to the upper end 12 u of the pole 12 and the body 20 positioned at the lower end 12 l of the pole 12 (as shown in fig. 6 a ). the plumb line 26 is then attached to the body 20 , typically by tying. the counterweight 24 is thus used to balance the body 20 and saves the motor and gear assembly therein from wear during use. additionally, the counterweight 24 will also help to reduce the drain on a battery or the like used to power the motor and gear assembly, as the counterweight 24 aids in movement of the body 20 and thus reduces the amount of power drain from the battery. if the apparatus 10 requires to be checked for accuracy (i.e. whether it is plumb), the body 20 is raised to the upper end 12 u of the pole 12 ( fig. 6 c ) the counterweight 24 is thus located within the bracket 18 u and the accuracy of the apparatus 10 can thus be checked and adjusted if required, as described above. referring particularly to fig. 2 , the body 20 includes a laser head 30 . laser head 30 includes a laser, such as a laser diode or the like, that is used to emit a beam of light. laser light is very coherent, even after travelling long distances. the laser head 30 is preferably interchangeable so that a variety of different types of lasers may be used for different purposes; that is one for longer distances, one for flat (horizontal) beams, etc. it will be appreciated that the laser head 30 can be changed so that the laser beam is a different colour. thus, a first apparatus 10 can be used in the same vicinity as a second apparatus 10 for a different purpose without affecting one another by changing the colour of the beam. alternatively, the laser head 30 may be provided with two or more lasers that can be operated independently of one another (e.g. they can be provided in a carousel-type arrangement). thus, two or more different coloured or types of laser can be selected without having to change the laser head 30 . laser head 30 is mounted to the body 20 using a mounting plate 32 to facilitate rotational movement thereof. the laser head 30 can be rotated around a substantially horizontal axis, as indicated by arrow 34 . plate 32 can be freely rotated so that the light emitted by the laser can define an arc or a circle, for example. optionally, the laser head 30 can be tilted to allow for variations in the diameter of the circle, arc or the like. it will be appreciated that rotation of the laser head 30 about the horizontal axis may be remotely controlled (e.g. by providing the head 30 with a motor and/or gear assembly or the like). plate 32 is advantageously provided with indication means 36 that allows a user to set the laser head 30 at angles between 0 and 360. the indication means 36 preferably comprise radial lines that are spaced around the circumference of plate 32 at various angles. it is also advantageous for the plate 32 to include a locking means (not shown), e.g. a grub screw or the like, to allow the plate 32 to be set at a particular angle (e.g. 45). plate 32 is mounted to body 20 using a swivel 38 that allows the laser head 30 to be rotated about a substantially vertical axis, as indicated by arrow 40 . swivel 38 preferably allows the head 30 to rotate freely so that the beam emitted by the laser can be used to provide a level on all surrounding walls. swivel 38 may also be provided with a locking means (not shown) to prevent rotation thereof. again, rotation of the swivel 38 and thus the laser head 30 about the vertical axis can be remotely controlled (e.g. by motorising the swivel 38 ). the movement of body 20 , and other functions of the apparatus 10 , are preferably remotely controlled. referring to fig. 5 there is shown a second embodiment of apparatus 100 . apparatus 100 is similar to apparatus 10 (like features being designated with the same reference numerals pre-fixed 1 ), but body 120 is configured for manual operation. in the embodiment shown in fig. 5 , body 120 is provided with a locking means 120 l, that may comprise a grub screw, nut and bolt or the like. the locking means 120 l is tightened to lock the body 120 on the pole 112 at the required location. for example, where a grub screw is used, the screw is rotated until one end of the screw engages the pole 112 , thus locking the body 120 in position. alternatively, if a nut and bolt are used, the body 120 may be provided with a clamp (not shown) so that tightening of the nut and bolt tightens the clamp on the pole 112 . the apparatus 100 is set up and used in a similar way as apparatus 10 , and thus has the same advantages. it should be noted that the mounting plate 32 and/or swivel 38 may be motorised. this would allow the plate 32 and/or swivel 38 to be rotated fast enough to facilitate a substantially continuous line to be shown on the wall surface or the like. modifications and improvements may be made to the foregoing without departing from the scope of the present invention.
|
067-411-666-536-475
|
US
|
[
"US",
"WO",
"AU",
"EP",
"JP",
"CA"
] |
A61K31/706,A61K31/70,A61K31/7068,C07D515/22,C07H19/12,C07H19/04,A61K47/30,A61P1/16,A61P31/12,A61P31/14,A61P31/18,A61P31/20,A61P35/00,A61P35/02,A61P43/00,C07H19/23,A61K31/7072,A61K31/53,C07D405/02
| 2002-09-24T00:00:00 |
2002
|
[
"A61",
"C07"
] |
1,3,5-triazines for treatment of viral diseases
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the present invention provides compounds and methods for treatment of viral diseases and cancer.
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1. a method for treating human immuno-deficiency virus (hiv) comprising administering to a subject in need of such treatment a therapeutically effective amount of a compound having the formula: wherein r 9 and r 10 are members independently selected from h, substituted or unsubstituted alkyl and acyl; r 3 is h; r 4 is h; r 5 is or 14 , wherein r 14 is a member selected from h and unsubstituted alkyl; r 6 is or 14 , wherein r 14 is a member selected from h, substituted or unsubstituted alkyl and p(o)(or 17 )(or 17 ), wherein each r 17 is independently selected from h, substituted alkyl, substituted or unsubstituted alkyloxy and substituted or unsubstituted phenyl; and r 8 is selected from h and unsubstituted alkyl. 2. the method of claim 1 , wherein said compound is given orally. 3. the method of claim 2 , wherein said compound is an enteric formulation. 4. the method of claim 3 , wherein said compound is delivered in an oral osmotic drug delivery device. 5. the method of claim 1 , wherein the hiv is resistant to nucleotide reverse transcriptase inhibitors. 6. the method of claim 1 , comprising administering to a subject in need of such treatment a therapeutically effective amount of a compound having the formula: 7. the method of claim 1 , comprising administering to a subject in need of such treatment a therapeutically effective amount of a compound having the formula: 8. the method of claim 1 , wherein r 6 has the formula: in which r 22 is a member selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl; l is a linker selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl; and ar is a substituted or unsubstituted aryl. 9. the method of claim 8 , wherein l comprises a moiety that is cleaved in vivo after entry of said compound into a cell. 10. the method of claim 1 , wherein r 6 has the formula: in which r 22 is a member selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl; l is a linker selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl; and n is an integer from 1 to 30. 11. the method of claim 10 , wherein l comprises a moiety that is cleaved in vivo after entry of said compound into a cell. 12. the method of claim 1 , wherein the compound is administered in combination with another antiviral drug. 13. the method of claim 12 , wherein the antiviral drug is a member selected from the group consisting of acyclovir, amantadine azidothymidine (azt or zidovudine), ribavirin, amantadine, vidarabine and vidarabine monohydrate (adenine arabinoside, ara-a). 14. the method of claim 1 , wherein the compound has the formula:
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cross-reference to related applications this application is a divisional application of u.s. application 10/670,915, filed sep. 24, 2003 currently pending, which is a non-provisional filing of united states provisional application no. 60/413,337, filed sep. 24, 2002, the disclosure of which is incorporated herein by reference in its entirety for all purposes. background of the invention rna viral diseases are responsible for the vast majority of viral morbidity and mortality of viral diseases of mankind, including aids, hepatitis, rhinovirus infections of the respiratory tract, flu, measles, polio and others. there are a number of chronic persistent diseases caused by rna or dna viruses that replicate through an rna intermediate which are difficult to treat, such as hepatitis b and c, and t-cell human leukemia. many common human diseases are caused by rna viruses that are replicated by a viral encoded rna replicase. included in this group are influenza (zurcher, et al., j. gen. virol. 77:1745 (1996), dengue fever (becker, virus - genes 9:33 (1994), and rhinovirus infections (horsnell, et al., j. gen. virol., 76:2549 (1995). important rna viral diseases of animals include feline leukemia and immunodeficiency, visna maedi of sheep, bovine viral diarrhea, bovine mucosal disease, and bovine leukemia. although some vaccines are available for dna viruses, diseases such as hepatitis b are still prevalent. hepatitis b is caused by a dna virus that replicates its genome through a rna intermediate (summers and mason, cell 29:4003 (1982). while an effective vaccine exists as a preventive, there is no efficacious treatment for chronic persistent hbv infection. chain terminating nucleoside analogs have been used extensively for the treatment of infections by dna viruses and retroviruses. these analogs are incorporated into dna by dna polymerases or reverse transcriptases. once incorporated, they cannot be further extended and thus terminate dna synthesis. unfortunately, there is immediate selective pressure for the development of resistance against such chain terminating analogs that results in development of mutations in the viral polymerase that prevent incorporation of the nucleoside analog. an alternative strategy is to utilize mutagenic deoxyribonucleosides (mdrn) or mutagenic ribonucleosides (mrn) that are preferentially incorporated into a viral genome. mdrn are incorporated into dna by viral reverse transcriptase or by a dna polymerase enzyme. mrn are incorporated into viral rnas by viral rna replicases. as a result, the mutations in the viral genome are perpetuated and accumulated with each viral replication cycle. with each cycle of viral infection, there ensues a chain like increase in the number of mutations in the viral genome. eventually the number of mutations in each viral genome is so large that no active virally encoded proteins are produced. 5-aza-2′-deoxycytidine (5-aza-dc) is an antineoplastic agent that has been tested in patients with leukemia and is thought to act predominantly by demethylating dna. 5-aza-cytidine (5-aza-c) has also been used to treat patients with leukemia. methylation is thought to silence tumor growth suppressor and differentiation genes. interestingly deamination of 5-aza-dc to 5-aza-2′-deoxyuridine (5-aza-du) has been shown to result in loss of antineoplastic activity (see e.g., momparler, et al., leukemia. 11:1-6 (1997)). 5-aza-cytidine (5-aza-c) has also been used to treat patients with leukemia. both 5-aza-c and 5-aza-dc were shown to inhibit hiv replication in vitro, although the mechanism of action was not determined (see e.g., bouchard et al, antimicrob. agents chemother. 34: 206-209 (2000)). more recently, 5-aza-c has been shown to be mutagenic to foot-and-mouth disease virus (see e.g., sierra et al., j. virol. 74(18): 8316-8323 (2000)). both 5-aza-c and 5-aza-dc are unstable compounds. 5-aza-dc is rapidly degraded upon reconstitution. at ph 7.0, a 10% degradation occurs at temperatures of 25° c. and 50° c. after 5 and 0.5 hours, respectively (see e.g., van groeningen et al., cancer res. 46:4831-4836 (1986)). thus, therapeutic use of 5-aza-c and 5-aza-dc is limited for treatment of both viral diseases and cancer. the present invention solves this and other problems. brief summary of the invention the present invention provides a genus of nucleoside or nucleotide analogues and method of using the analogues as antiviral and anti-cancer chemotherapeutic agents. thus, in a first aspect, there is provided a compound according to formula i: in formula i, the dashed circle indicates that the ring system may include one or more double bonds at any position, such that the valence of the intra-annular atoms is satisfied. the ring system may be aromatic (e.g., heteroaryl) or non-aromatic. the substituents r 2 , r 7 , r 8 are present or absent as dictated by the application of the laws of valency to a selected ring structure. the symbol y represents c, ch or n, and the symbol z represents c, ch or b. r 1 is a member selected from h, acyl, or 9 , sr 9 , nr 9 nhr 10 , nr 9 r 10 , ═o and ═nr 9 , in which r 9 and r 10 are members independently selected from h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl and substituted or unsubstituted aryl. the symbol r 2 represents a substituent that is a member selected from h, acyl, substituted or unsubstituted alkyl, or 11 , sr 11 , nr 11a , nr 12a , halogen, and ═o. the symbol r 11 represents a member selected from h, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, or substituted or unsubstituted heteroaryl. r 11a and r 12a are members independently selected from h, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. r 3 is a member selected from h, acyl, substituted or unsubstituted alkyl, nr 12 r 13 , nr 12 or 13 , sr 12 , (═o) and or 12 . the symbols r 12 and r 13 represent members independently selected from h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. r 4 and r 4a are members independently selected from h, halogen, ome and oh. in a preferred embodiment, the halogen is f. r 5 and r 6 are members independently selected from h, and or 14 . the symbol r 14 represents h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl, or substituted or unsubstituted aryl and p(o)(r 15 )(r 16 ). r 15 and r 16 are independently selected from or 17 , nr 17 r 18 , substituted or unsubstituted alkyl and substituted or unsubstituted nucleosides. r 17 and r 18 are independently selected from h, ch 2 ch cn, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. a member selected from r 5 and r 3 ; r 6 and r 3 ; and r 15 and r 16 together with the atoms to which they are attached, are optionally joined to form a ring system selected from substituted or unsubstituted cycloalkyl and substituted or unsubstituted heterocycloalkyl. in an exemplary embodiment, the ring system is a 5 or 6 membered ring system. r 7 and r 8 are independently selected from h, acyl, substituted or unsubstituted alkyl. r 1 and r 8 , together with the atoms to which they are attached are optionally joined into a ring system selected from substituted or unsubstituted cycloalkyl and substituted or unsubstituted heterocycloalkyl. in another aspect of the present invention, the nucleoside and nucleotide analogues (e.g., the compounds of formula i) of the present invention are used for treating a viral disease by administering a therapeutically effective amount of a compound of formula i to a patient with a viral disease. in some embodiments, the compounds are given orally. in other embodiments, the compound is given in an enteric formulation. in a further embodiment, the compound is delivered in an oral osmotic drug delivery device. when the compounds are given orally, it is generally preferred that they have a bioavailability that is greater than about 15%, more preferably greater than about 20% of the administered dose. in an exemplary embodiment, the compound is formulated as an acid addition salt, e.g. a quaternary ammonium salt. the salt is generally formed by contacting the compound with a mineral or an organic acid. in a preferred embodiment, the acid is a carboxylic acid, such as palmitic acid. the viral disease can be a viral disease caused by an rna virus, a dna virus, or a retrovirus. in some embodiments, the viral disease is caused by hiv. in a further embodiment, the hiv strain is resistant to nucleotide reverse transcriptase inhibitors or other treatments of hiv infection, including non-nucleoside reverse transcriptase inhibitors, or protease inhibitors. in other embodiments, the viral disease is caused by a virus of the flaviviridae family. in a further embodiment the viral disease is hepatitis c. in other embodiments, the viral disease is caused by a virus of the paramyxoviridae family. in a further aspect, the virus is hepatitis b virus or smallpox/vaccinia virus. in another aspect of the present invention the compounds of formula i are used to treat cancer, e.g., hematopoetic cancers. other aspects, objects and advantages of the present invention will be apparent from the detailed description that follows. brief description of the drawings fig. 1 is an illustration of the hydrophobic-hydrophobic stacking interactions of selected compositions of the invention. fig. 2 is an illustration of the complexes of the invention formed between the pharmacophore modified with a hydrophobic modifying group and a poly-ion. fig. 3 is an illustration of the complexes of the invention formed between the pharmacophore modified with a hydrophobic modifying group and a dendrimeric poly-ion. fig. 4 depicts the ec 50 values for 5-aza-dc, dhadc and 5-me-dhadc against wild-type hiv virus. the experiments were carried out in mt-2 cells infected with hiv strain lai. fig. 5 is an illustration of compounds 1-4. fig. 6 is an exemplary synthetic scheme for compounds 7 and 8. fig. 7 is an exemplary synthetic scheme for compounds 9 and 10. fig. 8 is an exemplary synthetic scheme for compounds 9, and 11-14. fig. 9 is an exemplary synthetic scheme for compounds 14-18. fig. 10 is an exemplary synthetic scheme for compounds 20-21. fig. 11 is an exemplary synthetic scheme for compounds 20-21. fig. 12 is an exemplary synthetic scheme for a compound of the invention including a modified phosphodiester group. fig. 13 is an exemplary synthetic scheme for a compound of the invention including a modified phosphodiester group derivatized with a hydrophobic moiety. fig. 14 is a retrosynthetic scheme for preparing a compound of the invention. fig. 15 is an exemplary synthetic scheme for compounds 23, 24 and 26. detailed description of the invention introduction the present invention is directed to a method of inducing viral mutagenesis, using hydrolytically stable derivatives and formulations of 5-aza-cytidine, 5-aza-2′-deoxycytidine and derivatives and variants thereof, which is useful in cell culture as well as in therapy for animals and humans. this method is advantageous in that it is useful against dna or rna viruses (i.e., viruses that have dna or rna genomes). in one embodiment, the methods of the invention are advantageous when used to target rna viruses (viruses with an rna genome), and retroviruses or other viruses otherwise replicated by an rna intermediate. in another embodiment, the methods of the invention are advantageous for targeting dna viruses such as hepatitis b virus, herpes viruses, and papilloma viruses. without being held to a mechanism of action, in one embodiment, the methods of the invention utilize miscoding nucleosides and nucleotides that are incorporated into both viral encoded and cellular encoded viral genomic nucleic acids, thereby causing miscoding in progeny copies of the genomic virus, e.g., by tautomerism, which promotes base mispairing (see, e.g., moriyama et al., nucleic acids symposium 42: 131-132 (1999); robinson et al., biochemistry 37: 10897-10905 (1998); anensen et al., mutation res. 476: 99-107 (2001); lutz et al., bioorganic & medicinal chem. letts. 8: 499-504 (1998); and klungland et al., toxicology letts. 119: 71-78 (2001)). the virus may be one in which the viral genomic nucleic acid is integrated into the cellular genome. examples of viruses that integrate their cellular genome include, but are not limited to, retroviruses. in one particularly preferred embodiment, the virus is hiv. other preferred viruses include hiv-1, hiv-2, htlv-1, htlv-ii, and siv. in another embodiment, the virus is a dna virus such as hepatitis b virus, herpes viruses (e.g., hsv, cmv, ebv), smallpox virus, or papilloma virus (e.g., hpv). alternatively, the viral genome can be episomal. these include many human and animal pathogens, e.g., flaviviruses such as dengue fever, west nile virus, and yellow fever, pestiviruses (a genus of the flaviviridae family) such as bvdv (bovine viral diarrhea virus), hepatitis c viruses (also a genus of the flaviviridae family), filoviruses such as ebola virus, influenza viruses, parainfluenza viruses, including respiratory syncytial virus, measles, mumps, the picornaviruses, including the echoviruses, the coxsackieviruses, the polioviruses, the togaviruses, including encephalitis, coronoviruses, rubella, bunyaviruses, reoviruses, including rotaviruses, rhabdoviruses, arenaviruses such as lymphocytic choriomeningitis as well as other rna viruses of man and animals. retroviruses that can be targeted include the human t-cell leukemia (htlv) viruses such as htlv-1 and htlv-2, adult t-cell leukemia (atl), the human immunodeficiency viruses such as hiv-1 and hiv-2 and simian immunodeficiency virus (siv). in some embodiments, the hiv virus is resistant to non-nucleoside reverse transcriptase inhibitors. in certain embodiments, the virus is hepatitis a or hepatitis b. see, e.g., fields virology (3rd ed. 1996). further information regarding viral diseases and their replication can be found in white and fenner, medical virology 4th ed. academic press (1994) and in principles and practice of clinical virology, ed. zuckerman, banatvala and pattison, john wiley and sons (1994). in addition, the compounds of the invention can be used to treat cancer. assays for detecting the mutagenic potential of a nucleoside or nucleotide analog are provided (see, e.g., example 1). in the assays, the nucleoside or nucleotide analog is incorporated into a viral nucleic acid in the presence of a nucleic acid template, the nucleic acid synthesized by a cellular or viral polymerase, and a determination is made regarding whether the incorporation causes a mutation in a progeny virus. optionally, naturally occurring (i.e., g, a, u, and/or c) nucleotides are also incorporated into the nucleic acid polymer. the method optionally comprises comparing the rate of incorporation of the nucleoside or nucleotide analog and any naturally occurring ribonucleoside in the assay into the nucleic acid. for additional examples of assays, see, e.g., u.s. pat. nos. 6,132,776, 6,130,036, 6,063,628, and 5,512,431 and patent applications u.s. ser. no. 10/226,799 and 60/314,728, which are incorporated herein by reference in their entirety. exemplary compounds for use in the methods of the invention include 5-aza-cytidine, 5-aza-2′-deoxycytidine, and derivatives and variants thereof. definitions where substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents which would result from writing the structure from right to left, e.g., —ch 2 o— is intended to also recite —och 2 —; —nhs(o) 2 — is also intended to represent —s(o) 2 hn—, etc. as used herein, “linking member” refers to an alkylene unit or a covalent chemical bond that includes at least one heteroatom. exemplary linking members include —c(o)nh—, —c(o)o—, —nh—, —s—, —o—, and the like. the term “targeting group” is intended to mean a moiety that is (1) able to direct the entity to which it is attached (e.g., therapeutic agent or marker) to a target region, e.g. cell; or (2) is preferentially activated at a target region, for example a region of viral infection. the targeting group can be a small molecule, which is intended to include both non-peptides and peptides. the targeting group can also be a macromolecule, which includes saccharides, lectins, receptors, ligand for receptors, proteins such as bsa, antibodies, and so forth. the term “alkyl,” by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain, or cyclic hydrocarbon radical, or combination thereof, which may be fully saturated, mono- or poly-unsaturated and can include di- and multivalent radicals, having the number of carbon atoms designated (i.e. c 1 -c 10 means one to ten carbons). examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. an unsaturated alkyl group is one having one or more double bonds or triple bonds. examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers. the term “alkyl,” unless otherwise noted, is also meant to include those derivatives of alkyl defined in more detail below, such as “heteroalkyl.” alkyl groups, which are limited to hydrocarbon groups, are termed “homoalkyl”. the term “alkylene” by itself or as part of another substituent means a divalent radical derived from an alkane, as exemplified, but not limited, by —ch 2 ch 2 ch 2 ch 2 —, and further includes those groups described below as “heteroalkylene.” typically, an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred in the present invention. a “lower alkyl” or “lower alkylene” is a shorter chain alkyl or alkylene group, generally having eight or fewer carbon atoms. the terms “alkoxy,” “alkylamino” and “alkylthio” (or thioalkoxy) are used in their conventional sense, and refer to those alkyl groups attached to the remainder of the molecule via an oxygen atom, an amino group, or a sulfur atom, respectively. “acyl” refers to a moiety that is a residue of a carboxylic acid from which an oxygen atom is removed, i.e., —c(o)r, in which r is substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. the term “heteroalkyl,” by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain, or cyclic hydrocarbon radical, or combinations thereof, consisting of the stated number of carbon atoms and at least one heteroatom selected from the group consisting of o, n, si and s, and wherein the nitrogen and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized. the heteroatom(s) o, n and s and si may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. examples include, but are not limited to, —ch 2 —ch 2 —o—ch 3 , —ch 2 —ch 2 —nh—ch 3 , —ch 2 —ch 2 —n(ch 3 )—ch 3 , —ch 2 —s—ch 2 —ch 3 , —ch 2 —ch 2 , —s(o)—ch 3 , —ch 2 —ch 2 —s(o) 2 —ch 3 , —ch═ch—o—ch 3 , —si(ch 3 ) 3 , —ch 2 —ch═n—och 3 , and —ch═ch—n(ch 3 )—ch 3 . up to two heteroatoms may be consecutive, such as, for example, —ch 2 —nh—och 3 and —ch 2 —o—si(ch 3 ) 3 . similarly, the term “heteroalkylene” by itself or as part of another substituent means a divalent radical derived from heteroalkyl, as exemplified, but not limited by, —ch 2 —ch 2 —s—ch 2 —ch 2 — and —ch 2 —s—ch 2 —ch 2 —nh—ch 2 —. for heteroalkylene groups, heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). still further, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. for example, the formula —c(o) 2 r′— represents both —c(o) 2 r′— and —r′c(o) 2 —. the terms “cycloalkyl” and “heterocycloalkyl”, by themselves or in combination with other terms, represent, unless otherwise stated, cyclic versions of “alkyl” and “heteroalkyl”, respectively. additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl, 2-piperazinyl, and the like. the term “aryl” means, unless otherwise stated, a polyunsaturated, typically aromatic, hydrocarbon substituent, which can be a single ring or multiple rings (up to three rings), which are fused together or linked covalently. the term “heteroaryl” refers to aryl groups (or rings) that contain from zero to four heteroatoms selected from n, o, and s, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. a heteroaryl group can be attached to the remainder of the molecule through a heteroatom. non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl, and 6-quinolyl. substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below. for brevity, the term “aryl” when used in combination with other terms (e.g., aryloxy, arylthioxy, arylalkyl) includes both aryl and heteroaryl rings as defined above. thus, the term “arylalkyl” is meant to include those radicals in which an aryl group is attached to an alkyl group (e.g., benzyl, phenethyl, pyridylmethyl and the like) including those alkyl groups in which a carbon atom (e.g., a methylene group) has been replaced by, for example, an oxygen atom (e.g., phenoxymethyl, 2-pyridyloxymethyl, 3-(1-naphthyloxy)propyl, and the like). the terms “halo” or “halogen,” by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. additionally, terms such as “haloalkyl,” are meant to include monohaloalkyl and polyhaloalkyl. for example, the term “halo(c 1 -c 4 )alkyl” is mean to include, but not be limited to, trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like. substituents for the alkyl and heteroalkyl radicals (including those groups often referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) can be one or more of a variety of groups selected from, but not limited to: —or′, ═o, ═nr′, ═n—or′, —nr′r″, —sr′, -halogen, —sir′r″r′″, —oc(o)r′, —c(o)r′, —co 2 r′, —conr′r″, —oc(o)nr′r″, —nr″c(o)r′, —nr′—c(o)nr″r′″, —nr″c(o) 2 r′, —nr—c(nr′r″r′″)═nr″″, —nr—c(nr′r″)═nr′″, —s(o)r′, —s(o) 2 r′, —s(o) 2 nr′r″, —nrso 2 r′, —cn and —no 2 in a number ranging from zero to (2m′+1), where m′ is the total number of carbon atoms in such radical. r′, r″, r′″ and r″″ each preferably independently refer to hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, e.g., aryl substituted with 1-3 halogens, substituted or unsubstituted alkyl, alkoxy or thioalkoxy groups, or arylalkyl groups. when a compound of the invention includes more than one r group, for example, each of the r groups is independently selected as are each r′, r″, r′″ and r″″ groups when more than one of these groups is present. when r′ and r″ are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 5-, 6-, or 7-membered ring. for example, —nr′r″ is meant to include, but not be limited to, 1-pyrrolidinyl and 4-morpholinyl. from the above discussion of substituents, one of skill in the art will understand that the term “alkyl” is meant to include groups including carbon atoms bound to groups other than hydrogen groups, such as haloalkyl (e.g., —cf 3 and —ch 2 cf 3 ) and acyl (e.g., —c(o)ch 3 , —c(o)cf 3 , —c(o)ch 2 och 3 , and the like). similar to the substituents described for the alkyl radical, substituents for the aryl and heteroaryl groups are varied and are selected from, for example: halogen, —or′, ═o, ═nr′, ═n—or′, —nr′r″, —sr′, -halogen, —sir′r″r′″, —oc(o)r′, —c(o)r′, —co 2 r′, —conr′r″, —oc(o)nr′r″, —nr″c(o)r′, —nr′—c(o)nr″r′″, —nr″c(o) 2 r′, —nr—c(nr′r″)═nr′″, —s(o)r′, —s(o) 2 r′, —s(o) 2 nr′r″, —nrso 2 r′, —cn and —no 2 , —r′, —n 3 , —ch(ph) 2 , fluoro(c 1 -c 4 )alkoxy, and fluoro(c 1 -c 4 )alkyl, in a number ranging from zero to the total number of open valences on the aromatic ring system. when a compound of the invention includes more than one r group, for example, each of the r groups is independently selected as are each r′, r″, r′″ and r″″ groups when more than one of these groups is present. two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -t-c(o)—(crr′) q —u—, wherein t and u are independently —nr—, —o—, —crr′— or a single bond, and q is an integer of from 0 to 3. alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -a-(ch 2 ) r —b—, wherein a and b are independently —crr′—, —o—, —nr—, —s—, —s(o)—, —s(o) 2 —, —s(o) 2 nr′— or a single bond, and r is an integer of from 1 to 4. one of the single bonds of the new ring so formed may optionally be replaced with a double bond. alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula —(crr′) s —x—(cr″r′″) d —, where s and d are independently integers of from 0 to 3, and x is —o—, —nr′—, —s—, —s(o)—, —s(o) 2 —, or —s(o) 2 nr′—. the substituents r, r′, r″ and r′″ are preferably independently selected from hydrogen or substituted or unsubstituted (c 1 -c 6 )alkyl. as used herein, the term “heteroatom” includes oxygen (o), nitrogen (n), sulfur (s) and silicon (si). “moiety” refers to the radical of a molecule that is attached to another moiety. the symbol “r” is a general abbreviation that represents a substituent group that is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocyclyl groups. “reactive functional group,” as used herein refers to groups including, but not limited to, olefins, acetylenes, alcohols, phenols, ethers, oxides, halides, aldehydes, ketones, carboxylic acids, esters, amides, cyanates, isocyanates, thiocyanates, isothiocyanates, amines, hydrazines, hydrazones, hydrazides, diazo, diazonium, nitro, nitriles, mercaptans, sulfides, disulfides, sulfoxides, sulfones, sulfonic acids, sulfinic acids, acetals, ketals, anhydrides, sulfates, sulfenic acids, isonitriles, amidines, imides, imidates, nitrones, hydroxylamines, oximes, hydroxamic acids, thiohydroxamic acids, allenes, ortho esters, sulfites, enamines, ynamines, ureas, pseudoureas, semicarbazides, carbodiimides, carbamates, imines, azides, azo compounds, azoxy compounds, and nitroso compounds. reactive functional groups also include those used to prepare bioconjugates, e.g., n-hydroxysuccinimide esters, maleimides and the like. methods to prepare each of these functional groups are well known in the art and their application to or modification for a particular purpose is within the ability of one of skill in the art (see, for example, sandler and karo, eds. o rganic f unctional g roup p reparations , academic press, san diego, 1989). “protecting group,” as used herein refers to a portion of a substrate that is substantially stable under a particular reaction condition, but which is cleaved from the substrate under a different reaction condition. a protecting group can also be selected such that it participates in the direct oxidation of the aromatic ring component of the compounds of the invention. for examples of useful protecting groups, see, for example, greene et al., p rotective g roups in o rganic s ynthesis , john wiley & sons, new york, 1991. as used herein the term “nucleoside,” includes both the naturally occurring nucleosides and modifications thereof. modifications include, but are not limited to, those providing chemical groups that incorporate additional charge, polarizability, hydrogen bonding, and electrostatic interaction to the nucleosides. such modifications include, but are not limited to, peptide nucleic acids (pnas), 2′-position sugar modifications, 5-position pyrimidine modifications, 8-position purine modifications, modifications at exocyclic amines, substitution of 4-thiouridine, substitution of 5-bromo or 5-iodo-uracil; backbone modifications, methylations, isobases, such as isocytidine and isoguanidine and the like. “nucleosides” can also include non-natural bases, such as, for example, nitroindole. modifications can also include derivitization with a quencher, a fluorophore or another moiety. “nucleotides” are phosphate esters of nucleosides. many modifications of nucleosides can be also be practiced on nucleotides. the symbol , whether utilized as a bond or displayed perpendicular to a bond indicates the point at which the displayed moiety is attached to the remainder of the molecule, solid support, etc. the term “pharmaceutically acceptable salts” includes salts of the active compounds prepared with relatively nontoxic acids or bases, depending on the particular substituents found on the compounds described herein. when compounds of the present invention contain relatively acidic functionalities, base addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired base, either neat or in a suitable inert solvent. examples of pharmaceutically acceptable base addition salts include sodium, potassium, calcium, ammonium, organic amino, or magnesium salt, or a similar salt. when compounds of the present invention contain relatively basic functionalities, acid addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired acid, either neat or in a suitable inert solvent. examples of pharmaceutically acceptable acid addition salts include those derived from inorganic acids like hydrochloric, hydrobromic, nitric, carbonic, monohydrogencarbonic, phosphoric, monohydrogenphosphoric, dihydrogenphosphoric, sulfuric, monohydrogensulfuric, hydriodic, or phosphorous acids and the like, as well as the salts derived from relatively nontoxic organic acids like acetic, propionic, isobutyric, maleic, malonic, benzoic, succinic, suberic, fumaric, lactic, mandelic, phthalic, benzenesulfonic, p-tolylsulfonic, citric, tartaric, methanesulfonic, palmitic and the like. also included are salts of amino acids such as arginate and the like, and salts of organic acids like glucuronic or galactunoric acids and the like (see, for example, berge et al., “pharmaceutical salts”, journal of pharmaceutical science, 1977, 66, 1-19). certain specific compounds of the present invention contain both basic and acidic functionalities that allow the compounds to be converted into either base or acid addition salts. the neutral forms of the compounds are preferably regenerated by contacting the salt with a base or acid and isolating the parent compound in the conventional manner. the parent form of the compound differs from the various salt forms in certain physical properties, such as solubility in polar solvents, but otherwise the salts are equivalent to the parent form of the compound for the purposes of the present invention. in addition to salt forms, the present invention provides compounds, which are in a prodrug form. prodrugs of the compounds described herein are those compounds that readily undergo chemical changes under physiological conditions to provide the compounds of the present invention. additionally, prodrugs can be converted to the compounds of the present invention by chemical or biochemical methods in an ex vivo environment. for example, prodrugs can be slowly converted to the compounds of the present invention when placed in a transdermal patch reservoir with a suitable enzyme or chemical reagent. certain compounds of the present invention can exist in unsolvated forms as well as solvated forms, including hydrated forms. in general, the solvated forms are equivalent to unsolvated forms and are encompassed within the scope of the present invention. certain compounds of the present invention may exist in multiple crystalline or amorphous forms. in general, all physical forms are equivalent for the uses contemplated by the present invention and are intended to be within the scope of the present invention. certain compounds of the present invention possess asymmetric carbon atoms (optical centers) or double bonds; the racemates, diastereomers, geometric isomers and individual isomers are encompassed within the scope of the present invention. the compounds of the invention may be prepared as a single isomer (e.g., enantiomer, cis-trans, positional, diastereomer) or as a mixture of isomers. in a preferred embodiment, the compounds are prepared as substantially a single isomer. methods of preparing substantially isomerically pure compounds are known in the art. for example, enantiomerically enriched mixtures and pure enantiomeric compounds can be prepared by using synthetic intermediates that are enantiomerically pure in combination with reactions that either leave the stereochemistry at a chiral center unchanged or result in its complete inversion. alternatively, the final product or intermediates along the synthetic route can be resolved into a single stereoisomer. techniques for inverting or leaving unchanged a particular stereocenter, and those for resolving mixtures of stereoisomers are well known in the art and it is well within the ability of one of skill in the art to choose and appropriate method for a particular situation. see, generally, furniss et al. (eds.), v ogel's e ncyclopedia of p ractical o rganic c hemistry 5 th e d ., longman scientific and technical ltd., essex, 1991, pp. 809-816; and heller, acc. chem. res. 23: 128 (1990). the compounds of the present invention may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. for example, the compounds may be radiolabeled with radioactive isotopes, such as for example tritium ( 3 h), iodine-125 ( 125 i) or carbon-14 ( 14 c). all isotopic variations of the compounds of the present invention, whether radioactive or not, are intended to be encompassed within the scope of the present invention. the term “viral disease” refers to a condition caused by a virus. a viral disease can be caused by a dna virus, an rna virus, or by a retrovirus. in some embodiments, viral diseases include virus of the flavaviridae family. the family flaviviridae includes the three genera of the family, the flaviviruses, the pestiviruses (e.g., bvdv), and the hepatitis c viruses (e.g., hcv). the family paramyxoviridae includes without limitation, parainfluenza virus, respiratory syncytial virus, newcastle disease virus, mumps virus and measles virus. dna virus includes the family poxyiridae. poxyiridae family members include vaccinia virus and variola virus, which can cause small pox. dna virus includes, but is not limited to, the hepatitis b virus, which replicates its genome through an rna intermediate. retrovirus includes hiv-1, hiv-2, htlv-1, htlv-ii, and siv. in a preferred embodiment, the compounds of the invention are used to treat an hiv strain that is resistant to nucleoside reverse transcriptase inhibitors (nrti). the four “naturally occurring nucleotides” in rna and dna contain adenine, guanine, uracil, thymine or cytosine. nucleotides which are complementary to one another are those that tend to form complementary hydrogen bonds between them and, specifically, the natural complement to a is u or t, the natural complement to u is a, the natural complement to t is a, the natural complement to c is g and the natural complement to g is c. a “nucleic acid” is a deoxyribonucleotide or ribonucleotide polymer in either single- or double-stranded form, and unless otherwise limited, encompasses analogs of natural nucleotides. a “nucleoside analog” as used herein is defined in more detail below and includes analogs of ribonucleosides and deoxyribonucleosides and the mono- di-, an triphosphates (nucleotides) thereof. as described above, they can be naturally occurring or non-naturally occurring, and derived from natural sources or synthesized. these monomeric units are nucleoside analogs (or “nucleotide” analogs if the monomer is considered with reference to phosphorylation). for instance, structural groups are optionally added to the sugar or base of a nucleoside for incorporation into an oligonucleotide, such as a methyl or allyl group at the 2′-o position on the sugar, or a fluoro group which substitutes for the 2′-o group, or a bromo group on the nucleoside base. the phosphodiester linkage, or “sugar-phosphate backbone” of the oligonucleotide analog is substituted or modified, for instance with methyl phosphonates or o-methyl phosphates. a “genomic nucleic acid” is a nucleic acid polymer homologous to a nucleic acid which encodes a naturally occurring nucleic acid polymer (rna or dna) packaged by a viral particle. typically, the packaged nucleic acid encodes some or all of the components necessary for viral replication. the genomic nucleic acid optionally includes nucleotide analogs. nucleic acids are homologous when they are derived from a nucleic acid with a common sequence (an “ancestral” nucleic acid) by natural or artificial modification of the ancestral nucleic acid. retroviral genomic nucleic acids optionally encode an rna competent to be packaged by a retroviral particle. such nucleic acids can be constructed by recombinantly combining a packaging site with a nucleic acid of choice. a “virally infected cell” is a cell transduced with a viral nucleic acid. the nucleic acid is optionally incorporated into the cellular genome, or is optionally episomal. the “mutation rate” of a virus or nucleic acid refers to the number of changes occurring upon copying the nucleic acid, e.g., by a polymerase. typically, this is measured over time, i.e., the number of alterations occurring during rounds of copying or generations of virus. a “polymerase” refers to an enzyme (dna or rna polymerase) that produces a polynucleotide sequence, complementary to a pre-existing template polynucleotide (dna or rna). for example, an rna polymerase may be either an rna viral polymerase or replicase or rna cellular polymerase. a “cellular polymerase” is a polymerase derived from a cell. the cell may be prokaryotic or eukaryotic. the cellular rna polymerase is typically an rna polymerase such as pol ii or pol iii. pol ii enzymes are most preferred. a “mammalian rna polymerase ii” is an rna polymerase ii derived from a mammal. a “human rna polymerase ii” is an rna polymerase ii derived from a human. a “murine rna polymerase ii” is an rna polymerase ii derived from a mouse. the polymerase is optionally naturally occurring, or artificially (e.g., recombinantly) produced. a “cell culture” is a population of cells residing outside of an animal. these cells are optionally primary cells isolated from a cell bank, animal, or blood bank, or secondary cells cultured from one of these sources, or long-lived artificially maintained in vitro cultures that are widely available. a “progressive loss of viability” refers to a measurable reduction in the replicative or infective ability of a population of viruses over time. a “viral particle” is a viral particle substantially encoded by an rna virus or a virus with an rna intermediate, such as bvdv, hcv, or hiv. the presence of non-viral or cellular components in the particle is a common result of the replication process of a virus, which typically includes budding from a cellular membrane. an “hiv particle” is a retroviral particle substantially encoded by hiv. the presence of non-hiv viral or cellular components in the particle is a common result of the replication process of hiv, typically including budding from a cellular membrane. in certain applications, retroviral particles are deliberately “pseudotyped” by co-expressing viral proteins from more than one virus (often hiv and vsv) to expand the host range of the resulting retroviral particle. the presence or absence of non-hiv components in an hiv particle does not change the essential nature of the particle, i.e., the particle is still produced as a primary product of hiv replication. where the methods discussed below require sequence alignment, such methods of alignment of sequences for comparison are well known in the art. optimal alignment of sequences for comparison may be conducted by the local homology algorithm of smith and waterman (1981) adv. appl. math. 2: 482; by the homology alignment algorithm of needleman and wunsch (1970) j. mol. biol. 48: 443; by the search for similarity method of pearson and lipman (1988) proc. natl. acad. sci. usa 85: 2444; by computerized implementations of these algorithms (including, but not limited to clustal in the pc/gene program by intelligenetics, mountain view, calif., gap, bestfit, fasta, and tfasta in the wisconsin genetics software package, genetics computer group (gcg), 575 science dr., madison, wis., usa); the clustal program is well described by higgins and sharp (1988) gene, 73: 237-244 and higgins and sharp (1989) cabios 5: 151-153; corpet, et al., (1988) nucleic acids research 16, 10881-90; huang, et al., (1992) computer applications in the biosciences 8, 155-65, and pearson, et al., (1994) methods in molecular biology 24, 307-31. typically, the alignments are visually inspected and refined manually after computer-aided adjustment. a preferred example of algorithm that is suitable for determining percent sequence identity and sequence similarity are the blast and blast 2.0 algorithms, which are described in altschul et al., nuc. acids res. 25:3389-3402 (1977) and altschul et al., j. mol. biol. 215:403-410 (1990), respectively. blast and blast 2.0 are used, with the default parameters described herein, to determine percent sequence identity for the nucleic acids and proteins of the invention. software for performing blast analyses is publicly available through the national center for biotechnology information (http://www.ncbi.nlm.nih.gov/). the blastn program (for nucleotide sequences) uses as defaults a wordlength (w) of 11, an expectation (e) of 10, m=5, n=−4 and a comparison of both strands. for amino acid sequences, the blastp program uses as defaults a wordlength of 3, and expectation (e) of 10, and the blosum62 scoring matrix (see henikoff & henikoff, proc. natl. acad. sci. usa 89:10915 (1989)) alignments (b) of 50, expectation (e) of 10, m=5, n=−4, and a comparison of both strands. as used herein, “cancer” includes solid tumors and hematological malignancies. the former includes cancers such as breast, colon, and ovarian cancers. the latter include hematopoietic malignancies including leukemias, lymphomas and myelomas. this invention provides new effective methods, compositions, and kits for treatment and/or prevention of various types of cancer. hematological malignancies, such as leukemias and lymphomas, are conditions characterized by abnormal growth and maturation of hematopoietic cells. leukemias are generally neoplastic disorders of hematopoietic stem cells, and include adult and pediatric acute myeloid leukemias (aml), chronic myeloid leukemia (cml), acute lymphocytic leukemia (all), chronic lymphocytic leukemia (cll), hairy cell leukemia and secondary leukemia. myeloid leukemias are characterized by infiltration of the blood, bone marrow, and other tissues by neoplastic cells of the hematopoietic system. cll is characterized by the accumulation of mature-appearing lymphocytes in the peripheral blood and is associated with infiltration of bone marrow, the spleen and lymph nodes. specific leukemias include acute nonlymphocytic leukemia, chronic lymphocytic leukemia, acute granulocytic leukemia, chronic granulocytic leukemia, acute promyelocytic leukemia, adult t-cell leukemia, aleukemic leukemia, a leukocythemic leukemia, basophylic leukemia, blast cell leukemia, bovine leukemia, chronic myelocytic leukemia, leukemia cutis, embryonal leukemia, eosinophilic leukemia, gross' leukemia, hairy-cell leukemia, hemoblastic leukemia, hemocytoblastic leukemia, histiocytic leukemia, stem cell leukemia, acute monocytic leukemia, leukopenic leukemia, lymphatic leukemia, lymphoblastic leukemia, lymphocytic leukemia, lymphogenous leukemia, lymphoid leukemia, lymphosarcoma cell leukemia, mast cell leukemia, megakaryocytic leukemia, micromyeloblastic leukemia, monocytic leukemia, myeloblastic leukemia, myelocytic leukemia, myeloid granulocytic leukemia, myelomonocytic leukemia, naegeli leukemia, plasma cell leukemia, plasmacytic leukemia, promyelocytic leukemia, rieder cell leukemia, schilling's leukemia, stem cell leukemia, subleukemic leukemia, and undifferentiated cell leukemia. lymphomas are generally neoplastic transformations of cells that reside primarily in lymphoid tissue. among lymphomas, there are two major distinct groups: non-hodgkin's lymphoma (nhl) and hodgkin's disease. lymphomas are tumors of the immune system and generally are present as both t cell- and as b cell-associated disease. bone marrow, lymph nodes, spleen and circulating cells are all typically involved. treatment protocols include removal of bone marrow from the patient and purging it of tumor cells, often using antibodies directed against antigens present on the tumor cell type, followed by storage. the patient is then given a toxic dose of radiation or chemotherapy and the purged bone marrow is then reinfused in order to repopulate the patient's hematopoietic system. other hematological malignancies include myelodysplastic syndromes (mds), myeloproliferative syndromes (mps) and myelomas, such as solitary myeloma and multiple myeloma. multiple myeloma (also called plasma cell myeloma) involves the skeletal system and is characterized by multiple tumorous masses of neoplastic plasma cells scattered throughout that system. it may also spread to lymph nodes and other sites such as the skin. solitary myeloma involves solitary lesions that tend to occur in the same locations as multiple myeloma. hematological malignancies are generally serious disorders, resulting in a variety of symptoms, including bone marrow failure and organ failure. treatment for many hematological malignancies, including leukemias and lymphomas, remains difficult, and existing therapies are not universally effective. while treatments involving specific immunotherapy appear to have considerable potential, such treatments are limited by the small number of known malignancy-associated antigens. moreover the ability to detect such hematological malignancies in their early stages can be quite difficult depending upon the particular malady. accordingly, there remains a need in the art for improved methods for treatment of hematological malignancies such as b cell leukemias and lymphomas and multiple myelomas. the present invention fulfills these and other needs in the field. other cancers are also of concern, and represent similar difficulties insofar as effective treatment is concerned. such cancers include those characterized by solid tumors. examples of other cancers of concern are skin cancers, including melanomas, basal cell carcinomas, and squamous cell carcinomas. epithelial carcinomas of the head and neck are also encompassed by the present invention. these cancers typically arise from mucosal surfaces of the head and neck and include salivary gland tumors. the present invention also encompasses cancers of the lung. lung cancers include squamous or epidermoid carcinoma, small cell carcinoma, adenocarcinoma, and large cell carcinoma. breast cancer is also included, both invasive breast cancer and non-invasive breast cancer, e.g., ductal carcinoma in situ and lobular neoplasia. the present invention also encompasses gastrointestinal tract cancers. gastrointestinal tract cancers include esophageal cancers, gastric adenocarcinoma, primary gastric lymphoma, colorectal cancer, small bowel tumors and cancers of the anus. pancreatic cancer and cancers that affect the liver are also of concern, including hepatocellular cancer. the present invention also includes treatment of bladder cancer and renal cell carcinoma. the present invention also encompasses prostatic carcinoma and testicular cancer. gynecologic malignancies are also encompassed by the present invention including ovarian cancer, carcinoma of the fallopian tube, uterine cancer, and cervical cancer. treatment of sarcomas of the bone and soft tissue are encompassed by the present invention. bone sarcomas include osteosarcoma, chondrosarcoma, and ewing's sarcoma. the present invention also encompasses malignant tumors of the thyroid, including papillary, follicular, and anaplastic carcinomas. in some embodiments, a “subject in need of treatment” is a mammal with a viral disease that is life-threatening, or that impairs health, or shortens the lifespan of the mammal. in other embodiments, a “subject in need of treatment” is a mammal with cancer that is life-threatening or that impairs health or shortens the lifespan of the mammal. a “pharmaceutically acceptable” component is one that is suitable for use with humans and/or animals without undue adverse side effects (such as toxicity, irritation, and allergic response) commensurate with a reasonable benefit/risk ratio. a “safe and effective amount” refers to the quantity of a component that is sufficient to yield a desired therapeutic response without undue adverse side effects (such as toxicity, irritation, or allergic response) commensurate with a reasonable benefit/risk ratio when used in the manner of this invention. in some embodiments “therapeutically effective amount” refers to an amount of a component effective to yield the desired therapeutic response, for example, an amount effective to enhance mutagenesis of a virus, or to diminish the ability of the virus to produce active proteins, or to inhibit replication of a virus, or to eliminate or diminish the ability of a virus to produce infectious particles, or to kill the virus or a virally infected cell. other embodiments encompass other therapeutic responses, for example, an amount of a component effective to halt or to delay the growth of a cancer, or to cause a cancer to shrink, or not metastasize. the specific safe and effective amount or therapeutically effective amount will vary with such factors as the particular condition being treated, the physical condition of the patient, the type of mammal being treated, the duration of the treatment, the nature of concurrent therapy (if any), and the specific formulations employed and the structure of the compounds or its derivatives. an “enteric formulation” is a formulation of a compound wherein the compound is stable in the acidic environment of the stomach, and after passage through the stomach, an active form of the compound is available for absorbtion in the intestinal tract. an “oral osmotic drug device” as used herein is a device that delivers a drug at a controlled rate in a region of the gastrointestinal tract having a ph less than 3.5, and then delivers all the drug in the immediately continuing region of the gastrointestinal tract having a ph greater than 3.5. methods to make and use an oral osmotic drug device are found, for example, in u.s. pat. no. 4,587,117, herein incorporated by reference. the compounds the present invention provides compounds that display antiviral activity, in addition to salts and prodrugs of such compounds. the compounds are generally nucleosides, nucleotides, nucleoside analogues, nucleotide analogues, salts and prodrugs thereof. the inventors have recognized that antiviral pharamacophores comprising highly active, yet biologically unstable nucleosides or nucleotides and nucleoside or nucleotide analogues are converted to useful therapeutic agents by altering selected properties of the pharmacophore. in an exemplary embodiment, the pharmacophore is stabilized by the attachment of the active species containing the pharmacophore to a modifying group that increases the lipophilicity of the pharmacophore. the combination of the pharmacophore and the modifying group preferably provides the pharmacophore in a prodrug format. prodrugs comprise inactive forms of active drugs in which a chemical group is present on the prodrug, which renders it inactive and/or confers solubility or some other property to the drug. prodrugs are generally inactive, or less active than the parent compound, but once the chemical group has been cleaved from the prodrug (e.g., by hydrolysis, heat, cavitation, pressure, and/or enzymes in the surrounding environment), the active drug is generated. prodrugs may be designed as reversible drug derivatives and utilized as modifiers to enhance drug transport to site-specific tissues. prodrugs are described in the art, for example, in sinkula et al., j. pharm. sci 64: 181-210 (1975) and in u.s. provisional patent application no. 60/480,037, filed jun. 20, 2003, which is herein incorporated by reference for all purposes. thus, the present invention provides, inter alia, novel nucleoside and nucleotide analogues that are covalently attached to a group that modifies the properties of the nucleoside or nucleotide analogue. in exemplary embodiments, the “modifying group” enhances the stability or bioavailability of nucleoside or nucleotide or its analogue. in the discussion that follows, the invention is exemplified by reference to lipophilic modifying groups. the focus of the discussion is for clarity of illustration, and those of skill in the art will appreciate that compounds including modifying groups other the lipophilic groups discussed herein are within the scope of the invention. thus, in a first aspect, there is provided a compound according to formula i: in formula i, the dashed circle indicates that the ring system may include one or more double bonds at any position, such that the valence of the intra-annular atoms is satisfied. the ring system may be aromatic (e.g., heteroaryl) or non-aromatic. the substituents r 2 , r 7 , r 8 are present or absent as dictated by the application of the laws of valency to a selected ring structure. the symbol y represents c, ch or n, and the symbol z represents c, ch or b. r 1 is a member selected from h, acyl, or 9 , sr 9 , nr 9 nhr 10 , nr 9 r 10 , ═o and ═nr 9 , in which r 9 and r 10 are members independently selected from h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl and substituted or unsubstituted aryl. the symbol r 2 represents a substituent that is a member selected from h, acyl, substituted or unsubstituted alkyl, or 11 , sr 11 , nr 11a , nr 12a , halogen, and ═o. the symbol r 11 represents a member selected from h, substituted or unsubstituted alkyl, substituted or unsubstituted heterocycloalkyl, or substituted or unsubstituted heteroaryl. r 11a and r 12a are members independently selected from h, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. r 3 is a member selected from h, acyl, substituted or unsubstituted alkyl, nr 12 r 13 , nr 12 or 13 , sr 12 , (═o) and or 12 . the symbols r 12 and r 13 represent members independently selected from h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. r 4 and r 4a are members independently selected from h, halogen, ome and oh. in a preferred embodiment, the halogen is f. r 5 and r 6 are members independently selected from h, and or 14 . the symbol r 14 represents h, substituted or unsubstituted alkyl, acyl, substituted or unsubstituted heteroalkyl, or substituted or unsubstituted aryl and p(o)(r 15 )(r 16 ). r 15 and r 16 are independently selected from or 17 , nr 17 r 18 , substituted or unsubstituted alkyl and substituted or unsubstituted nucleosides. r 17 and r 18 are independently selected from h, ch 2 ch cn, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. a member selected from r 5 and r 3 ; r 6 and r 3 ; and r 15 and r 16 together with the atoms to which they are attached, are optionally joined to form a ring system selected from substituted or unsubstituted cycloalkyl and substituted or unsubstituted heterocycloalkyl. in an exemplary embodiment, the ring system is a 5 or 6 membered ring system. r 7 and r 8 are independently selected from h, acyl, substituted or unsubstituted alkyl. r 1 and r 8 , together with the atoms to which they are attached are optionally joined into a ring system selected from substituted or unsubstituted cycloalkyl and substituted or unsubstituted heterocycloalkyl. in an exemplary embodiment, the invention provides a compound according to formula ii: in which the identity of each of the radicals is substantially as described above. in another exemplary embodiment, there is provided a compound according to formula iii: in an exemplary compound according to formula iii, r 11 cleaveable moiety, for example, a silyl group or substituted or unsubstituted alkyl ether, e.g., in a still further exemplary embodiment, the invention provides a compound of formula iv: exemplary compounds according to the formulae above include: still further exemplary compounds based upon a polynucleotide-like format include: in a further embodiment, the present invention provides a compound according to formula v: in which r 19 , r 20 , and r 21 are members independently selected from h, acyl and substituted or unsubstituted alkyl. compounds according to formula v, provide the active compound by elimination of the nitrogen “protecting group”: r═h, oh; r′ is a leaving group oalkyl, oaryl, oheteroaryl, salkyl, saryl, s(o)heteroaryl, s(o) 2 heteroaryl, s(o) 2 alkyl, s(o)aryl, s(o) 2 heteroaryl, cl, br, i, n(alk yl)2 ; r″, r′″, and r″″ are nitrogen protecting groups in an exemplary embodiment, r 6 has a structure according to formula vi or formula vii: in which r 22 represents substituted or unsubstituted alkyl or a substituted or unsubstituted heteroalkyl moiety. the symbol l represents a linker selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl; and ar is a member selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. the symbol n represents an integer from 1 to 30. an exemplary linker precursor contains at least two linking groups derived from reactive functional groups. typically, one linking group of the linker bonds to an oxygen of the phosphate (phosphodiester), while the other linking group of the linker bonds to a chemical functionality of the pharmaceutical agent. examples of chemical functionalities of linker groups include hydroxy, mercapto, carbonyl, carboxy, amino, ketone, and mercapto groups. exemplary linker groups include 6-aminohexanol, 6-mercaptohexanol, 10-hydroxydecanoic acid, glycine and other amino acids, 1,6-hexanediol, β-alanine, 2-aminoethanol, cysteamine (2-aminoethanethiol), 5-aminopentanoic acid, 6-aminohexanoic acid, 3-maleimidobenzoic acid, phthalide, α-substituted phthalides, the carbonyl group, aminal esters, and the like. other “bifunctional” linker groups include, but are not limited to, moieties such as sugars (e.g., polyol with reactive hydroxyl), amino acids, amino alcohols, carboxy alcohols, amino thiols, and the like. generally, at least one of the chemical functionalities of the linker group, the modifying group or the pharmacophore will be activated to allow for the formation of the pharmacophore-linker-modifying group complex. one skilled in the art will appreciate that a variety of chemical functionalities, including hydroxy, amino, and carboxy groups, can be activated using a variety of standard methods and conditions. for example, a hydroxyl group of the linker or pharmacophore can be activated through treatment with phosgene to form the corresponding chloroformate, or p-nitrophenylchloroformate to form the corresponding carbonate. in an exemplary embodiment, the compound of the invention includes a linker that includes a carboxyl functionality. carboxyl groups may be activated by, for example, conversion to the corresponding acyl halide, imidazolide or active ester. this reaction may be performed under a variety of conditions as illustrated in march, supra pp. 388-89. in a preferred embodiment, the acyl halide is prepared through the reaction of the carboxyl-containing group with oxalyl chloride. those of skill in the art will appreciate that the use of carboxyl-containing agents is merely illustrative, and that agents having many other functional groups can be incorporated within the compounds of the invention. typically, the compounds of the invention are prepared using standard chemical techniques to join the various components through their respective chemical functionalities. those of skill in the art will recognize that one can first attach the linker either to the pharmacophore or to the modifying group. the exemplary chemical functionalities shown in table 1 can be present on the pharmacophore, linker, or modifying group, depending on the synthesis scheme employed. table 1 provides examples of a first chemical functionality that is a component of either the pharmacaphore or a substituent and a second chemical functionality that is a component of either the pharmacaphore or a substituent. the exemplary linkages set forth in table 1 are produced by the covalent interaction of chemical functionality 1 and 2. the groups set forth in table 1 are also generally representative of “active groups,” which are found on core moieties of use in the present invention. table 1chemicalchemicalfunctionality 1functionality 2linkagehydroxycarboxyesterhydroxycarbonateaminecarbamateso 3sulfatepo 3phosphatecarboxyacyloxyalkylketoneketalaldehydeacetalhydroxyanhydridemercaptomercaptodisulfidecarboxyacyloxyalkylthioethercarboxythioestercarboxyamino amidemercaptothioestercarboxyacyloxyalkylestercarboxyacyloxyalkylamideaminoacyloxyalkoxycarbonylcarboxyanhydridecarboxyn-acylamidehydroxyesterhydroxyhydroxymethylketone esterhydroxyalkoxycarbonyloxyalkylaminocarboxyacyloxyalkylaminecarboxyacyloxyalkylamideaminoureacarboxyamidecarboxyacyloxyalkoxycarbonylamiden-mannich basecarboxyacyloxyalkyl carbamatephosphatehydroxyphosphateoxygen esteraminephosphoramidatemercaptothiophosphate esterketonecarboxyenol estersulfonamidecarboxyacyloxyalkyl sulfonamideestern-sulfonyl-imidate one skilled in the art will readily appreciate that many of these linkages may be produced in a variety of ways and using a variety of conditions. for the preparation of esters, see, e.g., march supra at 1157; for thioesters, see, march, supra at 362-363, 491, 720-722, 829, 941, and 1172; for carbonates, see, march, supra at 346-347; for carbamates, see, march, supra at 1156-57; for amides, see, march supra at 1152; for ureas and thioureas, see, march supra at 1174; for acetals and ketals, see, greene et al. supra 178-210 and march supra at 1146; for acyloxyalkyl derivatives, see, p rodrugs : t opical and o cular d rug d elivery , k. b. sloan, ed., marcel dekker, inc., new york, 1992; for enol esters, see, march supra at 1160; for n-sulfonylimidates, see, bundgaard et al., j. med. chem., 31:2066 (1988); for anhydrides, see, march supra at 355-56, 636-37, 990-91, and 1154; for n-acylamides, see, march supra at 379; for n-mannich bases, see, march supra at 800-02, and 828; for hydroxymethyl ketone esters, see, petracek et al. annals ny acad. sci., 507:353-54 (1987); for disulfides, see, march supra at 1160; and for phosphonate esters and phosphonamidates, see, e.g., copending application ser. no. 07/943,805, which is expressly incorporated herein by reference. in certain embodiments, one or more of the active groups are protected during one or more steps of the reaction to assemble the compound of the invention. those of skill in the art understand how to protect a particular functional group such that it does not interfere with a chosen set of reaction conditions. for examples of useful protecting groups, see, for example, greene et al., p rotective g roups in o rganic s ynthesis , john wiley & sons, new york, 1991. the linker can also serve to introduce additional molecular mass and chemical functionality into the compound of the invention. generally, the additional mass and functionality will affect the serum half-life and other properties of the compound. thus, through careful selection of linker groups, compounds of the invention with a range of serum half-lives can be produced. in another exemplary embodiment, the linker includes a bond that renders the compound of the invention susceptible to in vivo degradation. in a preferred embodiment, the bond is reversible (e.g., easily hydrolyzed) or partially reversible (e.g., partially or slowly hydrolyzed). cleavage of the bond can occur through biological or physiological processes. in other embodiments, the physiological processes will cleave bonds at other locations within the complex (e.g., removing an ester group or other protecting group that is coupled to an otherwise sensitive chemical functionality) before cleaving the bond between the agent and dendrimer, resulting in partially degraded complexes. other cleavages can also occur, for example, between the spacer and agent and the spacer and dendrimer. for rapid degradation of the complex after administration, circulating enzymes in the plasma can be used to cleave the dendrimer from the pharmaceutical agent. these enzymes can include non-specific aminopeptidases and esterases, dipeptidyl carboxy peptidases, proteases of the blood clotting cascade, and the like. alternatively, cleavage may occur through nonenzymatic processes. for example, chemical hydrolysis may be initiated by differences in ph experienced by the complex following delivery. in such a case, the pharmaceutical agent-dendrimer complex may be characterized by a high degree of chemical lability at physiological ph of 7.4, while exhibiting higher stability at an acidic or basic ph in the reservoir of the delivery device. an exemplary pharmaceutical agent-dendrimer complex, which is cleaved in such a process is a complex incorporating a n-mannich base linkage within its framework. in most cases, cleavage of the compound will occur during or shortly after administration. however, in certain embodiments, cleavage does not occur until the complex reaches the pharmaceutical agent's site of action. the susceptibility of the compound of the invention to degradation can be ascertained through studies of the hydrolytic or enzymatic conversion of the complex to the unbound pharmaceutical agent. generally, good correlation between in vitro and in vivo activity is found using this method. see, e.g., phipps et al., j. pharm. sciences 78:365 (1989). the rates of conversion may be readily determined, for example by spectrophotometric methods or by gas-liquid or high-pressure liquid chromatography. half-lives and other kinetic parameters may then be calculated using standard techniques. see, e.g., lowry et al. m echanism and t heory in o rganic c hemistry, 2nd ed., harper & row, publishers, new york (1981). in a preferred embodiment, one or more of the substituents (modifying groups) on the nucleoside or nucleotide (or analogue) core is a lipid, or is lipophilic; an embodiment of the invention that is illustrated by reference to compounds of the invention in which the substituent is a hydrophobic species, such as a lipid. a wide variety of lipids may be used in preparing the compositions of the invention. the lipids may be of either natural, synthetic or semi-synthetic origin, including for example, fatty acids, fatty alcohols, neutral fats, phosphatides, oils, glycolipids, surface-active agents (surfactants), aliphatic alcohols, waxes, terpenes and steroids. exemplary lipids which may be used to prepare the compounds of the present invention include, for example, fatty acids, lysolipids, fluorolipids, phosphocholines, such as those associated with platelet activation factors (paf) (avanti polar lipids, alabaster, ala.), including 1-alkyl-2-acetoyl-sn-glycero 3-phosphocholines, and 1-alkyl-2-hydroxy-sn-glycero 3-phosphocholines, phosphatidylcholine with both saturated and unsaturated lipids, including dioleoylphosphatidylcholine; dimyristoylphosphatidylcholine; dipentadecanoylphosphatidylcholine; dilauroylphosphatidylcholine; dipalmitoylphosphatidylcholine (dppc); distearoylphosphatidylcholine (dspc); and diarachidonylphosphatidylcholine (dapc); phosphatidylethanolamines, such as dioleoylphosphatidylethanolamine, dipalmitoyl-phosphatidylethanolamine (dppe) and distearoylphosphatidylethanolamine (dspe); phosphatidylserine; phosphatidylglycerols, including distearoylphosphatidyl-glycerol (dspg); phosphatidylinositol; sphingolipids such as sphingomyelin; glycolipids such as ganglioside gm1 and gm2; glucolipids; sulfatides; glycosphingolipids; phosphatidic acids, such as dipalmitoylphosphatidic acid (dppa) and distearoyl-phosphatidic acid (dspa); palmitic acid; stearic acid; arachidonic acid; oleic acid; lipids bearing polymers, such as chitin, hyaluronic acid, polyvinyl-pyrrolidone or polyethylene glycol (peg), also referred to herein as “pegylated lipids” with preferred lipid bearing polymers including dppe-peg (dppe-peg), which refers to the lipid dppe having a peg polymer attached thereto, including, for example, dppe-peg5000, which refers to dppe having attached thereto a peg polymer having a mean average molecular weight of about 5000; lipids bearing sulfonated mono-, di-, oligo- or polysaccharides; cholesterol, cholesterol sulfate and cholesterol hemisuccinate; tocopherol hemisuccinate; lipids with ether and ester-linked fatty acids; polymerized lipids (a wide variety of which are well known in the art); dicetyl phosphate; stearylamine; cardiolipin; phospholipids with short chain fatty acids of about 6 to about 8 carbons in length; synthetic phospholipids with asymmetric acyl chains, such as, for example, one acyl chain of about 6 carbons and another acyl chain of about 12 carbons; ceramides; non-ionic liposomes including niosomes such as polyoxyalkylene (e.g., polyoxyethylene) fatty acid esters, polyoxyalkylene (e.g., polyoxyethylene) fatty alcohols, polyoxyalkylene (e.g., polyoxyethylene) fatty alcohol ethers, polyoxyalkylene sorbitan fatty acid esters (such as, for example, the class of compounds referred to as tween™, including tween 20, tween 40 and tween 80, commercially available from ici americas, inc., wilmington, del.), including polyoxyethylated sorbitan fatty acid esters, glycerol polyethylene glycol oxystearate, glycerol polyethylene glycol ricinoleate, ethoxylated soybean sterols, ethoxylated castor oil, polyoxyethylene-polyoxypropylene polymers, and polyoxyethylene fatty acid stearates; sterol aliphatic acid esters including cholesterol sulfate, cholesterol butyrate, cholesterol isobutyrate, cholesterol palmitate, cholesterol stearate, lanosterol acetate, ergosterol palmitate, and phytosterol n-butyrate; sterol esters of sugar acids including cholesterol glucuronide, lanosterol glucuronide, 7-dehydrocholesterol glucuronide, ergosterol glucuronide, cholesterol gluconate, lanosterol gluconate, and ergosterol gluconate; esters of sugar acids and alcohols including lauryl glucuronide, stearoyl glucuronide, myristoyl glucuronide, lauryl gluconate, myristoyl gluconate, and stearoyl gluconate; esters of sugars and aliphatic acids including sucrose laurate, fructose laurate, sucrose palmitate, sucrose stearate, glucuronic acid, gluconic acid and polyuronic acid; saponins including sarsasapogenin, smilagenin, hederagenin, oleanolic acid, and digitoxigenin; glycerol dilaurate, glycerol trilaurate, glycerol dipalmitate, glycerol and glycerol esters including glycerol tripalmitate, glycerol distearate, glycerol tristearate, glycerol dimyristate, glycerol trimyristate; long chain alcohols including n-decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and n-octadecyl alcohol; 6-(5-cholesten-3β-yloxy)-1-thio-β-d-galactopyranoside; digalactosyldiglyceride; 6-(5-cholesten-3β-yloxy)-hexyl-6-amino-6-deoxy-1-thio-β-d-galact opyranoside; 6-(5-cholesten-3β-yloxy)hexyl-6-amino-6-deoxyl-1-thio-α-d-manno pyranoside; 12-(((7′-diethylamino-coumarin-3-yl)-carbonyl)-methylamino)-octadecanoic acid; n-[12-(((7′-diethylamino-coumarin-3-yl)-carbonyl)-methylamino)-octadecanoy 1]-2-aminopalmitic acid; cholesteryl(4′-trimethyl-ammonio)-butanoate; n-succinyldioleoylphosphatidylethanol-amine; 1,2-dioleoyl-sn-glycerol; 1,2-dipalmitoyl-sn-3-succinylglycerol; 1,3-dipalmitoyl-2-succinylglycerol; 1-hexadecyl-2-palmitoylglycero-phosphoethanolamine and palmitoylhomocysteine, and/or any combinations thereof. examples of polymerized lipids include unsaturated lipophilic chains such as alkenyl or alkynyl, containing up to about 50 carbon atoms. further examples are phospholipids such as phosphoglycerides and sphingolipids carrying polymerizable groups, and saturated and unsaturated fatty acid derivatives with hydroxyl groups, such as for example triglycerides of d-12-hydroxyoleic acid, including castor oil and ergot oil. polymerization may be designed to include hydrophilic substituents such as carboxyl or hydroxyl groups, to enhance dispersability so that the backbone residue resulting from biodegradation is water-soluble. suitable polymerizable lipids are also described, for example, in klaveness et al, u.s. pat. no. 5,536,490. if desired, the compound of the invention may comprise a cationic lipid, such as, for example, n-[1-(2,3-dioleoyloxy)propyl]-n,n,n-trimethylammonium chloride (dotma), 1,2-dioleoyloxy-3-(trimethylammonio)propane (dotap); and 1,2-dioleoyl-3-(4′-trimethylammonio)-butanoyl-sn-glycerol (dotb). exemplary anionic lipids include phosphatidic acid and phosphatidyl glycerol and fatty acid esters thereof, amides of phosphatidyl ethanolamine such as anandamides and methanandamides, phosphatidyl serine, phosphatidyl inositol and fatty acid esters thereof, cardiolipin, phosphatidyl ethylene glycol, acidic lysolipids, sulfolipids, and sulfatides, free fatty acids, both saturated and unsaturated, and negatively charged derivatives thereof. phosphatidic acid and phosphatidyl glycerol and fatty acid esters thereof are preferred anionic lipids. examples of cationic lipids include those listed hereinabove. a preferred cationic lipid for formation of aggregates is n-[1-(2,3-dioleoyloxy)propyl]-n,n,n-trimethylammonium chloride (“dotma”). synthetic cationic lipids may also be used. these include common natural lipids derivatized to contain one or more basic functional groups. examples of lipids which can be so modified include dimethyldioctadecyl-ammonium bromide, sphinolipids, sphingomyelin, lysolipids, glycolipids such as ganglioside gm1, sulfatides, glycosphingolipids, cholesterol and cholesterol esters and salts, n-succinyldioleoylphosphatidylethanolamine, 1,2-dioleoyl-sn-glycerol, 1,3-dipalmitoyl-2-succinylglycerol, 1,2-dipalmitoyl-sn-3-succinylglycerol, 1-exadecyl-2-palmitoylglycerophosphatidylethanolamine and palmitoylhomocystiene. specially synthesized cationic lipids also function in the embodiments of the invention. among these are, for example, n,n′-bis(dodecyaminocarbonyl-methylene)-n,n′-bis(β-n,n,n-trimethylammoniumethylaminocarbonylmethylene-ethylene-diamine tetraiodide; n,n″-bis hexadecylaminocarbonylmethylene)-n,n′,n″-tris hexaiodide; n,n′-bis(dodecylaminocarbonylmethylene)-n,n″-bis(β-n,n,n-trimethyl-ammoniumethylaminocarbonylmethylene)cyclohexylene-1,4-diamine tetraiodide; 1,1,7,7-tetra-(β-n,n,n,n-tetramethylammoniumethylaminocarbonylmethylene)-3-hexadecyl-aminocarbonylmethylene-1,3,7-triaazaheptane heptaiodide; and n,n,n′n′-tetraphosphoethanolaminocarbonylmethylene)diethylenetriamine tetraiodide. in those embodiments in which both cationic and non-cationic lipids are utilized, a wide variety of lipids, as described above, may be employed as the non-cationic lipid. preferably, the non-cationic lipid comprises one or more of dppc, dppe and dioleoylphosphatidylethanolamine. in lieu of the cationic lipids listed above, lipids bearing cationic polymers, such as polylysine or polyarginine, as well as alkyl phosphonates, alkyl phosphinates, and alkyl phosphites, may also be used in the stabilizing materials. those of skill in the art will recognize, in view of the present disclosure, that other natural and synthetic variants carrying positive charged moieties will also function in the invention. saturated and unsaturated fatty acids, which may be employed in the present compounds, include moieties that preferably contain from about 12 carbon atoms to about 22 carbon atoms, in linear or branched form. hydrocarbon groups consisting of isoprenoid units and/or prenyl groups can be also used. examples of suitable saturated fatty acids include, for example, lauric, myristic, palmitic, and stearic acids. examples of suitable unsaturated fatty acids include, for example, lauroleic, physeteric, myristoleic, palmitoleic, petroselinic, and oleic acids. examples of suitable branched fatty acids include, for example, isolauric, isomyristic, isopalmitic, and isostearic acids. other useful lipids or combinations thereof apparent to those skilled in the art, which are in keeping with the spirit of the present invention are also encompassed by the present invention. for example, carbohydrate-bearing lipids may be employed, as described in u.s. pat. no. 4,310,505, the disclosure of which is hereby incorporated herein by reference in its entirety. in addition to the lipids set forth above, the compounds of the present invention may include a moiety that is derived in whole or in part, from proteins or derivatives thereof. suitable proteins for use in the present invention include, for example, albumin, hemoglobin, α-1-antitrypsin, α-fetoprotein, aminotransferases, amylase, c-reactive protein, carcinoembryonic antigen, ceruloplasmin, complement, creatine phosphokinase, ferritin, fibrinogen, fibrin, transpeptidase, gastrin, serum globulins, myoglobin, immunoglobulins, lactate dehydrogenase, lipase, lipoproteins, acid phosphatase, alkaline phosphatase, α-1-serum protein fraction, α-2-serum protein fraction, β-protein fraction, γ-protein fraction and γ-glutamyl transferase. other stabilizing materials and vesicles formulated from proteins that may be used in the present invention are described, for example, in u.s. pat. nos. 4,572,203, 4,718,433, 4,774,958, and 4,957,656. other protein-based moieties, in addition to those described above and in the aforementioned patents, are apparent to one of ordinary skill in the art, in view of the present disclosure. in addition to the lipids and proteins discussed herein, embodiments of the present invention may also include polymers, which may be of natural, semi-synthetic (modified natural) or synthetic origin. polymer denotes a compound comprised of two or more repeating monomeric units, and preferably 10 or more repeating monomeric units. semi-synthetic polymer (or modified natural polymer) denotes a natural polymer that has been chemically modified in some fashion. examples of suitable natural polymers include naturally occurring polysaccharides, such as, for example, arabinans, fructans, fucans, galactans, galacturonans, glucans, mannans, xylans (such as, for example, inulin), levan, fucoidan, carrageenan, galatocarolose, pectic acid, pectins, including amylose, pullulan, glycogen, amylopectin, cellulose, dextran, dextrin, dextrose, glucose, polyglucose, polydextrose, pustulan, chitin, agarose, keratin, chondroitin, dennatan, hyaluronic acid, alginic acid, xanthin gum, starch and various other natural homopolymer or heteropolymers, such as those containing one or more of the following aldoses, ketoses, acids or amines: erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, dextrose, mannose, gulose, idose, galactose, talose, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, tagatose, mannitol, sorbitol, lactose, sucrose, trehalose, maltose, cellobiose, glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine, glucuronic acid, gluconic acid, glucaric acid, galacturonic acid, mannuronic acid, glucosamine, galactosamine, and neuraminic acid, and naturally occurring derivatives thereof. accordingly, suitable polymers include, for example, proteins, such as albumin. exemplary semi-synthetic polymers include carboxymethylcellulose, hydroxymethyl-cellulose, hydroxypropylmethylcellulose, methylcellulose, and methoxycellulose. exemplary synthetic polymers suitable for use in the present invention include polyphosphazenes, polyethylenes (such as, for example, polyethylene glycol (including, for example, the class of compounds referred to as pluronics™, commercially available from basf, parsippany, n.j.), polyoxyethylene, and polyethylene terephthlate), polypropylenes (such as, for example, polypropylene glycol), polyurethanes (such as, for example, polyvinyl alcohol (pva), polyvinyl chloride and polyvinylpyrrolidone), polyamides including nylon, polystyrene, polylactic acids, fluorinated hydrocarbon polymers, fluorinated carbon polymers (such as, for example, polytetrafluoroethylene), acrylate, methacrylate, and polymethylmethacrylate, and derivatives thereof. preferred are biocompatible synthetic polymers or copolymers prepared from monomers, such as acrylic acid, methacrylic acid, ethyleneimine, crotonic acid, acrylamide, ethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate (hema), lactic acid, glycolic acid, ε-caprolactone, acrolein, cyanoacrylate, bisphenol a, epichlorhydrin, hydroxyalkyl-acrylates, siloxane, dimethylsiloxane, ethylene oxide, ethylene glycol, hydroxyalkyl-methacrylates, n-substituted acrylamides, n-substituted methacrylamides, n-vinyl-2-pyrrolidone, 2,4-pentadiene-1-ol, vinyl acetate, acrylonitrile, styrene, p-amino-styrene, p-amino-benzyl-styrene, sodium styrene sulfonate, sodium 2-sulfoxyethyl-methacrylate, vinyl pyridine, aminoethyl methacrylates, 2-methacryloyloxy-trimethylammonium chloride, and polyvinylidene, as well as polyfunctional crosslinking monomers such as n,n′-methylenebisacrylamide, ethylene glycol dimethacrylates, 2,2′-(p-phenylenedioxy)-diethyl dimethacrylate, divinylbenzene, triallylamine and methylenebis-(4-phenylisocyanate), including combinations thereof. preferable polymers include polyacrylic acid, polyethyleneimine, polymethacrylic acid, polymethylmethacrylate, polysiloxane, polydimethylsiloxane, polylactic acid, poly(ε-caprolactone), epoxy resin, poly(ethylene oxide), poly(ethylene glycol), and polyamide (nylon) polymers. preferred copolymers include, but are not limited to, polyvinylidene-polyacrylonitrile, polyvinylidene-polyacrylonitrile-polymethylmethacrylate, polystyrene-polyacrylonitrile and poly d-1, lactide co-glycolide polymers. a preferred copolymer is polyvinylidene-polyacrylonitrile. other suitable biocompatible monomers and polymers will be apparent to those skilled in the art, in view of the present disclosure. in a still further exemplary embodiment, the invention provides tricyclic compounds according to formula vii, in which the radicals are substantially as described above. formulations many drugs are inherently hydrophobic and hence have limited solubility or ability to be dispersed in an aqueous medium, which reduces their bioavailability and makes them difficult to formulate or administer reducing their usefulness. contrary, other drugs are excessively hydrophilic and poorly absorbed when given orally. therefore, certain compounds provided by the present invention are purposely made hydrophobic. similarly, a number of potentially useful bio-active molecules are not sufficiently stable, or have a too short half-life in biological media for successful treatment, which also limits their use. as a result of these and other problems of pharmacokinetics, bioavailability, specificity, etc., there is a need to develop molecules that can help in the transport or delivery of bioactive or functional substances. thus, in another aspect, the invention provides formulations of compounds of the invention. in addition to the compound of the invention, the formulations include a second species that interacts with the compound of the invention to alter a characteristic of the compound, such as its water solubility. in an exemplary embodiment, the compound of the invention includes a lipid moiety, as described above. the second species includes a lipophilic domain that interacts with the lipid moiety of the compound of the invention. the second species also includes a hydrophilic moiety that enhances the water solubility of the complex formed between the compound of the invention and the second species. in an exemplary embodiment, the invention provides a formulation comprising a compound of the invention and a second compound having the formula: a-b wherein a is a hydrophobic domain; and b is a hydrophilic domain covalently bound to a. an exemplary embodiment of the formulations of the invention is set forth in fig. 2 , which is an illustration of the complexes of the invention formed between the pharmacophore modified with a hydrophobic modifying group and a poly-ion, such as a polycation. another exemplary embodiment is provided by fig. 3 , which is an illustration of the complexes of the invention formed between the pharmacophore modified with a hydrophobic modifying group and a dendrimeric poly-ion. in a preferred embodiment, the formulations of the invention are aqueous formulations. if desired, the formulations may form aggregates. an example of such formulations is constructed of one or more charged lipids in association with one or more polymer bearing lipids, optionally in association with one or more neutral lipids. the charged lipids may either be anionic or cationic. typically, the lipids are aggregated in the presence of a multivalent species, such as a counter ion, opposite in charge to the charged lipid. for delivery of prodrugs and/or bioactive agents to selective sites in vivo, aggregates of preferably under 2 microns, more preferably under 0.5 microns, and even more preferably under 200 nm are desired. most preferably the lipid aggregates are under 200 nm in size and may be as small as 5-10 nm in size. when the charged lipid is anionic, a multivalent (divalent, trivalent, etc.) cationic material may be used to form aggregates. it is contemplated that cations in all of their ordinary valence states will be suitable for forming aggregates of compounds of the invention. when the charged lipid is cationic, an anionic material, for example, may be used to form aggregates. preferably, the anionic material is multivalent, such as, for example, divalent. examples of useful anionic materials include monatomic and polyatomic anions such as carboxylate ions, sulfide ion, sulfite ions, sulfate ions, oxide ions, nitride ions, carbonate ions, and phosphate ions. anions of ethylene diamine tetraacetic acid (edta), diethylene triamine pentaacetic acid (dtpa), and 1,4,7,10-tetraazocyclododecane-n′,n′,n″,n″-tetraacetic acid (dota) may also be used. further examples of useful anionic materials include anions of polymers and copolymers of acrylic acid, methacrylic acid, other polyacrylates and methacrylates, polymers with pendant so 3 h groups, such as sulfonated polystyrene, and polystyrenes containing carboxylic acid groups. in an exemplary embodiment, the composition of the invention is charged and a polyion, e.g. a charged dendrimer is used to form an aggregate. dendrimers are polymers of spherical or other three-dimensional shapes that have precisely defined compositions and that possess a precisely defined molecular weight. dendrimers can be synthesized as water-soluble macromolecules through appropriate selection of internal and external moieties. see, u.s. pat. nos. 4,507,466 and 4,568,737, incorporated by reference herein. the first well-defined, symmetrical, dendrimer family was the polyamidoamine (pamam) dendrimers, which are manufactured by the dow chemical company. since the synthesis and characterization of the first dendrimers, a large array of dendrimers of diverse sizes and compositions has been prepared. see, for example, liu m. and frechet j. m. j., pharm. sci. tech. today 2(11): 393 (1999). dendritic macromolecules are characterized by a highly branched, layered structure with a multitude of chain ends. dendrimers are particularly well defined with a very regular and almost size monodisperse structure, while hyperbranched polymers are less well defined and have a broader polydispersity. dendritic macromolecules are usually constructed from ab x monomers. hyperbranched polymers are generally obtained via a polymerization reaction that generally takes place in a single series of propagation steps. dendrimers are generally obtained by multistep iterative syntheses using either a divergent (tomalia et al., u.s. pat. nos. 4,435,548; 4,507,466, 4,558,120; 4,568,737; 5,338,532) or a convergent growth approach (hawker et al., u.s. pat. no. 5,041,516). dendrimers have been conjugated with various pharmaceutical materials as well as with various targeting molecules that may function to direct the conjugates to selected body locations for diagnostic or therapeutic applications. see, for example, wo 8801178, incorporated by reference herein. dendrimers have been used to covalently couple synthetic porphyrins (e.g., hemes, chlorophyll) to antibody molecules as a means for increasing the specific activity of radiolabeled antibodies for tumor therapy and diagnosis. roberts et al., bioconjug. chemistry 1:305-308 (1990); tomalia et al., u.s. pat. no. 5,714,166. exemplary dendrimers of use in this aspect of the invention include the well-known pamam poly(amidoamine) dendrimers or astramol poly(propyleneimine), in part as a result of their easy transformation into ionically charged species. in an exemplary embodiment, the hydrophilic domain of component b, includes a hydrophilic oligomer or polymer. suitable hydrophilic groups include, for example, polyalkyleneoxides such as, for example, polyethylene glycol (peg) and polypropylene glycol (ppg), polyvinylpyrrolidones, polyvinylmethylethers, polyacrylamides, such as, for example, polymethacrylamides, polydimethylacrylamides and polyhydroxypropylmethacrylamides, polyhydroxyethyl acrylates, polyhydroxypropyl methacrylates, polymethyloxazolines, polyethyloxazolines, polyhydroxyethyloxazolines, polyhyhydroxypropyloxazolines, polyvinyl alcohols, polyphosphazenes, poly(hydroxyalkylcarboxylic acids), polyoxazolidines, polyaspartamide, and polymers of sialic acid (polysialics). the hydrophilic polymers are preferably selected from the group consisting of peg, ppg, polyvinylalcohol and polyvinylpyrrolidone and copolymers thereof, with peg and ppg polymers being more preferred and peg polymers being even more preferred. in another exemplary embodiment, the compound of the invention has an oral bioavailability of at least 15%, more preferably at least 20% of the administered dose. an exemplary formulation of a compound of the invention that provides the desired oral bioavailability is an acid addition salt of the heterocyclic compound of the invention. the acid addition salt may be either a salt of a mineral or organic acid, e.g., a carboxylic acid. in accordance with the above embodiment, the inventors have surprisingly discovered that carboxylic acid salts of the compounds of the invention provide the desired oral bioavailability. as shown in table 2, the oral bioavailability of an exemplary carboxylic acid salt of dhadc is approximately 23%, which is more than twice the oral bioavailability of the corresponding base. table 2 αdhadc-base (9)dhadc-base (9)dhadc-palmitate (27)(iv)(oral)oralcmax40,0341,8582,816(ng/ml)auc ∞74,9758,53817,552(ng-hr/ml)half-life1.80.80.7(hr)% oral1123bioavail-abilityα comparison of pharmacokinetics of 5,6-dihydro-5-aza-2′deoxycytidine (dhadc) base given to rats parenterally (iv) and orally to dhadc-palmitate. cmax: maximum concentration in plasma, auc: area under the curve carrier molecules the compounds of the invention and their formulations can also include a carrier molecule, useful to target the pharmacophore to a specific region within the body or tissue, or to a selected species or structure in vitro. selective targeting of an agent by its attachment to a species with an affinity for the targeted region is well known in the art. both small molecule and polymeric targeting agents are of use in the present invention. in an exemplary embodiment, a compound of the invention is linked to a targeting agent that selectively delivers it to a cell, organ or region of the body. exemplary targeting agents such as antibodies, ligands for receptors, lectins, saccharides, antibodies, and the like are recognized in the art and are useful without limitation in practicing the present invention. other targeting agents include a class of compounds that do not include specific molecular recognition motifs include macromolecules such as poly(ethylene glycol), polysaccharide, polyamino acids and the like, which add molecular mass to the ligand. the ligand-targeting agent conjugates of the invention are exemplified by the use of a nucleic acid-ligand conjugate. the focus on ligand-oligonucleotide conjugates is for clarity of illustration and is not limiting of the scope of targeting agents to which the ligands (or complexes) of the invention can be conjugated. moreover, it is understood that “ligand” refers to both the free ligand and its metal complexes. exemplary nucleic acid targeting agents include aptamers, antisense compounds, and nucleic acids that form triple helices. typically, a hydroxyl group of a sugar residue, an amino group from a base residue, or a phosphate oxygen of the nucleotide is utilized as the needed chemical functionality to couple the nucleotide-based targeting agent to the ligand. however, one of skill in the art will readily appreciate that other “non-natural” reactive functionalities can be appended to a nucleic acid by conventional techniques. for example, the hydroxyl group of the sugar residue can be converted to a mercapto or amino group using techniques well known in the art. aptamers (or nucleic acid antibody) are single- or double-stranded dna or single-stranded rna molecules that bind specific molecular targets. generally, aptamers function by inhibiting the actions of the molecular target, e.g., proteins, by binding to the pool of the target circulating in the blood. aptamers possess chemical functionality and thus, can covalently bond to ligands, as described herein. although a wide variety of molecular targets are capable of forming non-covalent but specific associations with aptamers, including small molecules drugs, metabolites, cofactors, toxins, saccharide-based drugs, nucleotide-based drugs, glycoproteins, and the like, generally the molecular target will comprise a protein or peptide, including serum proteins, kinins, eicosanoids, cell surface molecules, and the like. examples of aptamers include gilead's antithrombin inhibitor gs 522 and its derivatives (gilead science, foster city, calif.). see also, macaya et al proc. natl. acad. sci. usa 90: 3745-9 (1993); bock et al nature ( london ) 355: 564-566 (1992) and wang et al. biochem. 32: 1899-904 (1993). aptamers specific for a given biomolecule can be identified using techniques known in the art. see, e.g., toole et al. (1992) pct publication no. wo 92/14843; tuerk and gold (1991) pct publication no. wo 91/19813; weintraub and hutchinson (1992) pct publication no. 92/05285; and ellington and szostak, nature 346: 818 (1990). briefly, these techniques typically involve the complexation of the molecular target with a random mixture of oligonucleotides. the aptamer-molecular target complex is separated from the uncomplexed oligonucleotides. the aptamer is recovered from the separated complex and amplified. this cycle is repeated to identify those aptamer sequences with the highest affinity for the molecular target. for diseases that result from the inappropriate expression of genes, specific prevention or reduction of the expression of such genes represents an ideal therapy. in principle, production of a particular gene product may be inhibited, reduced or shut off by hybridization of a single-stranded deoxynucleotide or ribodeoxynucleotide complementary to an accessible sequence in the mrna, or a sequence within the transcript that is essential for pre-mrna processing, or to a sequence within the gene itself. this paradigm for genetic control is often referred to as antisense or antigene inhibition. additional efficacy is imparted by the conjugation to the nucleic acid of an alkylating agent, such as those of the present invention. antisense compounds are nucleic acids designed to bind and disable or prevent the production of the mrna responsible for generating a particular protein. antisense compounds include antisense rna or dna, single or double stranded, oligonucleotides, or their analogs, which can hybridize specifically to individual mrna species and prevent transcription and/or rna processing of the mrna species and/or translation of the encoded polypeptide and thereby effect a reduction in the amount of the respective encoded polypeptide. ching et al. proc. natl. acad. sci. u.s.a. 86: 10006-10010 (1989); broder et al. ann. int. med. 113: 604-618 (1990); loreau et al. febs letters 274: 53-56 (1990); holcenberg et al. wo91/11535; wo91/09865; wo91/04753; wo90/13641; wo 91/13080, wo 91/06629, and ep 386563). due to their exquisite target sensitivity and selectivity, antisense oligonucleotides are useful for delivering therapeutic agents, such as the ligands of the invention to a desired molecular target. the site specificity of nucleic acids (e.g., antisense compounds and triple helix drugs) is not significantly affected by modification of the phosphodiester linkage or by chemical modification of the oligonucleotide terminus. consequently, these nucleic acids can be chemically modified; enhancing the overall binding stability, increasing the stability with respect to chemical degradation, increasing the rate at which the oligonucleotides are transported into cells, and conferring chemical reactivity to the molecules. the general approach to constructing various nucleic acids useful in antisense therapy has been reviewed by van der krol et al., biotechniques 6: 958-976 (1988) and stein et al. cancer res. 48: 2659-2668 (1988). therefore, in an exemplary embodiment, the ligands of the invention are conjugated to a nucleic acid by modification of the phosphodiester linkage. moreover, aptamers, antisense compounds and triple helix drugs bearing compounds of the invention can also can include nucleotide substitutions, additions, deletions, or transpositions, so long as specific hybridization to or association with the relevant target sequence is retained as a functional property of the oligonucleotide. for example, some embodiments will employ phosphorothioate analogs which are more resistant to degradation by nucleases than their naturally occurring phosphate diester counterparts and are thus expected to have a higher persistence in vivo and greater potency (see, e.g., campbell et al, j. biochem. biophys. methods 20: 259-267(1990)). phosphoramidate derivatives of oligonucleotides also are known to bind to complementary polynucleotides and have the additional capability of accommodating covalently attached ligand species and will be amenable to the methods of the present invention. see, for example, froehler et al., nucleic acids res. 16(11): 4831 (1988). terminal modification also provides a useful procedure to conjugate the pharmacophore to the nucleic acid, modify cell type specificity, pharmacokinetics, nuclear permeability, and absolute cell uptake rate for oligonucleotide pharmaceutical agents. for example, an array of substitutions at the 5′ and 3′ ends to include reactive groups are known, which allow covalent attachment of the cytotoxins. see, e.g., o ligodeoxynucleotides : a ntisense i nhibitors of g ene e xpression , (1989) cohen, ed., crc press; p rospects for a ntisense n ucleic a cid t herapeutics for c ancer and aids, (1991), wickstrom, ed., wiley-liss; g ene r egulation : b iology of a ntisense rna and dna, (1992) erickson and izant, eds., raven press; and a ntisense rna and dna, (1992), murray, ed., wiley-liss. for general methods relating to antisense compounds, see, a ntisense rna and dna, (1988), d. a. melton, ed., cold spring harbor laboratory, cold spring harbor, n.y.). in another exemplary embodiment, the invention utilizes a peptide-based targeting moiety. generally speaking, peptides that are particularly useful as targeting ligands include natural, modified natural, or synthetic peptides that incorporate additional modes of resistance to degradation by vascularly circulating esterases, amidases, or peptidases. suitable targeting ligands, and methods for their preparation, will be readily apparent to one skilled in the art, in view of the disclosure herein. exemplary targeting ligands in the present invention include cell adhesion molecules (cam), among which are, for example, cytokines, integrins, cadherins, immunoglobulins and selectins. regarding targeting to specific cell types, for example, endothelial cells, suitable targeting ligands include, for example, one or more of the following: growth factors, including, for example, basic fibroblast growth factor (bfgf), acidic fibroblast growth factor (afgf), transforming growth factor-alpha (tgf-α), transforming growth factor-beta (tgf-β), platelet-derived endothelial cell growth factor (pd-ecgf) vascular endothelial growth factor (vegf) and human growth factor (hgf); angiogenin; tumor necrosis factors, including tumor necrosis factor-α (tnf-α) and tumor necrosis factor-β (tnf-β), and receptor antibodies and fragments thereof to tumor necrosis factor (tnf) receptor 1 or 2 family, including, for example, tnf-r1, tnf-r2, fas, tnfr-rp, ngf-r, cd30, cd40, cd27, ox40 and 4-1bb; copper-containing polyribonucleotide angiotropin with a molecular weight of about 4,500, as well as low molecular weight non-peptide angiogenic factors, such as 1-butyryl glycerol; the prostaglandins, including, for example, prostaglandin e 1 (pge 1 ) and prostaglandin e 2 (pge 2 ); nicotinamide; adenosine; dipyridamole; dobutamine; hyaluronic acid degradation products, such as, for example, degradation products resulting from hydrolysis of β-linkages, including hyalobiuronic acid; angiogenesis inhibitors, including, for example, collagenase inhibitors; minocycline; medroxyprogesterone; chitin chemically modified with 6-o-sulfate and 6-o-carboxymethyl groups; angiostatic steroids, such as tetrahydrocortisol; and heparin, including fragments of heparin, such as, for example, fragments having a molecular weight of about 6,000, admixed with steroids, such as, for example, cortisone or hydrocortisone; angiogenesis inhibitors, including angioinhibin (agm-1470—an angiostatic antibiotic); platelet factor 4; protamine; sulfated polysaccharide peptidoglycan complexes derived from the bacterial wall of an arthobacter species; fungal-derived angiogenesis inhibitors, such as fumagillin derived from aspergillus fumigatus ; d-penicillamine; gold thiomalate; thrombospondin; vitamin d 3 analogues; interferons, including, for example, α-interferon, β-interferon and γ-interferon; cytokines and cytokine fragments, such as the interleukins, including, for example, interleukin-1 (il-1), interleukin-2 (il-2), interleukin-3 (il-3), interleukin-5 (il-5) and interleukin-8 (il-8); erythropoietin; a 20-mer peptide or smaller for binding to receptor or antagonists to native cytokines; granulocyte macrophage colony stimulating factor (gmcsf); ltb 4 leukocyte receptor antagonists; heparin, including low molecular weight fragments of heparin or analogues of heparin; simple sulfated polysaccharides, such as cyclodextrins, including α-, β- and γ-cyclodextrin; tetradecasulfate; transferrin; ferritin; platelet factor 4; protamine; gly-his-lys complexed to copper; ceruloplasmin; (12r)-hydroxyeicosatrienoic acid; okadaic acid; lectins; antibodies; cd11a/cd18; and very late activation integrin-4 (vla-4). peptides that bind the interleukin-1 (il-1) receptor may be used. the cadherin family of cell adhesion molecules may also be used as targeting ligands, including for example, the e-, n-, and p-cadherins, cadherin-4, cadherin-5, cadherin-6, cadherin-7, cadherin-8, cadherin-9, cadherin-10, and cadherin-11; and most preferably cadherin c-5. further, antibodies directed to cadherins, such as, for example, the monoclonal antibody ec6c10, may be used to recognize cadherins expressed locally by specific endothelial cells. a wide variety of different targeting ligands can be selected to bind to the cytoplasmic domains of the elam molecules. targeting ligands in this regard may include lectins, a wide variety of carbohydrate or sugar moieties, antibodies, antibody fragments, fab fragments, such as, for example, fab′2, and synthetic peptides, including, for example, arginine-glycine-aspartic acid (r-g-d) which may be targeted to wound healing. while many of these materials may be derived from natural sources, some may be synthesized by molecular biological recombinant techniques and others may be synthetic in origin. peptides may be prepared by a variety of different combinatorial chemistry techniques as are now known in the art. targeting ligands derived or modified from human leukocyte origin, such as cd11a/cd18, and leukocyte cell surface glycoprotein (lfa-1), may also be used as these are known to bind to the endothelial cell receptor icam-1. the cytokine inducible member of the immunoglobulin superfamily, vcam-1, which is mononuclear leukocyte-selective, may also be used as a targeting ligand. vla-4, derived from human monocytes, may be used to target vcam-1. as with the endothelial cells discussed above, a wide variety of peptides, proteins and antibodies may be employed as targeting ligands for targeting epithelial cells. preferably, a peptide, including synthetic, semi-synthetic or naturally-occurring peptides, with high affinity to the epithelial cell target receptor may be selected, with synthetic peptides being more preferred. in connection with these preferred embodiments, peptides having from about 5 to about 15 amino acid residues are preferred. antibodies may be used as whole antibody or antibody fragments, for example, fab or fab′2, either of natural or recombinant origin. the antibodies of natural origin may be of animal or human origin, or may be chimeric (mouse/human). human recombinant or chimeric antibodies are preferred and fragments are preferred to whole antibody. in one embodiment of the invention, the targeting ligands are directed toward lymphocytes which may be t-cells or b-cells, with t-cells being the preferred target. to select a class of targeted lymphocytes, a targeting ligand having specific affinity for that class is employed. for example, an anti cd-4 antibody can be used for selecting the class of t-cells harboring cd-4 receptors, an anti cd-8 antibody can be used for selecting the class of t-cells harboring cd-8 receptors, an anti cd-34 antibody can be used for selecting the class of t-cells harboring cd-34 receptors, etc. a lower molecular weight ligand is preferably employed, e.g., fab or a peptide fragment. for example, an okt3 antibody or okt3 antibody fragment may be used. when a receptor for a class of t-cells or clones of t-cells is selected, the steroid prodrug will be delivered to that class of cells. using hla-derived peptides, for example, will allow selection of targeted clones of cells expressing reactivity to hla proteins. another useful area for targeted prodrug delivery involves the interleukin-2 (il-2) system. il-2 is a t-cell growth factor produced following antigen or mitogen induced stimulation of lymphoid cells. among the cell types producing il-2 are cd4 + and cd8 t -cells and large granular lymphocytes, as well as certain t-cell tumors. il-2 receptors are glycoproteins expressed on responsive cells. they are notable in connection with the present invention because they are readily endocytosed into lysosomal inclusions when bound to il-2. the ultimate effect of this endocytosis depends on the target cell, but among the notable in vivo effects are regression of transplantable murine tumors, human melanoma or renal cell cancer. il-2 has also been implicated in antibacterial and antiviral therapies and plays a role in allograft rejection. in addition to il-2 receptors, preferred targets include the anti-il-2 receptor antibody, natural il-2 and an il-2 fragment of a 20-mer peptide or smaller generated by phage display that binds to the il-2 receptor. although not intending to be bound by any particular theory of operation, il-2 can be conjugated to the prodrugs and/or other delivery vehicles and thus mediate the targeting of cells bearing il-2 receptors. endocytosis of the ligand-receptor complex would then deliver the steroid to the targeted cell, thereby inducing its death through apoptosis—independent and superceding any proliferative or activating effect that il-2 would promote alone. additionally, an il-2 peptide fragment which has binding affinity for il-2 receptors can be incorporated either by direct attachment to a reactive moiety on the steroid prodrug or via a spacer or linker molecule with a reactive end such as an amine, hydroxyl, or carboxylic acid functional group. such linkers are well known in the art and may comprise from 3 to 20 amino acid residues. alternatively, d-amino acids or derivatized amino acids may be used which avoid proteolysis in the target tissue. still other systems which can be used in the present invention include igm-mediated endocytosis in b-cells or a variant of the ligand-receptor interactions described above wherein the t-cell receptor is cd2 and the ligand is lymphocyte function-associated antigen 3 (lfa-3), as described, for example, by wallner et al, j. experimental med., 166: 923-932 (1987), the disclosure of which is hereby incorporated by reference herein in its entirety. the targeting ligand may be incorporated in the present stabilizing materials in a variety of ways. generally speaking, the targeting ligand may be incorporated in the present stabilizing materials by being associated covalently or non-covalently with one or more of the stabilizing materials which are included in the compositions including, for example, the prodrugs, lipids, proteins, polymers, surfactants, and/or auxiliary stabilizing materials. in preferred form, the targeting ligand may be associated covalently with one or more of the aforementioned materials contained in the present stabilizing materials. preferred stabilizing materials of the present invention comprise prodrugs, lipid, protein, polymer or surfactant compounds. in these compositions, the targeting ligands are preferably associated covalently with the prodrug, lipid, protein, polymer or surfactant compounds. the covalent linking of the targeting ligands to the pharmacophores in the present compositions, including the prodrugs, and lipid components is accomplished using synthetic organic techniques which are readily apparent to one of ordinary skill in the art in view of the present disclosure. for example, the targeting ligands may be linked to the materials, including the lipids, via the use of well-known coupling or activation agents. as known to the skilled artisan, activating agents are generally electrophilic, which can be employed to elicit the formation of a covalent bond. exemplary activating agents include, for example, carbonyldiimidazole (cdi), dicyclohexylcarbodiimide (dcc), diisopropylcarbodiimide (dic), methyl sulfonyl chloride, castro's reagent, and diphenyl phosphoryl chloride. the covalent bonds optionally involve crosslinking and/or polymerization. crosslinking preferably refers to the attachment of two chains of polymer molecules by bridges, composed of an element, a group, or a compound, which join certain carbon atoms of the chains by covalent chemical bonds. for example, crosslinking may occur in polypeptides that are joined by the disulfide bonds of the cystine residue. crosslinking may be achieved, for example, by (1) adding a chemical substance (crosslinking agent) and exposing the mixture to heat, or (2) subjecting a polymer to high-energy radiation. a variety of crosslinking agents, or “tethers”, of different lengths and/or functionalities are described, for example, in r. l. lunbland, techniques in protein modification, crc press, inc., ann arbor, mich., pp. 249-68 (1995), the disclosures of which is hereby incorporated herein by reference in its entirety. exemplary crosslinkers include, for example, 3,3′-dithiobis(succinimidylpropionate), dimethyl suberimidate, and its variations thereof, based on hydrocarbon length, and bis-n-maleimido-1,8-octane. standard peptide methodology may be used to link the targeting ligand to the compound of the invention utilizing linker groups having two unique terminal functional groups. bifunctional hydrophilic polymers, and especially bifunctional pegs, may be synthesized using standard organic synthetic methodologies. in addition, many of these materials are available commercially, such as, for example, α-amino-ω-carboxy-peg that is commercially available from shearwater polymers (huntsville, ala.). an advantage of using a peg material as the linking group is that the size of the peg can be varied such that the number of monomeric subunits of ethylene glycol may be as few as, for example, about 5, or as many as, for example, about 500 or even greater. accordingly, the “tether” or length of the linkage may be varied, as desired. this may be important depending, for example, on the particular targeting ligand employed. in an exemplary embodiment, the terminus of the hydrophilic spacer, such as polyethylene glycol ethylamine, which contains a reactive group, such as an amine or hydroxyl group, is used to bind a targeting ligand to a compound of the invention. for example, polyethylene glycol ethylamine may be reacted with n-succinimidylbiotin or p-nitrophenylbiotin to introduce onto the spacer a useful coupling group. the carrier molecules may also be used as a backbone for compounds of the invention that are poly- or multi-valent species, including, for example, species such as dimers, trimers, tetramers and higher homologs of the compounds of the invention. the poly- and multi-valent species can be assembled from a single species or more than one species of the invention. for example, a dimeric construct can be “homo-dimeric” or “heterodimeric.” moreover, poly- and multi-valent constructs in which a compound of the invention, or a reactive analogue thereof, is attached to an oligomeric or polymeric framework (e.g., polylysine, dextran, hydroxyethyl starch and the like) are within the scope of the present invention. the framework is preferably polyfunctional (i.e. having an array of reactive sites for attaching compounds of the invention). moreover, the framework can be derivatized with a single species of the invention or more than one species of the invention. moreover, the properties of the carrier molecule can be selected to afford compounds having water-solubility that is enhanced relative to analogous compounds that are not similarly functionalized. thus, any of the substituents set forth herein can be replaced with analogous radicals that have enhanced water solubility. for example, it is within the scope of the invention to, for example, replace a hydroxyl group with a diol, or an amine with a quaternary amine, hydroxylamine or similar more water-soluble moiety. in a preferred embodiment, additional water solubility is imparted by substitution at a site not essential for the activity towards the ion channel of the compounds set forth herein with a moiety that enhances the water solubility of the parent compounds. methods of enhancing the water-solubility of organic compounds are known in the art. such methods include, but are not limited to, functionalizing an organic nucleus with a permanently charged moiety, e.g., quaternary ammonium, or a group that is charged at a physiologically relevant ph, e.g. carboxylic acid, amine. other methods include, appending to the organic nucleus hydroxyl- or amine-containing groups, e.g. alcohols, polyols, polyethers, and the like. representative examples include, but are not limited to, polylysine, polyethyleneimine, poly(ethyleneglycol) and poly(propyleneglycol). suitable functionalization chemistries and strategies for these compounds are known in the art. see, for example, dunn, r. l., et al., eds. p olymeric d rugs and d rug d elivery s ystems , acs symposium series vol. 469, american chemical society, washington, d.c. 1991. pharmaceutical formulations in another preferred embodiment, the present invention provides a pharmaceutical formulation comprising a dendrimer-agent conjugate and a pharmaceutically acceptable carrier. the compounds described herein, or pharmaceutically acceptable addition salts or hydrates thereof, can be delivered to a patient using a wide variety of routes or modes of administration. suitable routes of administration include, but are not limited to, inhalation, transdermal, oral, rectal, transmucosal, intestinal and parenteral administration, including intramuscular, subcutaneous and intravenous injections. the compounds described herein, or pharmaceutically acceptable salts, and/or hydrates thereof, may be administered singly, in combination with other compounds of the invention, and/or in cocktails combined with other therapeutic agents. of course, the choice of therapeutic agents that can be co-administered with the compounds of the invention will depend, in part, on the condition being treated. for example, when administered to a patient undergoing cancer treatment, the compounds may be administered in cocktails containing other bioactive agents, such as anti-cancer agents and/or supplementary potentiating agents. the compounds may also be administered in cocktails containing agents that treat the side-effects of radiation therapy, such as anti-emetics, radiation protectants, etc. other suitable bioactive agents include, for example, antineoplastic agents, such as platinum compounds (e.g., spiroplatin, cisplatin, and carboplatin), methotrexate, adriamycin, taxol, mitomycin, ansamitocin, bleomycin, cytosine arabinoside, arabinosyl adenine, mercaptopolylysine, vincristine, busulfan, chlorambucil, melphalan (e.g., pam, l-pam or phenylalanine mustard), mercaptopurine, mitotane, procarbazine hydrochloride dactinomycin (actinomycin d), daunorubicin hydrochloride, doxorubicin hydrochloride, mitomycin, plicamycin (mithramycin), aminoglutethimide, estramustine phosphate sodium, flutamide, leuprolide acetate, megestrol acetate, tamoxifen citrate, testolactone, trilostane, amsacrine (m-amsa), asparaginase (l-asparaginase) erwina asparaginase, etoposide (vp-16), interferon α-2a, interferon α-2b, teniposide (vm-26), vinblastine sulfate (vlb), vincristine sulfate, bleomycin, bleomycin sulfate, methotrexate, adriamycin, and arabinosyl; blood products such as parenteral iron, hemin, hematoporphyrins and their derivatives; biological response modifiers such as muramyldipeptide, muramyltripeptide, microbial cell wall components, lymphokines (e.g., bacterial endotoxin such as lipopoly-saccharide, macrophage activation factor), sub-units of bacteria (such as mycobacteria and corynebacteria ), the synthetic dipeptide n-acetyl-muramyl-l-alanyl-d-isoglutamine; anti-fungal agents such as ketoconazole, nystatin, griseofulvin, flucytosine (5-fc), miconazole, amphotericin b, ricin, and β-lactam antibiotics (e.g., sulfazecin); hormones and steroids such as growth hormone, melanocyte stimulating hormone, estradiol, beclomethasone dipropionate, betamethasone, betamethasone acetate and betamethasone sodium phosphate, vetamethasone disodium phosphate, vetamethasone sodium phosphate, cortisone acetate, dexamethasone, dexamethasone acetate, dexamethasone sodium phosphate, flunsolide, hydrocortisone, hydrocortisone acetate, hydrocortisone cypionate, hydrocortisone sodium phosphate, hydrocortisone sodium succinate, methylprednisolone, methylprednisolone acetate, methylprednisolone sodium succinate, paramethasone acetate, prednisolone, prednisolone acetate, prednisolone sodium phosphate, prednisolone tebutate, prednisone, triamcinolone, triamcinolone acetonide, triamcinolone diacetate, triamcinolone hexacetonide and fludrocortisone acetate; vitamins such as cyanocobalamin neinoic acid, retinoids and derivatives such as retinol palmitate, and α-tocopherol; peptides, such as manganese super oxide dimutase; enzymes such as alkaline phosphatase; anti-allergic agents such as amelexanox; anti-coagulation agents such as phenprocoumon and heparin; circulatory drugs such as propranolol; metabolic potentiators such as glutathione; antituberculars such as para-aminosalicylic acid, isoniazid, capreomycin sulfate cycloserine, ethambutol hydrochloride ethionamide, pyrazinamide, rifampin, and streptomycin sulfate; antivirals such as acyclovir, amantadine azidothymidine (azt or zidovudine), ribavirin, amantadine, vidarabine, and vidarabine monohydrate (adenine arabinoside, ara-a); antianginals such as diltiazem, nifedipine, verapamil, erythrityl tetranitrate, isosorbide dinitrate, nitroglycerin (glyceryl trinitrate) and pentaerythritol tetranitrate; anticoagulants such as phenprocoumon, heparin; antibiotics such as dapsone, chloramphenicol, neomycin, cefaclor, cefadroxil, cephalexin, cephradine erythromycin, clindamycin, lincomycin, amoxicillin, ampicillin, bacampicillin, carbenicillin, dicloxacillin, cyclacillin, picloxacillin, hetacillin, methicillin, nafcillin, oxacillin, penicillin g, penicillin v, ticarcillin rifampin and tetracycline; antinflammatories such as diffinisal, ibuprofen, indomethacin, meclofenamate, mefenamic acid, naproxen, oxyphenbutazone, phenylbutazone, piroxicam, sulindac, tolmetin, aspirin and salicylates; antiprotozoans such as chloroquine, hydroxychloroquine, metronidazole, quinine and meglumine antimonate; antirheumatics such as penicillamine; narcotics such as paregoric; opiates such as codeine, heroin, methadone, morphine and opium; cardiac glycosides such as deslanoside, digitoxin, digoxin, digitalin and digitalis; neuromuscular blockers such as atracurium besylate, gallamine triethiodide, hexafluorenium bromide, metocurine iodide, pancuronium bromide, succinylcholine chloride (suxamethonium chloride), tubocurarine chloride and vecuronium bromide; sedatives (hypnotics) such as amobarbital, amobarbital sodium, aprobarbital, butabarbital sodium, chloral hydrate, ethchlorvynol, ethinamate, flurazepam hydrochloride, glutethimide, methotrimeprazine hydrochloride, methyprylon, midazolam hydrochloride, paraldehyde, pentobarbital, pentobarbital sodium, phenobarbital sodium, secobarbital sodium, talbutal, temazepam and triazolam; local anesthetics such as bupivacaine hydrochloride, chloroprocaine hydrochloride, etidocaine hydrochloride, lidocaine hydrochloride, mepivacaine hydrochloride, procaine hydrochloride and tetracaine hydrochloride; general anesthetics such as droperidol, etomidate, fentanyl citrate with droperidol, ketamine hydrochloride, methohexital sodium and thiopental sodium; and radioactive particles or ions such as strontium, iodide rhenium and yttrium. in certain preferred embodiments, the bioactive agent is a monoclonal antibody, such as a monoclonal antibody capable of binding to melanoma antigen. the active compound(s) of the invention are administered per se or in the form of a pharmaceutical composition wherein the active compound(s) is in admixture with one or more pharmaceutically acceptable carriers, excipients or diluents. pharmaceutical compositions for use in accordance with the present invention are typically formulated in a conventional manner using one or more physiologically acceptable carriers comprising excipients and auxiliaries, which facilitate processing of the active compounds into preparations which, can be used pharmaceutically. proper formulation is dependent upon the route of administration chosen. for injection, the agents of the invention may be formulated in aqueous solutions, preferably in physiologically compatible buffers such as hanks's solution, ringer's solution, or physiological saline buffer. for transmucosal administration, penetrants appropriate to the barrier to be permeated are used in the formulation. such penetrants are generally known in the art. for oral administration, the compounds can be formulated readily by combining the active compound(s) with pharmaceutically acceptable carriers well known in the art. such carriers enable the compounds of the invention to be formulated as tablets, pills, dragees, capsules, liquids, gels, syrups, slurries, suspensions and the like, for oral ingestion by a patient to be treated. pharmaceutical preparations for oral use can be obtained by combining the dendrimer with a solid excipient, optionally grinding the resulting mixture, and processing the mixture of granules, after adding suitable auxiliaries, if desired, to obtain tablets or dragee cores. suitable excipients are, for example, fillers such as sugars, including lactose, sucrose, mannitol, or sorbitol; cellulose preparations such as, for example, maize starch, wheat starch, rice starch, potato starch, gelatin, gum tragacanth, methyl cellulose, hydroxypropylmethyl-cellulose, sodium carboxymethylcellulose, and/or polyvinylpyrrolidone (pvp). if desired, disintegrating agents may be added, such as the cross-linked polyvinyl pyrrolidone, agar, or alginic acid or a salt thereof such as sodium alginate. dragee cores are provided with suitable coatings. for this purpose, concentrated sugar solutions may be used, which may optionally contain gum arabic, talc, polyvinyl pyrrolidone, carbopol gel, poly(ethylene oxide), and/or titanium dioxide, lacquer solutions, and suitable organic solvents or solvent mixtures. dyestuffs or pigments may be added to the tablets or dragee coatings for identification or to characterize different combinations of active compound doses. pharmaceutical preparations, which can be used orally, include push-fit capsules made of gelatin, as well as soft, sealed capsules made of gelatin and a plasticizer, such as glycerol or sorbitol. the push-fit capsules can contain the active ingredients in admixture with filler such as lactose, binders such as starches, and/or lubricants such as talc or magnesium stearate and, optionally, stabilizers. in soft capsules, the active compounds may be dissolved or suspended in suitable liquids, such as fatty oils, liquid paraffin, or liquid polyethylene glycols. in addition, stabilizers may be added. all formulations for oral administration should be in dosages suitable for such administration. for buccal administration, the compositions may take the form of tablets or lozenges formulated in conventional manner. for administration by inhalation, the compounds for use according to the present invention are conveniently delivered in the form of an aerosol spray presentation from pressurized packs or a nebulizer, with the use of a suitable propellant, e.g., dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. in the case of a pressurized aerosol the dosage unit may be determined by providing a valve to deliver a metered amount. capsules and cartridges of e.g., gelatin for use in an inhaler or insufflator may be formulated containing a powder mix of the compound and a suitable powder base such as lactose or starch. the compounds may be formulated for parenteral administration by injection, e.g., by bolus injection or continuous infusion. formulations for injection may be presented in unit dosage form, e.g., in ampoules or in multi-dose containers, with an added preservative. the compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilizing and/or dispersing agents may be added, such as the cross-linked polyvinyl pyrrolidone, agar, or alginic acid or a salt thereof such as sodium alginate. pharmaceutical formulations for parenteral administration include aqueous solutions of the active compounds in water-soluble form. additionally, suspensions of the active compounds may be prepared as appropriate oily injection suspensions. suitable lipophilic solvents or vehicles include fatty oils such as sesame oil, or synthetic fatty acid esters, such as ethyl oleate or triglycerides, or liposomes. aqueous injection suspensions may contain substances, which increase the viscosity of the suspension, such as sodium carboxymethyl cellulose, sorbitol, or dextran. optionally, the suspension may also contain suitable stabilizers or agents, which increase the solubility of the compounds to allow for the preparation of highly, concentrated solutions. alternatively, the active ingredient may be in powder form for constitution with a suitable vehicle, e.g., sterile pyrogen-free water, before use. the compounds may also be formulated in rectal compositions such as suppositories or retention enemas, e.g., containing conventional suppository bases such as cocoa butter or other glycerides. in addition to the formulations described previously, the compounds may also be formulated as a depot preparation. such long acting formulations may be administered by implantation or transcutaneous delivery (e.g., subcutaneously or intramuscularly), intramuscular injection or a transdermal patch. thus, for example, the compounds may be formulated with suitable polymeric or hydrophobic materials (e.g., as an emulsion in an acceptable oil) or ion exchange resins, or as sparingly soluble derivatives, for example, as a sparingly soluble salt. the pharmaceutical compositions also may comprise suitable solid or gel phase carriers or excipients. examples of such carriers or excipients include but are not limited to calcium carbonate, calcium phosphate, various sugars, starches, cellulose derivatives, gelatin, and polymers such as poly(ethylene oxide). microarrays the invention also provides microarrays including immobilized compounds of the invention and compounds functionalized with compounds of the invention. moreover, the invention provides methods of interrogating microarrays using probes that are functionalized with compounds of the invention. the immobilized species and the probes are selected from substantially any type of molecule, including, but not limited to, small molecules, peptides, enzymes nucleic acids and the like. nucleic acid microarrays consisting of a multitude of immobilized nucleic acids are revolutionary tools for the generation of genomic information, see, debouck et al., in supplement to nature genetics, 21:48-50 (1999). the discussion that follows focuses on the use of compounds of the invention in conjunction with nucleic acid microarrays. this focus is intended to be illustrative and does not limit the scope of materials with which this aspect of the present invention can be practiced. thus, in another preferred embodiment, the compounds of the present invention are utilized in a microarray format. the compound of the invention, or species bearing a compound of the invention can themselves be components of a microarray or, alternatively they can be utilized as a tool to screen components of a microarray. in an exemplary embodiment, the microarrays comprise n probes that comprise identical or different nucleic acid sequences. alternatively, the microarray can comprise a mixture of n probes comprising groups of identical and different nucleic acid sequences identical nucleic acid sequences). in a preferred embodiment, n is a number from 2 to 100, more preferably, from 10 to 1,000, and more preferably from 100 to 10,000. in a still further preferred embodiment, the n probes are patterned on a substrate as n distinct locations in a manner that allows the identity of each of the n locations to be ascertained. in yet another preferred embodiment, the invention also provides a method for preparing a microarray of n probes. the method includes attaching the probes to selected regions of a substrate. a variety of methods are currently available for making arrays of biological macromolecules, such as arrays nucleic acid molecules. one method for making ordered arrays of probes on a substrate is a “dot blot” approach. in this method, a vacuum manifold transfers a plurality, e.g., 96, aqueous samples of probes from 3 millimeter diameter wells to a substrate. the probe is immobilized on the porous membrane by baking the membrane or exposing it to uv radiation. a common variant of this procedure is a “slot-blot” method in which the wells have highly-elongated oval shapes. another technique employed for making ordered arrays of probes uses an array of pins dipped into the wells, e.g., the 96 wells of a microtiter plate, for transferring an array of samples to a substrate, such as a porous membrane. one array includes pins that are designed to spot a membrane in a staggered fashion, for creating an array of 9216 spots in a 22×22 cm area. see, lehrach, et al., h ybridization f ingerprinting in g enome m apping and s equencing , g enome a nalysis , vol. 1, davies et al, eds., cold springs harbor press, pp. 39-81 (1990). an alternate method of creating ordered arrays of probes is analogous to that described by pirrung et al. (u.s. pat. no. 5,143,854, issued 1992), and also by fodor et al., ( science, 251: 767-773 (1991)). this method involves synthesizing different probes at different discrete regions of a particle or other substrate. this method is preferably used with relatively short probe molecules, e.g., less than 20 bases. a related method has been described by southern et al. ( genomics, 13: 1008-1017 (1992)). khrapko, et al., dna sequence, 1: 375-388 (1991) describes a method of making an nucleic acid matrix by spotting dna onto a thin layer of polyacrylamide. the spotting is done manually with a micropipette. the substrate can also be patterned using techniques such as photolithography (kleinfield et al, j. neurosci. 8:4098-120 (1998)), photoetching, chemical etching and microcontact printing (kumar et al., langmuir 10: 1498-511 (1994)). other techniques for forming patterns on a substrate will be readily apparent to those of skill in the art. the size and complexity of the pattern on the substrate is limited only by the resolution of the technique utilized and the purpose for which the pattern is intended. for example, using microcontact printing, features as small as 200 nm are layered onto a substrate. see, xia, y., j. am. chem. soc. 117:3274-75 (1995). similarly, using photolithography, patterns with features as small as 1 μm are produced. see, hickman et al., j. vac. sci. technol. 12:607-16 (1994). patterns which are useful in the present invention include those which include features such as wells, enclosures, partitions, recesses, inlets, outlets, channels, troughs, diffraction gratings and the like. in a presently preferred embodiment, the patterning is used to produce a substrate having a plurality of adjacent wells, indentations or holes to contain the probes. in general, each of these substrate features is isolated from the other wells by a raised wall or partition and the wells do not fluidically communicate. thus, a particle, or other substance, placed in a particular well remains substantially confined to that well. in another preferred embodiment, the patterning allows the creation of channels through the device whereby an analyte or other substance can enter and/or exit the device. in another embodiment, the probes are immobilized by “printing” them directly onto a substrate or, alternatively, a “lift off” technique can be utilized. in the lift off technique, a patterned resist is laid onto the substrate, an organic layer is laid down in those areas not covered by the resist and the resist is subsequently removed. resists appropriate for use with the substrates of the present invention are known to those of skill in the art. see, for example, kleinfield et al., j. neurosci. 8:4098-120 (1998). following removal of the photoresist, a second probe, having a structure different from the first probe can be bonded to the substrate on those areas initially covered by the resist. using this technique, substrates with patterns of probes having different characteristics can be produced. similar substrate configurations are accessible through microprinting a layer with the desired characteristics directly onto the substrate. see, mrkish et al. ann. rev. biophys. biomol. struct. 25:55-78 (1996). the methods the compounds of the present invention can be used to treat viral diseases. in addition, the compounds of the present invention can be used to treat cancer and other diseases of deregulated cellular proliferation. without wishing to be bound by theory, for treatment of viral diseases, the nucleoside and nucleotide analogues of the present invention are incorporated into the viral genome. the nucleoside and nucleotide analogues have phosphodiester linkages or acquire phosphodiester linkages, allowing them to be incorporated and extended by a polymerase. the nucleoside and nucleotide analogues have altered base-pairing properties allowing incorporation of mutations into the viral genome, dramatically increasing the viral mutation rate. the increase in viral mutation rate results in decreased viability of progeny virus, thereby inhibiting viral replication. in presently preferred embodiments, 5-aza-2′-deoxycytidine, 5-aza-cytidine, and derivatives and variants thereof are used to treat dna viruses, rna viruses, and retrovirus infections. the compounds of the present invention can also be used to treat cancer. without wishing to be bound by theory, the nucleoside and nucleotide analogues of the present invention are incorporated into the nucleic acids of a cancerous cell, either dna or rna. the nucleoside and nucleotide analogues have phosphodiester linkages or acquire phosphodiester linkages, allowing them to be incorporated and extended by a polymerase. in one embodiment, the nucleoside and nucleotide analogues have altered base-pairing properties allowing incorporation of mutations into the genome of the cancer cell, dramatically increasing the mutation rate in the cancer cell. the increased mutation rate results in decreased viability of progeny cells, leading to death of the cancer cells, or a diminished growth rate, or inability to metastasize. in another embodiment, mutations are incorporated into transcription products, e.g., mrna molecules that encode proteins or trna molecules useful for translation of proteins. the mutated transcription products encode mutated proteins, for example, proteins with altered amino acid sequences or truncations that lead, in turn to the inactivation of the protein. the inability of the cancer cell to consistently encode active protein can also result in death of the cancer cells, or a diminished growth rate, or inability to metastasize, or inability to proliferate. assays for mutagenic nucleosides and nucleotides in one embodiment, preferred nucleoside analogs of the present invention include 5-aza-cytidine, 5-aza-2′-deoxycytidine, and derivatives and variants thereof including nucleotides, which can be incorporated and extended by a polymerase. generally, such analogs have phosphodiester linkages allowing them to be extended by the polymerase molecule after their incorporation into rna or dna. thus, unlike certain viral inhibitors which cause chain termination (e.g., analogs lacking a 3′-hydroxyl group), the preferred analogs of the present invention are non-chain-terminating analogs that generally do not result in the termination of rna or dna synthesis upon their incorporation. instead, they are preferably error-inducing analogs, which can be incorporated into an dna or rna product but which effectively alter the base-pairing properties at the position of their incorporation, thereby causing the introduction of errors in the rna or dna sequence at the site of incorporation. determination of parameters concerning the incorporation of altered nucleotides by a polymerase such as, human rna polymerase ii and viral polymerases/replicates or the phosphorylation of nucleoside analogs by cellular kinase, is made by methods analogous to those used for incorporation of deoxynucleoside triphosphates by dna polymerases (boosalis, et al., j. biol. chem. 262: 14689-14698 (1987). those of skill in the art will recognize that such assays can also be used to determine the ability of a compound to inhibit a cellular polymerase or to determine the replicative capability of a virus that has been treated with an altered nucleotide. in selected situations direct determination of the frequency of mutations that are introduced into the viral genome (ji and loeb, virol., 199: 323-330 (1994) can be made. the nucleoside or nucleotide analog is incorporated by a cellular polymerase or viral polymerase into the dna or rna copy of the genomic nucleic acid with an efficiency of at least about 0.1%, preferably at least about 5%, and most preferably equal to that of a naturally occurring complementary nucleic acid when compared in equal amounts in an in vitro assay. thus, an error rate of about 1 in 1000 bases or more would be sufficient to enhance mutagenesis of the virus. the ability of the nucleoside or nucleotide analog to cause incorrect base pairing may be determined by testing and examining the frequency and nature of mutations produced by the incorporation of an analog into dna or rna. it has been reported, for example, that the mutation rates in lytic rna viruses (such as influenza a) are higher than in dna viruses, at about 300-fold times higher, drake, pnas, usa 90: 4171-4175 (1993). retroviruses, however, apparently normally mutate at an average rate about an order of magnitude lower than lytic rna viruses. id. for example, in the case of hiv, the viral rna or the incorporated hiv dna is copied by reverse transcriptase and then dna polymerase using a pcr reaction with complementary primers and all four deoxynucleoside triphosphates. the region of the genome copied corresponds to a 600 nucleotide segment in the reverse transcriptase gene. the copied dna or rna after 70 rounds of pcr is treated with restriction enzymes that cleave the primer sequences, and ligated into a plasmid. after transfection of e. coli , individual clones are obtained and the amplified segment within the plasmid is sequenced. mutations within this region are determined by computer-aided analysis, comparing the individual sequences with control viral sequences obtained by parallel culturing of the same virus in the absence of the rna analog. for each nucleotide, determinations are carried out after ten sequential rounds of viral passage or at the point of extinction for viral detection. analogous procedures would be effective for other viruses of interest and would be readily apparent to those of skill in the art. incorporation of an analog by a cellular or viral rna polymerase, by reverse transcriptase (or other viral enzyme) or by dna polymerase may be compared directly, or separately and the separate test results subsequently compared. a comparison of incorporation of analogs among the polymerases of interest can be carried out using a modification of the “minus” sequencing gel assay for nucleotide incorporation. a 5′- 32 p-labeled primer is extended in a reaction containing three of the four nucleoside triphosphates and an analog in the triphosphate form. the template can be either rna or dna, as appropriate. elongation of the primer past the template nucleotide that is complementary to the nucleotide that is omitted from the reaction will depend and be proportional to the incorporation of the analog. the amount of incorporation of the analog is calculated as a function of the percent of oligonucleotide that is extended on the sequencing gel from one position to the next. incorporation is determined by autoradiography followed by either densitometry or cutting out each of the bands and counting radioactivity by liquid scintillation spectroscopy. those of skill in the art will recognize that similar experiments can be done to determine the incorporation of the compounds of the present invention into nucleic acids of cancer cells. when a nucleoside or nucleotide analog of the invention is administered to virally infected cells, either in vitro or in vivo, a population of cells is produced comprising a highly variable population of replicated homologous viral nucleic acids. this population of highly variable cells results from administering mutagenic nucleoside or nucleotide analogs to virally infected cells and increasing the mutation rate of the virus population. thus, the highly variable population of viruses is an indicator that the mutation rate of the virus was increased by the administration of the nucleoside or nucleotide analogs. measuring the variability of the population provides an assessment of the viability of the viral population. in turn, the viability of the viral population is a prognostic indicator for the health of the cell population. for example, low viability for an hiv population in a human patient corresponds to an improved outlook for the patient. in some embodiments, the mutagenic nucleoside or nucleotide analog of choice will be water-soluble and have the ability to rapidly enter the target cells. lipid soluble analogs are also encompassed by the present invention. the nucleoside or nucleotide analog will be phosphorylated by cellular kinases, if necessary, and incorporated into rna or dna. assays of viral replication those of skill in the art recognize that viral replication or infectivity correlates with the ability of a virus to cause disease. that is, a highly infectious virus is more likely to cause disease than a less infectious virus. in a preferred embodiment, a virus that has incorporated mutations into its genome as a result of treatment with the compounds of this invention will have diminished viral infectivity compared to untreated virus. those of skill in the art are aware of methods to assay the infectivity of a virus. (see, e.g., condit, principles of virology, in fields virology, 4th ed. 19-51 (knipe et al., eds., 2001)). for example, a plaque-forming assay can be used to measure the infectivity of a virus. briefly, a sample of virus is diluted into appropriate medium and serial dilutions are plated onto confluent monolayers of cells. the infected cells are overlaid with a semisolid medium so that each plaque develops from a single viral infection. after incubation, the plates are stained with an appropriate dye so that plaques can be visualized and counted. some viruses do not kill cells, but rather transform them. the transformation phenotype can be detected, for example formation of foci after loss of contact inhibition. the virus is serially diluted and plated onto monolayers of contact inhibited cells. foci can be detected with appropriate dye and counted to determine the infectivity of the virus. another method to determine infectivity of viruses is the endpoint method. the method is appropriate for viruses that do not form plaques or foci, but that do have a detectable pathology or cytopathic effect (cpe) in cultured cells, embryonated eggs, or animals. a number of phenotypes are measurable as cpe, including rounding, shrinkage, increased refractility, fusion, syncytia formation, aggregation, loss of adherence or lysis. serial dilutions of virus are applied to an appropriate assay system and after incubation, cpe is assayed. statistical methods are available to determine the precise dilution of virus required for infection of 50% of the cells. (see, e.g., spearman, br. j. psychol. 2:227-242 (1908); and reed and muench, am. j. hyg. 27:493-497 (1938)). the ability of a drug to inhibit viral replication or infectivity is expressed as the ec 50 of the drug, or the effective concentration that prevents 50% of viral replication. methods described above to determine the infectivity of a virus are useful to determine the ec 50 of a drug. the ability of a drug to kill cells is expressed as the ic 50 , or the concentration of drug that inhibit cellular proliferation. methods to determine the ic 50 , of a drug are known to those of skill in the art and include determination of cell viability after incubation with a range of concentrations of the drug. treatment of hiv strains resistant to nucleoside reverse transcriptase inhibitors the compounds of the invention can be used to treat hiv infections and other retroviral infections. the compounds of the present invention are particularly well suited to treat hiv strains that are resistant to nucleoside reverse transcriptase inhibitors. as of 2001, sixteen antiviral drugs were approved for the treatment of hiv infection. seven are nucleoside/nucleotide analog chain terminators or nucleoside reverse trascriptase inhibitors (nrti), six are protease inhibitors, and three are non-nucleoside reverse transcriptase inhibitors (nnrti). until recently, zidovudine was the mainstay of anti hiv drugs. the administration of zidovudine to patients with advanced hiv disease has been shown to prolong survival, to improve neurologic function, to transiently improve cd4+ lymphocyte counts, and to decrease the rate of antigenemia. however, the short-term benefits observed with zidovudine monotherapy, together with the emergence of zidovudine resistance during chronic treatment suggested that combination chemotherapy would be required for prolonged control of hiv infection (see e.g., loveday et al., lancet. 345: 820-824 (1995); volberding, et al., j. infect. dis. 171: s150-s154. (1995)). in 1996, clinical trial results demonstrated that protease inhibitors could dramatically reduce the amount of hiv in a patient's blood and in combination therapy regimens could, in some cases, result in undetectable viral rna by pcr. a combination chemotherapy clinical trial of saquinavir, zidovudine and zalcitabine demonstrated increased cd4+ counts and decreased viral burden that were significantly greater than a two drug regimen (see, e.g., collier et al., new engl. j. med. 334: 1011-1017 (1996)). however, as with nucleoside analogs, there is evidence that cross-resistance develops to protease inhibitors (see e.g., condra et al., nature 374: 569-571 (1995)). in fact, simultaneous mutations of the hiv genome coding for resistance to protease inhibitors and nrti have been described (shafer et al., ann. intern. med. 128: 906-911 (1998)). of note, combination therapy regimens (highly active antiretroviral therapy or haart), typically initiated with triple drug therapy, are expensive and because of their complexity and side effects adversely affect the patients' quality of life. full therapeutic benefit may require near perfect adherence to the dosage, frequency, timing and dietary restrictions of many agents (see, e.g., stone clin. infect. dis. 33: 865-872 (2001)). furthermore, if virologic, immunologic or clinical failure develops during triple therapy a regimen of five or more drugs may be necessary, so called mega-haart (bhiva writing committee. hiv med. 1: 76-101 (2000)). thus, novel hiv therapeutics with a low likelihood of viral resistance are required in the marketplace. one embodiment of this invention describes a novel class of nucleoside and nucleotide analogs for activity against a panel of hiv strains resistant to conventional nrti. routine screening of candidate 5-aza-dc formulations and derivatives was performed against hiv lai. candidates with high activity against hiv lai were also screened for activity against strains of hiv with preexisting resistance to nucleoside reverse transcriptase inhibitors (nrti). hiv strains resistant to nrti are known and mutations in the reverse transcriptase (rt) enzyme responsible for the resistance have been analyzed. resistance mutations in hiv rt appear to only increase the pre-existing capabilities of wild type rt rather than creating new ones. two mechanisms of resistance toward nrti have been described: an increase in efficiency of discrimination between an nrti and a naturally occurring nucleoside, and excision of an nrti by pyrophosphorolysis in the presence of nucleotides (see, e.g., isel et al., j. biol. chem. 276: 48725-48732 (2001)). decrease in affinity of hiv rt for a nrti usually involves alterations in the sugar moiety of an analog, e.g., mutations m184v or q151m (see, e.g., sluis-cremer et al., cell. mol. life. sci. 57: 1408-1422 (2000)). alternatively, chain terminators may be removed by pyrophosphorolysis, or reverse nucleotide polymerization, where pyrophosphate acts as acceptor molecule for the removal of the chain terminator. removal of the chain-terminator frees rt to incorporate the natural nucleotide substrate and rescue viral replication. atp has also been proposed as an acceptor molecule for the removal of chain-terminators and is referred to as primer unblocking (see, e.g., naeger et al., nucleosides nucleotides nucleic acids 20: 635-639 (2001)). viral resistance is less likely to emerge after treatment with mutagenic nucleotide analogues than after treatment with nrti. for example, mutagenic nucleotide analogues apply less selective pressure to a viral population for emergence of resistant variants than approved antivirals, which attempt to immediately halt viral replication. mutagenic nucleotide analogues adversely affect all viral proteins. decreased affinity of hiv rt for a modified nucleoside sugar is one mechanism of viral resistance. mutagenic nucleotide analogues have unmodified sugars. for example, it has been shown that rt may recognize the absence of a 3′-oh group, resulting in cross-resistance among chain terminators (see, e.g., huang et al., science 282: 1669-75 (1998)). mutagenic nucleotide analogues, like natural ds, have a 3′-oh. because mutagenic nucleotide analogues do not terminate replication, pyrophosphorolysis, the other principal mechanism of viral resistance to conventional nucleoside analogs, is unlikely to be applicable to mdrn. pyrophosphorolysis by rt results in the excision of a chain terminator preventing dna chain elongation. cross resistance between nrti and mutagenic nucleoside or nucleotide analogues can be tested by determining the ec 50 for a mutagenic nucleoside or nucleotide analogue in a wild-type hiv strain and in an hiv strain resistant to one or more nrti's. if the ec 50 for the mutagenic nucleoside or nucleotide analogue is higher in the nrti resistant strain than in the wild-type strain, it suggests that cross-resistance has occurred. experiments have demonstrated that cross-resistance is unlikely to develop between nrti and mutagenic nucleoside or nucleotide analogues. a panel of three hiv nrti resistant strains (aids research and reference reagent program, division of aids, niaid, nih), where resistance is achieved by pyrophosphorolysis or enhanced rt discrimination, were used to test the effectiveness of 5-aza-2′-deoxycytidine (5-aza-dc), a mutagenic nucleoside or nucleotide analogue. these strains have most of the mutations in susceptibility to nrti present in routine clinical samples (see, e.g., hertogs, antiviral drug discovery and development summit. strategic research institute, ny, n.y. (2001)), namely: 1) hiv-1 lai-m184v: the m184v mutation confers resistance to lamivudine (3tc). m184v also decreases the likelihood of incorporation of 3tc-tp by interaction with the sulfur of the oxathiolane ring but interestingly also enhances sensitivity to zidovudine perhaps by reducing pyrophosphorolytic activity (see e.g., boyer et al., j. virol. 76: 3248-3256 (2002)). 2) hiv-1 rtmdr1, with 74v, 41l, 106a and 215y mutations. rtmdr1 is resistant to zidovudine, didanosine, nevirapine and other non-nucleoside reverse transcriptase inhibitors. template/primer repositioning may play a role in the decreased dna synthesis processivity associated with the 74v mutation for didanosine. resistance mutations 41l and 215y enhance pyrophosphorolysis (see e.g., sluis-cremer et al., supra). 3) hiv-1 rtmc, with 67n, 70r, 215f and 219q mutations. rtmc is resistant to zidovudine. all of these mutations enhance pyrophosphorolysis (id.). the ec 50 of 5-aza-dc for the wild-type hiv strain lai was similar to the ec 50 of 5-aza-dc for nrti resistant strains. in contrast, the ec 50 of azt or 3tc for the wild-type hiv strain lai was markedly different than the ec 50 of azt or 3tc for the appropriate nrti resistant strain (e.g., rtmc, m184v, or rtmdr1). other nrti mutants are available and can be assayed in a similar manner (gonzales et al., program and abstracts of the forty-second interscience conference on antimicrobials and chemotherapy. abstract no. 3300 (2002)). mutations include: m41l, e44d, a62v, k65r, d67n, t69dn, t69s_ss, k70r, l74v, v75t, f77l, y115f, f116y, v118i, q151m, m184v, l210w, t215f and k219qe. treatment of cancer the compounds of the present invention can be used to treat cancer. because malignant cells replicate more rapidly than nonmalignant cells, the compounds of the invention are preferentially incorporated into malignant cells. in a preferred embodiment, leukemias and other hematopoetic cancers are treated using the compounds of the present invention. without wishing to be bound by theory, the nucleoside and nucleotide analogues of the present invention are incorporated into the nucleic acids of a cancerous cell, either dna or rna. the nucleoside and nucleotide analogues have phosphodiester linkages or obtain phosphodiester linkages, allowing them to be incorporated and extended by a polymerase. in one embodiment, the nucleoside and nucleotide analogues have altered base-pairing properties allowing incorporation of mutations into the genome of the cancer cell, dramatically increasing the mutation rate in the cancer cell. the increased mutation rate results in decreased viability of progeny cells, leading to death of the cancer cells, or a diminished growth rate, or inability to metastasize. in another embodiment, mutations are incorporated into transcription products, e.g., mrna molecules that encode proteins or trna molecules useful for translation of proteins. the mutated transcription products encode mutated proteins, for example, proteins with altered amino acid sequences or trancations that lead, in turn to the inactivation of the protein. the inability of the cancer cell to consistently encode active protein can also result in death of the cancer cells, a diminished growth rate, inability to metastasize, or inability to proliferate. those of skill in the art are aware of methods to test the effectiveness of compounds in treating cancer. for example, cancer cells of interest can be grown in culture and incubated in the presence varying concentrations of the compounds of the present invention. frequently, uptake of vital dyes, such as mtt, is used to determine cell viability and cell proliferation. when inhibition of cell proliferation is seen, the ic 50 of the compound can be determined, essentially as described above. those of skill in the art will also know to test the compounds of the present invention in animal models, for example, nude mice injected with transformed cells. the data gathered in tissue culture models and animal models can be extrapolated by those of skill in the art for use in human patients. combination therapies the compounds of the invention can also be used in combination with other drugs to treat viral diseases or cancers. for example, mutagenic nucleoside analogs can be used in combination with other antiviral therapies, such as nucleoside reverse transcriptase inhibitors, (e.g., zidovudine (zdv or azt), didanosine (ddi), zalcitabine (ddc), stavudine (d4t), lamivudine (3tc), abacavir (abc), and tenofovir tenofovir disoproxil fumarate (tdf)), non-nucleoside reverse transcriptase inhibitors, (e.g., nevirapine (nvp), delavirdine (dlv), and efavirenz (efv)), protease inhibitors, (e.g., invirase, fortovase, norvir, crixivan, viracept, agenerase, kaletra, reyataz, fosamprenavir, and tipranavir) integrase inhibitors, fusion inhibitors or immunomodulators, such as interferon. drugs that induce viral replication, such as diacylglycerol analogues, (e.g., hamer et al. journal of virology. 77:10227-10236 (2003)), might also benefit from combination with a viral mutagen. these drugs may have utility in decreasing the size of the viral reservoir. mutagenic nucleoside analogues can also be used in combination with cytokines such as il-2. (see, e.g., kedzierski and crowe, antiviral chem . & chemo. 12:133-150 (2001)). combination of such compounds with a viral mutagen, would allow incorporation of mutagenic nucleosides into the viral genome producing less fit viruses and ultimately resulting in viral extinction. for cancer treatment mutagenic nucleoside analogs can be used in combination with other anticancer therapies, e.g. radiation, chemotherapeutic agents, hormone analogues, immunostimulants, interferons, cytokines, and antibodies. administration the pharmaceutical preparation is preferably in unit dosage form. in such form the preparation is subdivided into unit doses containing appropriate quantities of the active component. the unit dosage form can be a packaged preparation, the package containing discrete quantities of preparation, such as packeted tablets, capsules, and powders in vials or ampoules. also, the unit dosage form can be a capsule, tablet, cachet, or lozenge itself, or it can be the appropriate number of any of these in packaged form. the compounds (in the form of their compositions) are administered to patients by the usual means known in the art, for example, orally or by injection, infusion, infiltration, irrigation, and the like. for administration by injection and/or infiltration or infusion, the compositions or formulations according to the invention may be suspended or dissolved as known in the art in a vehicle suitable for injection and/or infiltration or infusion. such vehicles include isotonic saline, buffered or unbuffered and the like. depending on the intended use, they also may contain other ingredients, including other active ingredients, such as isotonicity agents, sodium chloride, ph modifiers, colorants, preservatives, antibodies, enzymes, antibiotics, antifungals, antivirals, other anti-infective agents, and/or diagnostic aids such as radio-opaque dyes, radiolabeled agents, and the like, as known in the art. however, the compositions of this invention may comprise a simple solution or suspension of a compound or a pharmaceutically acceptable salt of a compound, in distilled water or saline. alternatively, the therapeutic compounds may be delivered by other means such as intranasally, by inhalation, or in the form of liposomes, nanocapsules, vesicles, and the like. compositions for intranasal administration usually take the form of drops, sprays containing liquid forms (solutions, suspensions, emulsions, liposomes, etc.) of the active compounds. administration by inhalation generally involves formation of vapors, mists, dry powders or aerosols, and again may include solutions, suspensions, emulsions and the like containing the active therapeutic agents routes and frequency of administration of the therapeutic compositions described herein, as well as dosage, will vary from individual to individual, and may be readily established using standard techniques. preferably, between 1 and 100 doses may be administered over a 52-week period. when treating a viral disease, a suitable dose is an amount of a compound that, when administered as described above, is capable of killing or limiting the infectivity of a virus. when treating cancer, a suitable dose is an amount of a compound that, when administered as described above, is capable of killing or slowing the growth of, cancers or cancer cells. in general, an appropriate dosage and treatment regimen provides the active compound(s) in an amount sufficient to provide therapeutic and/or prophylactic benefit. a response can be monitored by establishing an improved clinical outcome (e.g., longer viral disease-free survival or in cancer patients, more frequent remissions, complete or partial, or longer disease-free survival) in treated patients as compared to non-treated patients. a therapeutic amount of a compound described in this application, means an amount effective to yield the desired therapeutic response, for example, an amount effective to kill or limit the infectivity of a virus, when treating a viral disease. when treating a patient with cancer, a therapeutic amount of a compound described in this application is for example, an amount effective to delay or halt the growth of a cancer or to cause a cancer to shrink or not metastasize. for treatment of both viral diseases and cancer, if what is administered is not the compound (or compounds), but an enantiomer, prodrug, salt or metabolite of the compound (or compounds), then the term “therapeutically effective amount” means an amount of such material that produces in the patient the same blood concentration of the compound in question that is produced by the administration of a therapeutically effective amount of the compound itself. similarly, if an enantiomer, prodrug or metabolite of the compositions, or a salt of the compositions or of any of these other compounds, is being administered, then one therapeutically effective amount of such a compound is that amount that produces a therapeutically relevant blood concentration of the compositions in a patient. oral dosages optimally range from 500 mg to 2 grams for treatment of viral diseases or cancer. those of skill in the art are aware of the routine experimentation that will produce an appropriate dosage range for a patient in need of treatment by oral administration or any other method of administration of a drug, e.g., intravenous administration or parenteral administration, for example. those of skill are also aware that results provided by in vitro or in vivo experimental models can be used to extrapolate approximate dosages for a patient in need of treatment. patients that can be treated with the a compound described in this application, and the pharmaceutically acceptable salts, prodrugs, enantiomers and metabolites of such compounds, according to the methods of this invention include, for example, patients that have been diagnosed as having hiv infection, hepatitis b, hepatitis c, or small pox or vaccinia virus. other patients that can be treated with the a compound described in this application, and the pharmaceutically acceptable salts, prodrugs, enantiomers and metabolites of such compounds, according to the methods of this invention include, for example, patients that have been diagnosed as having lung cancer, bone cancer, pancreatic cancer, skin cancer, cancer of the head and neck, cutaneous or intraocular melanoma, uterine cancer, ovarian cancer, rectal cancer or cancer of the anal region, stomach cancer, colon cancer, breast cancer, gynecologic tumors (e.g., uterine sarcomas, carcinoma of the fallopian tubes, carcinoma of the endometrium, carcinoma of the cervix, carcinoma of the vagina or carcinoma of the vulva), hodgkin's disease, cancer of the esophagus, cancer of the small intestine, cancer of the endocrine system (e.g., cancer of the thyroid, parathyroid or adrenal glands), sarcomas of soft tissues, cancer of the urethra, cancer of the penis, prostate cancer, chronic or acute leukemia, solid tumors of childhood, lymphocytic lymphomas, cancer of the bladder, cancer of the kidney or ureter (e.g., renal cell carcinoma, carcinoma of the renal pelvis), or neoplasms of the central nervous system (e.g., primary cns lymphoma, spinal axis tumors, brain stem gliomas or pituitary adenomas). in further aspects of the present invention, the compositions described herein may be used to treat hematological malignancies including adult and pediatric aml, cml, all, cll, myelodysplastic syndromes (mds), myeloproliferative syndromes (mps), secondary leukemia, multiple myeloma, hodgkin's lymphoma and non-hodgkin's lymphomas. within such methods, pharmaceutical compositions are typically administered to a patient. as used herein, a “patient” refers to any warm-blooded animal, preferably a human. kits for administering the compounds may be prepared containing a composition or formulation of the compound in question, or an enantiomer, prodrug, metabolite, or pharmaceutically acceptable salt of any of these, together with the customary items for administering the therapeutic ingredient. all references and patent publications referred to herein are hereby incorporated by reference herein. as can be appreciated from the disclosure provided above, the present invention has a wide variety of applications. accordingly, the following examples are offered for illustration purposes and are not intended to be construed as a limitation on the invention in any way. examples example 1 5-aza-dc is a potent mutagen of hiv 5-aza-2′-deoxycytidine (5-aza-dc) is a potent viral mutagen that is capable of eradicating hiv in a single passage. viral stocks for test of antiviral activity the strains of hiv-1 used for primary drug screening are hiv-1 lai or the appropriate strain of nrti resistant hiv for studies of cross-resistance. virus was propagated on mt-2 cells at an multiplicity of infection (moi) of 0.01 to generate virus stocks. briefly, the mt-2 cells were suspended in rpmi 1640 media supplemented with 10% fetal bovine serum, streptomycin and penicillin (crpmi) and grown in a 37° c. incubator containing 5% co 2 . serial dilution of the virus and infection of mt-2 cells were followed by an elisa detecting the capsid protein of hiv-1 (p24) and used to determine the titer of the virus stocks (50% tissue culture infectious dose (tcid 50 )). the elisa was performed according to the manufacturer's instructions. the mt-2 cells are also used for visualizing the cytopathic effects of hiv-1 growth (e.g. syncytia formation). treatment of hiv-1-infected cells with mutagenic nucleoside or nucleotide analogues 0.1 ml of a 3×10 5 cells/ml mt-2 cell suspension were seeded in 96-well plates at 3×10 4 cells/well. the compounds to be assayed were diluted in a separate 96-well at ten times (10×) the concentration needed for the screen. 22 μl of the 10× compounds was then added to the wells in triplicate except for six control wells, containing uninfected mt-2 cells alone (3 wells) and untreated hiv-infected mt-2 cells (3 wells). this was followed by the addition of hiv-1 at an moi of 0.01, except for the three wells serving as the uninfected control. 0.1 ml of crpmi was added to the uninfected well instead of virus. after the addition of virus, the 96-well plate was centrifuged at 1,200×g for two hours to enhance the adsorption of the virus by the mt-2 cells (see, e.g., o'doherty, j. virol. 74:10074-10080 (2000)). after the centrifugation step, the 96-well plate was then incubated in a 37° c. incubator containing 5% co2 for three days. at the end of this time period the virus and cells were mixed by gentle pipetting followed by a 1 minute spin at 600×g to pellet the cells. the supernatant of each well was then serially diluted 1,000-fold into new 96-well plates to serve as inoculum for the next passage and assayed by elisa for the amount of p24 produced. the next passage was performed as described above, except that the virus used to infect the cells was derived from the 1,000-fold dilution plate. to generate an ec 50 value, half-log concentrations of mutagenic nucleoside or nucleotide analogue capable of eradicating virus in a single passage are tested as above to generate a dose-response curve. ec 50 values were determined for the following compounds: 5-aza-dc, 5-aza-du, dh-aza-dc, and 5-methyl-5,6-dihydro-5-azadeoxycytidine (medhadc). 5-aza-dc has an ec 50 (effective concentration that prevents 50% of viral replication) of 3 nm against the wild-type hiv strain lai. results are shown in fig. 4 . the ec 50 values for the other compounds are 3 μm for dhadc and 10 μm for medhadc. assessment of the frequency of mutations to the viral genome induced by mutagenic nucleoside analogues the viral genomic dna from cells treated with the deoxyribonucleoside analog 5-aza-dc (30 μm) was purified using a qiagen dneasy® kit. 1 μg of genomic dna was used to amplify a 1 kb region of the hiv-1 rt proviral dna by pcr. the pcr product was then cloned into a topo® cloning vector. a millipore miniprep kit was used to purify plasmid containing proviral inserts. about 45 positive clones were sequenced in both directions by a beckman coulter ceq 8000. the sequencing results were analyzed and assembled using the dnastar stagman program. each mutated base was counted and the mutation rate was calculated over the total number of sequenced nucleotides. the results were compared with the background mutation rate generated from untreated control virus and are shown in table 3. sixty-one mutations were found in 26,187 bases sequenced in the 5-aza-dc treated cells. only one mutation in the drug-free control could be confirmed by sequencing in both directions and thus, the mutation rate in the control may be overestimated. thus, sequencing of a fragment of the nucleic acid encoding hiv reverse transcriptase has confirmed that 5-aza-dc is mutagenic to the viral genome. table 3mutations/gπatπcaπtaπcgπtcπganalognucleotide%aπccπttπacπatπggπc5-aza-dc61/26,1870.223246801013none6/11,0230.05451 assessment of mutagenic nucleoside analogue cytotoxicity for each compound, cytotoxicity was evaluated on mt-2 cells. mt-2 cells were seeded at 3×10 4 cells/well in 96-well plates. the cells were treated with compounds at half-log serial dilutions from 100 μm to 0.32 μm in triplicate. after 5 days growth in a 37° c. incubator containing 5% co 2 , mtt was added to a final concentration of 0.5 mg/ml and then incubated for four hours at 37° c. 10% sds in 0.02 n hcl was added to lyse the cells overnight at 37° c. the plates were read on a tecan genius microplate reader at wavelengths of 570 nm/650 nm. the dose response curve was graphed by comparing the treated cells with the untreated control and the ic 50 was determined for each compound. for 5-aza-dc, the ic 50 was greater than 10 μm. for dhadc, the ic 50 was greater than 1 mm. the ic 50 for 5-me-dhadc was not determined. example 2 5-aza-dc is effective against wild-type hiv strains and nrti resistant hiv strains assessment of sensitivity of nrti-resistant hiv strains to mutagenic nucleoside analogue to determine if there is resistance of hiv nrti resistant strains to mutagenic nucleoside analogues, nrti resistant strains were grown in the presence of 5-aza-dc to determine whether the ec 50 for 5-aza-dc is different from the wt strain (hiv-1 lai). an ec 50 higher for the nrti-resistant strains than for the wt strain suggests that there is cross-resistance between 5-aza-dc and the particular nrti. the ec 50 experiment was performed in a similar manner described above for the drug screen against hiv-lai. growth of hiv nrti resistant strains in the presence of the appropriate concentration of nrti was used as a positive control. three hiv nrti resistant strains (hiv-1 lai-m184v, hiv-1 rtmdr1, with 74v, 41l, 106a and 215y mutations, and hiv-1 rtmc, with 67n, 70r, 215f and 219q mutations) were used to test the effectiveness of 5-aza-dc. results are shown in table 4. these experiments demonstrate that hiv strains with resistance to nrti are not cross-resistant with 5-aza-dc. the ec 50 of 5-aza-dc for the wild-type hiv strain lai was similar to the ec 50 of 5-aza-dc for nrti resistant strains. in contrast, the ec 50 of azt or 3tc for the wild-type hiv strain lai was markedly different than the ec 50 of azt or 3tc for the appropriate nrti resistant strain (e.g., rtmc, m184v, or rtmdr1). other nrti mutants are available and can be assayed in a similar manner (gonzales et al., program and abstracts of the forty-second interscience conference on antimicrobials and chemotherapy. abstract no. 3300 (2002)). mutations include: m41l, e44d, a62v, k65r, d67n, t69dn, t69s_ss, k70r, l74v, v75i, f77l, y115f, f116y, v118i, q151m, m184v, l210w, t215f and k219qe. table 4hivstrain5-aza-dc (ec 50 ) nmazt (ec 50 ) nm3tc (ec 50 ) nmlai31045(wild type)rtmc5300330m184v1010>32,000rtmdr11060n.d. table 4: ec 50 's of 5-aza-dc versus zidovudine (azt) and lamivudine (3tc) against wild type hiv lai and drug resistant strains. example 3 5-aza-c is effective against riboviruses 5-aza-c was effective against two model riboviruses: measles virus and bovine viral diarrhea virus. viral stocks for test of antiviral activity measles virus (mv) and bovine viral diarrhea virus (bvdv) are members of two distinct ribovirus families, paramyxoviridae and flaviviridae. for primary screening, drug activities were tested against these two viruses. mv nagahata strain was used for drug testing. compared to some laboratory strains, this virus strain replicates lytically in primary human embryonic lung cells and causes extensive cytopathic effect during acute infection. the virus stock was prepared by growing the virus on cv-1 cells at a moi of 0.01. the titer of the virus stock was determined by plaque formation assay after series dilution. the bvdv strain used for drug testing was the singer strain. this virus also causes a cytopathic effect that is measurable and allows estimation of the level of infection. the visible cytopathology can be used as an endpoint for titrating the virus by 50% tissue culture infectious dose (tcid 50 ). the bvdv was propagated in bovine turbinate (bt cells). the virus tcid 50 was determined by counting the cytopathic effect at the endpoint dilution. briefly, confluent bt cells in 96-well plates were infected with the virus at 8 independent serial 10-fold dilutions. all the plates were incubated for five days at 37° c. in 5% co 2 . each well was scored as positive or negative appearance of visible cytopathic effect. the titers were calculated by the method of reed and muench, am. j. hyg. 27:493-497 (1938), and the mean titer and standard deviation for each of the 3 replicates for each drug concentration and the positive and negative control were calculated. treatment of mv- or bvdv-infected cells with mutagenic nucleoside analogs virus susceptible cells (cv-1 or bt cells) were seeded in 96-well plates at 2×10 4 cells/well. the virus was inoculated onto the cell monolayers at a moi of 0.001˜0.002 to keep 30 plaque forming units (pfu) in each well. the inoculum was maintained in 37° c. for about one hour and the supernatant was discarded. fresh media containing appropriate drug concentration was added in each well. untreated control was run in parallel. each drug was tested in triplicate. three days after infection, cytopathic effect (cpe) was examined in the untreated control wells. when the untreated control cells showed more than 90% cpe, the infected cells were harvested. the plates went through one “freeze-thaw” cycle to release intracellular virus. the virus stock was saved for next round of passage. the virus titer was determined as described above. virus at a titer of 10 5 ˜10 6 pfu/ml was produced by this method. the following results were obtained. 5-aza-c was effective against bvdv as a surrogate for hepatitis c virus, with an ec50 of 10 μm. 5-aza-c was effective against measles virus with an ec 50 of 15 μm. assessment of the frequency of mutations to the viral genome induced by ribonucleoside analogs. the mutagenicity of test analogs showing antiviral activities will be evaluated. studies with ribavirin indicate that the mutation rate is related to the concentration of introduced analogs (see e.g., crotty et al., nature med. 8(12):1375-1379 (2000)). in order to shorten the duration of the experiment, the infected cells are treated with test analogs at 2 mm so that a high mutation rate can be achieved. this dosage is usually toxic to cells and no progeny virus is produced. cells are inoculated with bvdv or mv and incubated for 4 hours. the incubation allows the virus to express the proteins necessary for viral rna replication. the test analogs are then added and incubated for another 24 hours. viral rna is extracted with a qiagen rneasy kit. about 1 μg of rna is primed with viral gene specific oligonucleotides and cdna will be synthesized using m-mlv reverse transcriptase. about 1 kb fragments covering bvdv variable region e2, and conserved region ns3 is amplified from 1 μg cdna by pcr. the pcr products is cloned into an invitrogen topo© cloning vector. a millipore miniprep kit is used to screen plasmids containing viral inserts. about 40 positive clones are subjected to sequence reaction. each sample is sequenced from two directions. sequence results were assembled by using the dnastar stagman program. each mutated base is counted and mutation rate is calculated over the total number of sequenced nucleotides. the results are compared with the background control generated from untreated control virus. assessment of cytotoxicity for each test analog, cytotoxicity is evaluated on bt cells. bt cells are seeded at 1×10 4 , 4×10 4 , 1×10 5 cells/well in 24-well plates. the next day the cells are treated with drugs at concentrations of 0, 100 μm, 300 μm and 1,000 μm. each dose is tested in duplicate. after the cells are grown for three generations, mtt at final concentration of 1 μg/μl is added in the media and the cells are incubated for three hours. 10% sds in 0.02n hcl will be added to lyse the cells overnight. the plates are read on a tecan genius microplate reader at wavelengths of 570/650 nm. the dose response curve is graphed by comparing the treated cells with the untreated control. the dosage that inhibits 50% of cell growth (ic 50 ) is then determined. for those analogs showing antiviral activity, cytotoxicity is further examined in t lymphoid cem cells by using the same method. example 4 synthesis materials and methods 5-azacytidine (1) and 2′-deoxy-5-azacytidine (2) (scheme 1) are commercially available from sigma.5-azauridine (3)compound 3 was synthesized following a literature procedure (nucl. acid chemistry (l. b. townsend and r. s. tipson eds) part 1, p 455-459, n-y 1978).5,6-dihydro-5-azauridine (4)compound 4 was synthesized from 5-azauridine according to (piskala a., {hacek over (c)}esneková b., veselý j. nucl. acids symp. ser . no 18 (1978) pp 57-60). example 4a synthesis of 1-(2-deoxy-3,5-di-o-p-toluoyl-β-d-ribofuranosyl)-4-amino-1,2-dihydro-1,3,5-triazin-2-one (5) the desired compound was synthesized by (niedballa u., vorbrüggen h. j. org. chem . vol. 39, no. 25, 1974, pp 3672-3674) as a white crystalline powder, m.p. 195-196° (from ethyl acetate). example 4b synthesis of 1-(2-deoxy-3,5-di-o-p-toluoyl-α-d-ribofuranosyl)-4-amino-1,2-dihydro-1,3,5-triazin-2-one (6) the desired compound was isolated as a side reaction product from the above synthesis of compound 5 as a white crystalline powder, m.p. 210-211° (from ch 2 cl 2 -hexanes), 220° (from ethanol). nmr (dmso-d 6 ) δ 8.44 (s, 1h, h-6), 7.91 (d, 2h, ar), 7.71 (d, 2h, ar), 7.51 (d j=8.7 hz, 2h, nh 2 ), 7.36 (d, 2h, ar), 7.28 (d, 2h, ar), 6.11 (d j=5.7 hz, 1h, h-1′), 5.53 (d, 1h, h-4′), 5.11 (t, 1h), 4.45 (d, 2h), 2.86 (m, 1h), 2.50 (m, 1h), 2.39 (s, 3h, me), 2.37 (s, 3h, me). nmr (cdcl 3 ) δ 8.25 (s, 1h, h-6), 7.92 (d, 2h, ar), 7.69 (d, 2h, ar), 6.88 (br s, 2h, nh 2 ), 7.26 (d, 2h, ar), 7.19 (d, 2h, ar), 6.27 (d j=6.3 hz, 1h, h-1′), 5.61 (d, 1h, h-4′), 4.88 (t, 1h), 4.55 (d, 2h), 3.00-2.87 (m, 1h), 2.67 (m, 1h), 2.42 (s, 3h, me), 2.38 (s, 3h, me). example 4c synthesis of 1-(2-deoxy-3,5-di-o-p-toluoyl-β-d-ribofuranosyl)-4-amino-1,2,5,6-tetrahydro-1,3,5-triazin-2-one (7) (scheme 2) to a suspension of 5 (0.50 g, 1.08 mmol) in acetic acid (5 ml) was added nabh 4 in 2 portions (2×0.040 g, 2.11 mmol) with ice cooling in 15 min interval. the mixture was stirred for another 15 min at 0° c. and evaporated. the residual oil was suspended in chcl 3 (150 ml), washed with sat. nahco 3 solution (70 ml) and dried over na 2 so 4 . the solution was filtered through celite, concentrated by partial evaporation and applied to a silica gel column (1.5×22 cm). the column was eluted with ch 2 cl 2 -meoh mixtures (5-15% v/v meoh, 700 ml). the product fractions were combined and evaporated, crystallized from meoh-ether (1:2) giving 0.3 g of 7 as a solid. ms es + 467 [m+h + ]. example 4d synthesis of 1-(2-deoxy-3,5-di-o-p-toluoyl-α-d-ribofuranosyl)-4-amino-1,2,5,6-tetrahydro-1,3,5-triazin-2-one (8) compound 8 was synthesized by analogy to 7 starting from 6. nmr (dmso-d 6 ) δ 7.92-7.85 (m, 4h, ar), 7.38-7.30 (m, 4h, ar), 6.27 (dd j=8.2+4.8 hz, 1h, h-1′), 5.46 (m, 1h, h-4′), 4.58 (q, 2h, ch 2 ), 4.56 (m, 1h), 4.37 (m, 2h), 3.5 (br s, 3h, nh, nh 2 ), 2.78 (m, 1h), 2.50 (m, 1h), 2.39 (s, 3h, me), 2.38 (s, 3h, me). ms es + 467 [m+h + ]. example 4e synthesis of 1-(2-deoxy-β-ribofuranosyl)-4-amino-1,2,5,6-tetrahydro-1,3,5-triazin-2-one (2′-deoxy-5,6-dihydro-5-azacytidine) (9) method a (reduction of 2). to a suspension of 2′-deoxy-5-azacytidine (2) (0.045 g, 0.2 mmol) in 96% ethanol (2.9 ml) was added nabh 4 (40 mg, 1.06 mmol), and the mixture was stirred for 10 min at rt. water (4 ml) was added to the mixture giving a clear solution that was directly used for rp hplc purification using a gradient of mecn in 0.1 m triethylammonium bicarbonate buffer. the main fraction after evaporation provided 0.04 g of 9 as a solid. ms es + 231 [m+h + ]. method b (deprotection of 7, scheme 3). to a solution of 7 (50 mg) in meoh (5 ml) was added 25% aq. nh 3 (2 ml) giving a suspension that became a solution upon stirring overnight. the mixture was evaporated, redissolved in water and purified by rp preparative hplc using a gradient of mecn in 0.1 m triethylammonium bicarbonate buffer. the main fraction after evaporation gave 0.03 g of 9 as a solid. ms es + 231 [m+h + ]. method c (via reduction of ribo-compound 1, scheme 4, five steps). step 1. synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5-azacytidine (11) compound 11 was prepared by analogy to the process described for tips-protection of compound 2 in (goggard a. j., marquez v. e. tetrahedron letters , vol. 29, no. 15, 1988, pp 1767-1770). compound 11 was obtained as a colorless solid with m.p. 249°. step 2. synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-5-azacytidine (12) 0.57 g of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5-azacytidine was suspended in 10 ml of thf under nitrogen. nabh 4 (0.34 g, 9 mmol, 7.7 eq.) was added and the reaction mixture was sonicated for 3 min. after stirring for 2 h at room temperature, 100 ml of saturated nacl was added and the mixture was extracted 3 times with 150 ml of etoac. the organic fractions were dried over na 2 so 4 , filtered and evaporated. the product was isolated by silica gel lc in etoac with meoh gradient. ms es − 487.0 [m−h + ], yield of 12 is 0.27 g (47%). step 3. synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-n4-isobutyryl-5-azacytidine (13) (scheme 5) 265 mg of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-5-azacytidine was dissolved in a 1:1 mix of pyridine and dichloromethane (10 ml) and cooled to 0° c. chlorotrimethylsilane (344 μl, 5 eq.) was added followed after 15 min by isobutyryl chloride (341 μl, 6 eq.). after 1.5 h of stirring the reaction was quenched with 10 ml of meoh, evaporated, dissolved in etoac (100 ml) and extracted twice with saturated nacl (50 ml). the organic layer was dried with na 2 so 4 , evaporated and the residue was redissolved in meoh and left overnight at room temperature. then the solution was evaporated and the product was isolated by flash chromatography (meoh gradient in dichloromethane). ms es − 557.1 [m−h + ], yield 180 mg (59%). step 4. synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n4-isobutyryl-5-azacytidine (14) 80 mg of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-n 4 -isobutyryl-5-azacytidine was dissolved in 4 ml of dry dmf and 1,1′-thiocarbonyldiimidazole (77 mg, 3 eq.) was added. after overnight incubation at ambient temperature the reaction mixture was diluted with 50 ml of etoac and extracted with water (4×50 ml). the organic fraction was dried over na 2 so 4 , filtered, evaporated to oil, coevaporated with toluene twice and dissolved in 10 ml of toluene. the solution was degassed with argon for 45 min, 107 μl of tributyltin hydride (5 eq.) and 13 mg of 2,2′-azobis(isobutyronitrile) were added. the reaction mixture was heated at 80° c. for 3 h, cooled, evaporated and separated by flash chromatography on silica gel (meoh gradient in dichloromethane). the main product showed expected es + ms signals at 543.3 [m+h + ] and 565.5 [m+na + ], yield 18 mg (23%). step 5. synthesis of 2′-deoxy-5,6-dihydro-5-azacytidine (9) 6 mg of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n 4 -isobutyryl-5-azacytidine was dissolved in 2 ml of meoh and treated with 6 ml of 25% aq. nh 3 over 16 h at room temperature. the solution was evaporated to dryness, coevaporated with toluene and dissolved in 2 ml of thf. to the solution 0.5 ml of 1 m tetrabutylammonium fluoride was added and the reaction mixture was incubated for 1 h. solvent was removed by evaporation and the product was isolated on rp hplc. appropriate fractions were pooled, evaporated to dryness, co-evaporated with meoh and the product was repurified on a preparative tlc plate (1×250×250 mm, elution with isopropanol-water-conc. nh 4 oh (15:4:1)). the product-containing band was scratched out and the product was eluted with meoh-water (7:3) mixture. ms es + 231.0 [m+h + ], 253.2 [m+na + ], yield 1.7 mg (67%). ms es + 231 [m+h + ]. example 4f synthesis of 1-(2-deoxy-α-d-ribofuranosyl)-4-amino-1,2,5,6-tetrahydro-1,3,5-triazin-2-one (10) compound 10 was synthesized by analogy to the preparation of 9 by deprotection of 8 with ammonia using method b. compound 10 was obtained as a solid. example 4g synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-n4-isobutyryl-5-aza-5-n-methylcytidine (15) 18 mg of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n 4 -isobutyryl-5-azacytidine, 0.1 ml of n,n-diisopropyl-n-ethylamine and 1.0 ml of dimethylsulfate were incubated for 1 h at room temperature. the product was isolated by flash chromatography on silica gel (meoh gradient in dichloromethane). es + ms signals at 573.2 [m+h + ], 595.3 [m+na + ] and 1167.2 [2m+na + ], yield 14 mg (77%). example 4h synthesis of 5,6-dihydro-5-aza-5-n-methylcytidine (16) 14 mg of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5,6-dihydro-n 4 -isobutyryl-5-aza-5-n-methylcytidine was dissolved in 2 ml of meoh and treated with 6 ml of concentrated nh4oh during 16 h at room temperature. the solution was evaporated to dryness, co-evaporated with toluene and dissolved in 2 ml of thf. to the solution 0.5 ml of 1 m tetrabutylammonium fluoride was added and the reaction mixture was incubated for 1 h. solvent was removed by evaporation and the product was isolated on rp hplc. appropriate fractions were pooled, evaporated to dryness, coevaporated with meoh and the product was repurified on a preparative tlc plate (1×250×250 mm, elution with isopropanol(15):water(4):conc. nh 4 oh(1)). the band containing product was scratched out and the product was eluted with meoh(7):water(3) mixture. ms es + 261.0 [m+h + ], 520.9 [2m+h + ], yield 5.5 mg (86%). ms/ms of the 261.0 mass ion generated the expected fragment with m/z 128.9, corresponding to the 5,6-dihydro-5-aza-5-n-methylcytosine base. example 4i synthesis of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n4-isobutyryl-5-aza-5-n-methylcytidine (17) a mixture of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n 4 -isobutyryl-5-azacytidine (14) (11 mg), 0.1 ml of n,n-diisopropyl-n-ethylamine and 1.0 ml of dimethylsulfate was incubated for 1 h at room temperature. the product 17 was isolated by flash chromatography on silica gel (meoh gradient in dichloromethane). es + ms signals at 557.3 [m+h + ] and 579.3 [m+na + ], yield 9 mg (80%). example 4j synthesis of 2′-deoxy-5,6-dihydro-5-aza-5-n-methylcytidine (18) a solution of 3′,5′-o-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2′-deoxy-5,6-dihydro-n 4 -isobutyryl-5-aza-5-n-methylcytidine (17) (9 mg) in meoh (2 ml) was treated with concentrated nh 4 oh (6 ml) and kept at room temperature for 16 h. the solution was evaporated to dryness, coevaporated with toluene, dissolved in thf (2 ml) and treated with a solution of 1 m tetrabutylammonium fluoride in thf (0.5 ml). the reaction mixture was left at room temperature for 1 h. solvent was removed by evaporation and the product was isolated on rp hplc. appropriate fractions were pooled, evaporated to dryness, coevaporated with meoh and the product was further purified on a preparative tlc plate (1×250×250 mm, elution with isopropanol-water-conc. nh 4 oh (15:4:1)). the product-containing band was scratched out and the product was eluted with meoh-water (7:3) mixture. ms es + 245.0 [m+h + ], 267.1 [m+na + ], yield 18 was 3.7 mg (93%). ms/ms of the 245.0 mass ion generated the expected fragment with m/z 128.9, corresponding to the 5,6-dihydro-5-aza-5-n-methylcytosine base. example 4k synthesis of 6-methyl-5-azacytosine (19) (scheme 6) 8.4 g of dicyandiamide was suspended in a mixture of 16 ml of ac 2 o and 1 ml of acoh. the reaction mixture was refluxed during 16 h. after cooling the reaction mixture was evaporated to dryness. the product was isolated on preparative rp hplc (ch 3 cn gradient 0-20% over 20 min in 0.1 m triethylammonium bicarbonate buffer (ph 7.0)). retention time was 6.7 min, λmax=237 nm, ms es − =125, yield 30%. example 4l 6-methyl-5-azacytidine (20) compound 20 was synthesized according to (hanna n. b., zajicek j., piskala a. nucleosides & nucleotides 16, 1997, p. 129-144) with 8% yield starting from 6-methyl-5-azacytosine (19). example 4m synthesis of 6-methyl-2′-deoxy-5-azacytidine (21) 30 mg of 6-methyl-5-azacytosine, 5 mg of (nh 4 ) 2 so 4 and 5 ml of hexamethyldisilazane were refluxed overnight at 125° c. (external oil bath temperature). the clear solution was evaporated to solid and co-evaporated with 5 ml of xylene. to the residue 70 mg of the 3,5-bistoluoyl-1-chloro-2-deoxyribose was added and the mixture was suspended in 2 ml of ch 3 cn. incubation with stirring was continued for 24 h and then a mixture of 173 mg acona and 0.3 ml acoh, diluted to 1 ml with water was added. after 1 h the mixture was diluted with 20 ml of water and extracted twice with 20 ml of ethyl acetate. the organic layer was dried over na 2 so 4 , filtered, evaporated and the products were separated by silica gel chromatography. yield of β-anomer 25%, α-anomer (23%). the protected nucleoside was treated with 0.02 m naome in meoh for 4 h to remove toluoyl protecting groups. the resulting nucleosides were isolated on pr hplc. example 4n syntheses of 6-phenyl-5-azacytosine (22) and 6-phenyl-5-azacytidine (23) (scheme 7) were carried out according to published procedure (hanna n. b., masojidkova m., fiedler p., piskala a. collect. czech. chem. commun. 63, 1998, p. 222-230). yield of the base was 43%, nucleoside—16%. example 4o synthesis of 5-azacytidine and 6-methyl-5-azacytidine prodrugs (scheme 8) 8.3 mg of the nucleoside was suspended in 1 ml of thf and 11 ul (4 eq.) of n-methylimidazole was added. the reaction mixture was cooled to −78° c. and 4-bromophenyl-n-methoxyalaninylphosphorochloridate (15 mg) in 0.5 ml of thf was added dropwise during 30 min. after 1 h another 10 mg of the phosphorochloridate was added, the mixture was allowed to warm to room temperature and incubated overnight. the mixture was evaporated and separated by rp hplc. 5-azacytidine prodrug was eluted at 23 min (0-20% ch 3 cn in 23 min), λmax=226 nm, yield approximately 15%. 6-methyl-5-azacytidine prodrug was eluted at 24 min, λmax 225 nm, yield approximately 12%. the 5-azacytidine phospholipid prodrugs are synthesized by scheme 9. 5-azacytidine prodrugs, activated by biological reduction are synthesized by scheme 10. example 4p 1-(β-d-ribofuranosyl)-4-amino-1,2,5,6-tetrahydro-1,3,5-triazin-2-one (5,6-dihydro-5-azacytidine) (23) and 6-oxo-5-azacytidine (24) (scheme 11) were synthesized by (beisler, j. a. abbasi, m. m. kelley, j. a. driscoll, j. s. j. carbohydrates. nucleosides. nucleotides, 4(5), 1977, pp 281-299). example 4q 2′-deoxy-5,6-dihydro-5-azauridine (26) is synthesized by a reduction of 2′-deoxy-5-azauridine (25) by analogy to the reduction of compound 3 to 4 (piskala a., {hacek over (c)}esneková b., veselý j. nucl. acids symp. ser. no 18 (1978) pp 57-60) example 4r synthesis of 2′-deoxy-5,6-dihydro-5-azacytidine palmitate (27) to a solution of (9) (0.26 g, 1.13 mmol) in meoh (50 ml) was added a solution of palmitic acid (0.29 g, 1.13 mmol) in hot meoh (10 ml) and evaporated. the residue was triturated with ether and filtered giving 0.57 g (quantitative yield) of a colorless product with m.p. 123-124°. ms es+ 231 [m+h+]. example 5 in vitro assays demonstrate that dhadc is safe and effective against hiv infection in vitro passaging assays of dhadc passaging experiments were performed for dhadc (also referred to as sn1212), to demonstrate that viral eradication is possible in vitro. the experiment was carried out in quadruplicate in the presence of sn1212 at a concentration of 100 nm. levels of p24 fell permanently below the limit of detection (4 ng/ml) by passage 8. no infectious virus was recovered after passage 12. (data not shown.) dhadc is a viral mutagen. assessment of dhadc viral mutagenicity was carried out as described above for 5-aza-dc. mutagenesis of the sense strand of a 0.9 kb fragment of reverse transcriptase of hiv nl4-3 was determined after a single passage in sn1212 (50 μm) and compared to an untreated control. results are shown in table 5. table 5mutations/g→at→ca→ta→cg→tg→canalognucleotide%a→gc→tt→ac→at→gc→gsn121237/24,8280.01517121133control32/28,6580.0112730110 the mutation rate induced by 50 μm sn1212 in hiv rt is 1.4-fold higher than control (0.0015 in dhadc treated versus 0.0011 in control). the dominant mutations are c t transitions (enhanced 4.6-fold by sn1212), with a minority of transversions (pyrimidine purine). in contrast, 5-oh-dc demonstrated only a 1.14-fold increase in overall mutation rate over background. dhadc does not cause significant mutagenesis of cellular dna. sn1212 is a poor substrate for polymerase-α, the cellular polymerase responsible for most dna synthesis. (data not shown.) an hgprt assay was also performed to test mutagenesis of cellular dna by dhadc. the assay was performed on cho (chinese hamster ovary) cells and mutants were selected for resistance to 6-thioguanine (6-tg). ems (ethyl methyl sulfonate), a known mutagen, was used as a positive control. sn1212 at a concentration of 1 mm did not increase above background the mutation frequency of a cellular gene, hgprt. (data not shown.) of note, the ec 50 of dhadc against hiv is in the range of 10 nm, while no significant mutation to cellular dna is noted at 1 mm, a 10,000-fold difference. mitochondrial toxicity is also a safety concern with nucleoside analogs. sn1212 was also analyzed for mitochondrial toxicity. sn1212 does not demonstrate evidence of mitochondrial toxicity by either an increase in lactate production or inhibition of mitochondrial dna at the highest dose tested, 320 μm. (data not shown.) dhadc is effective against wild-type hiv strains and nrti resistant hiv strains. the effectiveness of dhadc was tested against wild-type hiv strains and nrti resistant hiv strains as described in example 2. the following strains were tested: hiv-1 lai, wild-type; hiv-1 lai-m184v-m184v mutation with resistance to lamivudine (3tc); hiv-1 rtmdr1-74v, 41l, 106a and 215y mutations with resistance to zidovudine, didanosine, nevirapine and other non-nucleoside reverse transcriptase inhibitors; and hiv-1 rtmc-67n, 70r, 215f and 219q with resistance to zidovudine. results are shown in table 6. table 6hiv strainsn1212 (ec 50 ) μmazt (ec 50 ) nm3tc (ec 50 ) nmwild-type61045rtmc6300330m184v610>32,000rtmdr1660n.d. the ec 50 's of sn1212 were the same in wild-type and the three mutant hiv strains, confirming the lack of cross-resistance between sn1212 and nrti. furthermore, based on hiv passaging experiments designed to favor the emergence of resistant strains performed with sn1212, it appears unlikely that de novo resistance will develop to sn1212. example 6: in vivo assays demonstrate that dhadc, or prodrugs thereof, are safe and effective against hiv infection dhadc is effective in treating hiv infections in a mouse model. sn1212 was administered at up to 100 mg/kg/day subcutaneously in scid-hu thy/liv mice for 21 days, without any significant toxicity being demonstrated. after completion of this toxicology experiment, sn1212 was tested in hiv infected scid-hu mice. while sn1212 did not demonstrate reduction in p24 or hiv rna, it demonstrated a significant decrease in viral infectivity when compared to untreated animals at a dose of 10 mg/kg (see, e.g., table 7). the discordance between viral infectivity and conventional surrogate markers of viral load, such as p24 or hiv rna, is not surprising, as it has also been observed in vitro, and reflects the increased proportion of non-infectious viral particles in the presence of sn1212. it is also interesting to note that, of the treated groups, the immunologic profile of the sn1212 groups most closely resemble that of the uninfected group. this is compatible with the finding that infection with less “fit” viruses provides a relative clinical benefit by preserving cellular immunity. table 7drug/dosecd4+ cd8+cd4+cd8+p24hiv-1 rnaviral titer(mg/kg/day)(%)(%)(%)(pg/10 6 cells)(log copies/10 6 cells)(viruses/10 6 cells)sn1212 (100)6310115705.124.9sn1212 (10)70139.55105.315.2**3tc (30)776.94.20**2.0**0**ndc*637.95.92505.466.5uninfected65129.4000*no drug control.**p < 0.05 a prodrug of sn1212, sn1461, is not toxic in animals. sn1461 is a prodrug that in humans is converted predominantly in the liver to sn1212. sn1461 has been tested for pharmacokinetic characteristics in a number of animal species. in rats, sn1461 has a half-life of 3.9 hours and an oral bioavailability of 43%, while in beagles; sn1461 has a half-life of 2.1 hours and an oral bioavailability of 51%, prior to formulation enhancements. a single dose of up to 1 g/kg of sn1461 has been given orally to rats and up to 2 g/kg to dogs in a dose escalation study without evidence of toxicity. the present invention provides a novel class of mutagenic compounds, and methods of using and preparing these compounds. while specific examples have been provided, the above description is illustrative and not restrictive. any one or more of the features of the previously described embodiments can be combined in any manner with one or more features of any other embodiments in the present invention. furthermore, many variations of the invention will be apparent to those skilled in the art upon review of the specification. the scope of the invention should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims along with their full scope of equivalents. all publications and patent documents cited in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication or patent document were so individually denoted. by their citation of various references in this document, applicants do not imply that any particular reference is “prior art” to their invention.
|
068-401-442-925-030
|
DE
|
[
"AT",
"DE",
"JP",
"WO",
"EP",
"CA",
"US",
"ES"
] |
A01G7/06,A01N25/00,A01N25/28,A01N25/34
| 1996-03-16T00:00:00 |
1996
|
[
"A01"
] |
injection method for administering microparticles containing active substances to plants
|
described is a method of injecting into plants a free-flowing solid, semi-solid or liquid agent designed to give controlled release of at least one active substance, the method using pressure-operated equipment without needles. the method is characterized in that the microparticles in the agent have a maximum diameter of 100 νm and contain the following constituents: a) 0.5-70 % by wt. of at least one active substance, b) 10-70 % by wt. of at least one biodegradable polymer, c) up to 20 % by wt. of formulation auxiliaries.
|
process for the administration of a flowable solid, semi-solid, or liquid medium exhibiting controlled release of at least one active substance to plants by means of injection using needle-free, pressure-actuated devices, characterized in that the medium comprises active substance-containing microparticles of a maximum size of 100 µm in the form of monolithic microspheres wherein the active substance is homogenously distributed in a polymer matrix or in the form of active substance cores surrounded by polymer material, which microparticles contain the following components: a) 0.5 - 70%-wt. of at least one active substance, b) 10 - 70%-wt. of at least one biodegradable polymer, c) up to 20%-wt. of formulation adjuvants, the active substance release being, at least partially, determined by the degradation of the polymer. the process according to claim 1 characterized in that the microparticles are present as dispersion in an aqueous phase. the process according to any one of claims 1 or 2 characterized in that the biologically degradable polymers are selected from the group consisting of polylactic acid, polyglycolic acid, polylactides as well as their copolymers, cellulose and its derivatives, aliphatic polyesters, and polysaccharides. the process according to claim 3 characterized in that water-soluble polysaccharides, such as starch, alginic acids and their salts, carragheenans, and pectins are used as biologically degradable polymers.
|
examples include: aliphatic polyesters, such as poly-e-caprolactone (tone.rtm. p787), poly-3-hydroxybutanoic acid copolymers, poly-3-hydroxyvaleric acid copolymers, polyethylene succinate, polybutylene succinate (bionolle.rtm.) polysaccharides, such as starch, sodium alginate (manucol.rtm. lb) calcium alginate, carragheenan, and pectins cellulose and its derivatives, e.g., mixed esters, cellulose acetate butyrate polylactic acid and polyglycolic acid and their derivatives, such as poly-l-lactide, poly-d,l,-lactide, and lactide-glycolide copolymers. the ratio between the polymeric active substance carrier material and the active substances may vary according to the desired effect; however, it must correspond to the composition as defined in claim 1. a preferred embodiment of the particles used in the process according to the present invention has the following components: a) 35-60%-wt. of an active substance b) 45-50%-wt. of a biodegradable polymer c) 5-10%-wt. of additives. biological degradation leads to simultaneous active substance release, and it is initiated by hydrolytic and/or enzymatic bioerosion in the plant. degradation of the products applied by means of the process according to the present invention mainly results in fragments that are known as to their biocompatibility and which can be metabolized in natural metabolic pathways of the plant. intensity and scope of particle decomposition in the plant organism depend on the kind of polymeric materials used. thus, their period of degradation can be adapted to the indicated requirements by adequate choice of starting materials. this property particularly suits the diversity of individually required active substance supply found in plant cultivation. for example, in diseases involving a high degree of initial infestation, water-soluble particulate active substance carriers, e.g., made of specific polysaccharides, may be used which are subject to a relatively rapid hydrolytic degradation under the conditions prevailing in the conductive paths of the plant. the resulting rapid active substance release results in the desired rapid onset of action. active substance release from the microparticles used in the process according to the present invention cannot only take place by bioerosion of the polymeric carrier, but also by diffusion from the polymeric matrix. this is the case in particular when the particles are formed as microspherules, i.e., when the active substance is physically bound in the polymer matrix, without a separate capsule wall. diffusion-controlled release also takes place when polymeric carrier materials are hydrophobic and less available to the metabolism of higher plants than to that of microorganisms. for example, this applies to polyhydroxy butyrate/polyhydroxy valerate copolymers. microcapsules whose matrices remain intact in the use region serve as active substance depot preparation, and they are therefore used in injections for long-term treatments, e.g., in treating the death of elms. it is essential for the present invention that microparticles having a maximum size of 100 .mu.m be used. the particular advantage of this dimensioning is the particle mobility in the plant that can be achieved thereby. in contrast to prior art particulate active substance carriers whose particle diameters are in the range of 100-3000 .mu.m, the size of the particles used in the injection process according to the present invention corresponds to the average size of plant cells (10-100 .mu.m), thus their transport in the tissue region which is particularly important for substance distribution in the leaves can considerably be improved because the microbeads are diffusible owing to their relatively small size with given stability. in addition there is the advantage of good mobility in the plant's paths of conduction; this also applies to plants having small-luminal sieve tubes. particles based on water-soluble polysaccharides (e.g., starch, alginates, carragheenan and pectins) represent a preferred embodiment of the particulate active substance carriers used in the process according to the present invention. since their polymer matrix can quite rapidly be converted into osmotically effective substances (e.g., oligosaccharides) within the plant organism, they are preferably transported in the phloem. this is particularly advantageous when growing parts of the plant (meristems) are to be provided with active substances. among the active substances which can be injected by means of the process according to the present invention in particulate form, those are to be mentioned which are capable of influencing processes in the animal or plant organism. these primarily include systemically active plant protection agents, for example, insecticides, acaricides, fungicides, and bactericides. systemic insecticides include, for example, butocarboxim, dimethoate, fenoxycarb, methamyl, oxamyl, oxydemeton-methyl, pirimicarb, or propoxur. systemic acaricides include, for example, clofentizine, fenbutatin oxide, and hexythiazox. systemic fungicides include, for example, benomyl, bromuconazole, bitertanole, etaconazole, flusilazol, furalaxyl, fosetyl-al, imazalil, metalaxyl, penconazole, propiconazole, thiabendazol, triadimefon, triadimenol, or triforine. flumequine, for example, is to be mentioned among the systemic bactericides. systemic growth regulators include, for example, ethephon and .beta.-indolylacetic acid (iaa). another advantage achievable by means of the present invention is the fact that the desired injection media may be present both in flowable and solid form. the problem of needle occlusion occurring in conventional injection systems is avoided because here nozzle injection of small-sized microparticles is concerned. particularly preferable is a process wherein the composition according to the present invention, which is to be injected, is formulated in liquid vehicles. suitable liquid vehicles include water, npkmineral fertilizer solution, and vegetable oils. water is to be emphasized as particularly preferable. adjuvants may be added as required. these may include dispersants, such as polysorbat 80, or thickeners, such as carboxymethylcellulose. depending on the production method in the process according to the present invention, other adjuvants known to the skilled artisan may also be included. example 1 8.8 g poly-d,l-lactide-co-glycolide (molar ratio 50:50) is dissolved in 240 ml dichloromethane and placed in a reaction vessel equipped with a stirrer. 0.36 g of the active substance al-fosetyl is suspended at a stirring rate of 500 rpm. subsequently, 54 g sesame oil is progressively added under continued stirring. after complete addition of sesame oil, the mixture comprising the raw microcapsules is continuously dispersed in a thin jet under constant stirring (at 1000 rpm) in 4l of a caprylic-capric acid triglyceride (miglyol.rtm. 812, viscosity 27 to 33 mpa.s) at 20.degree. c. hardening of the microcapsules takes place within a period of 60 min. the microcapsules thus obtained are filtered off, washed twice with isopropanol, and dried. the particles comprise 2.8%-wt. of the active substance. the average particle diameter amounts to 25.5 .mu.m. immediately prior to use, 270 mg microcapsules is suspended at 37.degree. c. in 120 ml water. the suspension thus obtained is filled into a pressure-actuated injection device without needle (type demo-jet) and injected at a pressure of 8.1 bar into the plant tissue at the basis of a partially lignified biennal sprout (rubus idaeus).
|
069-015-199-356-544
|
US
|
[
"US",
"WO"
] |
H01J37/34,C23C14/34,C23C14/35,C23C14/06,C23C14/30,C23C14/54
| 2017-04-07T00:00:00 |
2017
|
[
"H01",
"C23"
] |
high-power resonance pulse ac hedp sputtering source and method for material processing
|
a method of sputtering using a high energy density plasma (hedp) magnetron includes configuring an anode and cathode target magnet assembly in a vacuum chamber with a sputtering cathode target and substrate, applying regulated unipolar voltage pulses to a tunable pulse forming network, and adjusting amplitude and frequency of the unipolar voltage pulses to cause a resonance mode associated with the tunable pulse forming network and an output ac waveform generated from the pulse forming network. the output ac waveform is operatively coupled to the sputtering cathode target, and the output ac waveform includes a negative voltage exceeding the amplitude of the unipolar voltage pulses during sputtering discharge of the hedp magnetron. an increase in the amplitude of the unipolar voltage pulses causes a constant amplitude of the negative voltage of the output ac waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer on the substrate. a corresponding apparatus and computer-readable medium are disclosed.
|
1 . a method of sputtering a layer on a substrate using a high energy density plasma (hedp) magnetron, the method comprising: positioning the hedp magnetron in a vacuum chamber with a sputtering cathode target and the substrate; providing feed gas; applying a plurality of unipolar voltage pulses comprising high frequency voltage oscillations to a pulse forming network, the pulse forming network comprising a plurality of inductors and capacitors; and adjusting an amplitude and a frequency associated with the plurality of unipolar voltage pulses to cause a resonance mode associated with the pulse forming network and an output ac voltage waveform generated from the pulse forming network, the output ac voltage waveform operatively coupled to the sputtering cathode target from the hedp magnetron, the output ac voltage waveform comprising a negative voltage and a positive voltage, an increase in the amplitude of the unipolar voltage pulses causing an increase in amplitude of the positive voltage of the output ac voltage waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer from the hollow cathode target material atoms and ions on the substrate. 2 . the method, as defined by claim 1 , further comprising applying a negative bias voltage to the substrate, thereby attracting positively charged sputtered hollow cathode target material ions to the substrate, a value of the negative bias voltage being in a range of about 0 v to 500 v. 3 . the method, as defined by claim 1 , wherein the sputtering cathode target comprises a hollow cathode shape. 4 . the method, as defined by claim 1 , wherein the feed gas comprises a noble gas, the noble gas comprising at least one of ar, ne, kr, xe, he. 5 . the method, as defined by claim 1 , wherein the feed gas comprises a mixture of a noble gas and a reactive gas, the reactive gas being reactive with target material atoms. 6 . the method, as defined by claim 1 , wherein the feed gas comprises a mixture of a noble gas and a gas that comprises cathode target material atoms. 7 . the method as defined by claim 1 , wherein the sputtering cathode target comprises a flat cathode target shape instead of hollow cathode target shape. 8 . the method, as defined by claim 1 , further comprising rotating the hollow cathode target magnet assembly at a speed in a range of 1 to 400 revolutions per minute. 9 . the method, as defined by claim 1 , wherein the substrate is a semiconductor wafer with a diameter in a range of 25 mm to 450 mm. 10 . the method, as defined by claim 1 , wherein the substrate is a razor blade. 11 . the method, as defined by claim 1 , wherein the substrate comprises a film used to manufacture a memory device. 12 . the method, as defined by claim 1 , further comprising providing the hollow cathode target material comprising at least one of the following elements: b, c, al, si, p, s, ga, ge, as, se, in, sn, sb, te, i, tl, pb, bi, sc, ti, cr, mn, fe, co, ni, cu, zn, y, zr, nb, mo, tc, ru, rh, pd, ag, cd, lu, hf, ta, w, re, os, ir, pt, au, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, be, mg, ca, sr, ba. 13 . the method, as defined by claim 1 , wherein the substrate is a part of car engine, the substrate comprising at least one of a valve, injector head, crank shaft, bushing, bearing, sprocket, cell phone, mobile phone, iphone, ipod, touch screen. 14 . the method, as defined by claim 1 , wherein the substrate is at least one of a cutting tool, drill beat, insert for cutting tool. 15 . an apparatus that sputters a layer on a substrate using a high energy density plasma (hedp) magnetron, the apparatus comprising: an anode; a feed gas; a hedp magnetron comprising a hollow cathode target magnet assembly, the hollow cathode target assembly and the anode configured to be positioned in a vacuum chamber with the substrate; a high-power pulse power supply, the high-power pulse power supply providing a plurality of unipolar negative voltage pulses with high frequency voltage oscillations comprising an amplitude and a frequency of unipolar negative voltage pulses; and a pulse forming network comprising a plurality of inductors and capacitors, the amplitude and the frequency of the plurality of unipolar negative voltage pulses comprising high frequency voltage oscillations adjusted to cause a resonance mode associated with the pulse forming network and an output ac voltage waveforms generated from the pulse forming network, the output ac voltage waveforms operatively coupled to the hollow cathode target assembly, the output ac voltage waveforms comprising a negative voltage and a positive voltage during sputtering discharge of the hedp magnetron, an increase in the amplitude of the unipolar negative pulsed oscillatory voltage waveforms causing an increase in amplitude of the positive voltage of the output ac voltage waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer from the hollow cathode target material atoms and ions on the substrate. 16 . the apparatus, as defined by claim 15 , further comprising a negative bias voltage power supply, the negative bias voltage power supply operatively coupling a negative bias voltage to the substrate, thereby attracting positively charged sputtered hollow cathode target material ions to the substrate, a value of the negative bias voltage being in a range of about 10 v to 500 v. 17 . the apparatus, as defined by claim 15 , wherein a value of a magnetic field disposed parallel to a surface of the hollow sputtering cathode target is in a range of about 150 g to 1000 g. 18 . the apparatus, as defined by claim 15 , wherein the feed gas comprises a noble gas, the noble gas comprising at least one of he, ar, kr, xe, ne. 19 . the apparatus, as defined by claim 15 , wherein the feed gas comprises a mixture of a noble gas and a reactive gas, the reactive gas. 20 . the apparatus, as defined by claim 15 , wherein the feed gas comprises a mixture of a noble gas and a gas that comprises cathode target material atoms. 21 . the apparatus, as defined by claim 15 , wherein the sputtering cathode target has a flat cathode target shape instead of hollow cathode target shape. 22 . the apparatus, as defined by claim 15 , wherein the magnet assembly rotates at a speed in a range of 1 to 400 revolutions per minute. 23 . a method of sputtering a layer on a substrate using a high energy density plasma (hedp) magnetron, the method comprising: positioning an hedp magnetron in a vacuum chamber with a sputtering cathode target and the substrate; providing feed gas; applying a pulsed ac voltage waveform comprising a frequency, amplitude, and duration to a pulse forming network, the pulse forming network comprising a step-up transformer, diode bridge, and a plurality of inductors and capacitors; and adjusting an amplitude and a frequency associated with the pulsed ac voltage waveforms to cause a resonance mode associated with the pulse forming network and an output asymmetric high voltage ac waveform generated from the pulse forming network, the output asymmetric high voltage ac waveform operatively coupled to the sputtering cathode target from hedp magnetron, the output asymmetric high voltage ac waveform comprising a negative voltage and a positive voltage, an increase in the amplitude of the unipolar voltage pulses causing an increase in amplitude of the positive voltage of the output ac voltage waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer from the hollow cathode target material atoms and ions on the substrate. 24 . the method, as defined by claim 23 , further comprising applying a negative bias voltage to the substrate, thereby attracting positively charged sputtered hollow cathode target material ions to the substrate, a value of the negative bias voltage being in a range of about 0 v to 500 v. 25 . the method, as defined by claim 23 , wherein the sputtering cathode target comprises a hollow cathode shape. 26 . a computer-readable medium storing instructions that, when executed by a processing device, perform a method of sputtering a layer on a substrate using a high energy density plasma (hedp) magnetron, the operations comprising: configuring an anode and a cathode target magnet assembly to be positioned in a vacuum chamber with a sputtering hollow cathode target and the substrate; applying plurality of unipolar negative pulsed oscillatory voltage waveforms to a pulse forming network, the pulse forming network comprising a plurality of inductors and capacitors; and adjusting an amplitude and a frequency associated with the plurality of unipolar negative pulsed oscillatory voltage waveforms to cause a resonance mode associated with the pulse forming network and an output ac voltage waveforms generated from the pulse forming network, the output ac voltage waveforms operatively coupled to the sputtering cathode target, the output ac voltage waveforms comprising a negative voltage exceeding an amplitude of the unipolar negative pulsed oscillatory voltage waveforms during sputtering discharge of the hedp magnetron, an increase in the amplitude of the unipolar negative pulsed oscillatory voltage waveforms causing an increase in amplitude of the positive voltage of the output ac voltage waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer from hollow cathode target material atoms and ions on the substrate.
|
cross-reference to related applications this application is a continuation-in-part application of international application no. pct/us17/48438, filed aug. 24, 2017, which claims the benefit of u.s. provisional application no. 62/482,993, filed apr. 7, 2017, the disclosures of which are incorporated by reference herein in their entireties. background field the disclosed embodiments generally relate to a high energy density plasma (hedp) magnetically enhanced sputtering source and a method for sputtering hard thin films on a surface of a substrate. summary the disclosed embodiments relate to a high energy density plasma (hedp) magnetically enhanced sputtering source, apparatus, and method for sputtering hard coatings in the presence of high-power pulse asymmetrical alternating current (ac) voltage waveforms. the high-power pulse asymmetric ac voltage waveform is generated by having a regulated voltage source with variable power feeding a regulated voltage to the high-power pulse supply with programmable pulse voltage duration and pulse voltage frequency producing at its output a train of regulated amplitude unipolar negative voltage pulses with programmed pulse frequency and duration and supplying these pulses to a tunable pulse forming network (pfn) including a plurality of inductors and capacitors for pulse applications connected in a specific format coupled to a magnetically enhanced sputtering source. by adjusting the pulse voltage amplitude, duration, and frequency of the unipolar negative voltage pulses and tuning the values of the inductors and capacitors in the pfn coupled to a magnetically enhanced sputtering source, a resonance pulsed asymmetric ac discharge is achieved. another method to produce a resonance pulsed asymmetric ac discharge is to have fixed unipolar pulse power supply parameters (amplitude, frequency, and duration) feeding a pulse forming network, in which the numerical values of the inductors and capacitors, as well as the configuration can be tuned to achieve the desired resonance values on the hedp source to form a layer on the substrate. the tuning of the pfn can be done manually with test equipment, such as an oscilloscope, voltmeter and current meter or other analytical equipment; or electronically with a built-in software algorithm, variable inductors, variable capacitors, and data acquisition circuitry. the negative voltage from the pulse asymmetric ac voltage waveform generates high density plasma from feed gas atoms and sputtered target material atoms between the cathode sputtering target and the anode of the magnetically enhanced sputtering source. the positive voltage from the pulse asymmetrical ac voltage waveform attracts plasma electrons to the cathode sputtering area and generates positive plasma potential. the positive plasma potential accelerates gas and sputtered target material ions from the cathode sputtering target area towards the substrate that improve deposition rate and increase ion bombardment on the substrate. the reverse electron current during positive voltage can be up to 50% from the discharge current during negative voltage. in some embodiments, the magnetically enhanced sputtering source is a hollow cathode magnetron. the hollow cathode magnetron includes a hollow cathode sputtering target, and the tunable pfn that has a plurality of capacitors and inductors. the resonance mode associated with the tunable pfn is a function of the input unipolar voltage pulse amplitude, duration, and frequency generated by the high-power pulse power supply, inductance, resistance and capacitance of the hollow cathode magnetron or any other magnetically enhanced device, the inductance, capacitance, and resistance of the cables between the tunable pfn and hollow cathode magnetron, and a plasma impedance of the hollow cathode magnetron sputtering source itself as well as the sputtered target material. in some embodiments, rather than the hollow cathode magnetron, a cylindrical magnetron is connected to an output of the tunable pfn. in some embodiments, rather than the hollow cathode magnetron, a magnetron with flat target is connected to the output of the tunable pfn. in the resonance mode, the output negative voltage amplitude of the high-power pulse voltage mode asymmetrical ac waveform on the magnetically enhanced device exceeds the negative voltage amplitude of the input unipolar voltage pulses into the tunable pfn by 1.1-5 times. the unipolar negative high-power voltage output can be in the range of 400v-5000v. in the resonance mode, the absolute value of the negative voltage amplitude of the asymmetrical ac waveform can be in the range of 750-10000 v. in the resonance mode, the output positive voltage amplitude of the asymmetrical ac waveform can be in the range of 100-5000 v. in some cases, the resonance mode of the negative voltage amplitude of the output ac voltage waveform can reach a maximum absolute value while holding all other component parameters (such as the pulse generator output, pfn values, cables and hedp source) constant, wherein a further increase of the input voltage to the tunable pfn does not result in a voltage amplitude increase on the hedp source, but rather an increase in the duration of the negative pulse in the asymmetric ac voltage waveform on the hedp source. sputtering processes are performed with a magnetically and electrically enhanced hedp plasma source positioned in a vacuum chamber. as mentioned above, the plasma source can be any magnetically enhanced sputtering source with a different shape of sputtering cathode target. magnetic enhancement can be performed with electromagnets, permanent magnets, stationary magnets, moveable magnets, and/or rotatable magnets. in the case of a magnetron sputtering source, the magnetic field can be balanced or unbalanced. a typical power density of the hedp sputtering process during a negative portion of the high voltage ac waveform is in the range of 0.1-20 kw/cm 2 . a typical discharge current density of the hedp sputtering process during a negative portion of the high voltage ac waveform is in the range of 0.1-20 a/cm 2 . in the case of the hollow cathode magnetron sputtering source, the magnetic field lines form a magnetron configuration on a bottom surface of the hollow cathode target from the hollow cathode magnetron. magnetic field lines are substantially parallel to the bottom surface of the hollow cathode target and partially terminate on the bottom surface and side walls of the hollow cathode target. the height of the side walls can be in the range of 5-100 mm. due to the presence of side walls on the hollow cathode target, electron confinement is significantly improved when compared with a flat target in accordance with the disclosed embodiments. in some embodiments, an additional magnet assembly is positioned around the walls of the hollow cathode target. in some embodiments, there is a magnetic coupling between additional magnets and a magnetic field forms a magnetron configuration. since the high-power resonance asymmetric ac voltage waveform can generate hedp plasma and, therefore, significant power on the magnetically enhanced sputtering source, the high-power resonance asymmetric ac voltage waveform is pulsed in programmable bursts to prevent damage to the magnetically enhanced sputtering source from excess average power. the programmable duration of the high-power resonance asymmetric ac voltage waveforms pulse bursts can be in the range of 0.1-100 ms. the frequency of the programmable high-power resonance asymmetric ac voltage waveforms pulse bursts can be in the range of 1 hz-10000 hz. in some embodiments, the high-power resonance asymmetric ac voltage waveform is continuous or has a 100% duty cycle assuming the hedp plasma source can handle the average power. the frequency of the pulsed high-power resonance asymmetric ac voltage waveform inside the programmable pulse bursts can be programmed in the range of 100 hz-400 khz with a single frequency or mixed frequency. the magnetically enhanced hedp sputtering source includes a magnetron with a sputtering cathode target, an anode, a magnet assembly, a regulated voltage source connected to a high-power pulsed power supply with programmable output pulse voltage amplitude, frequency, and duration. the pulsed power supply is connected to the input of the tunable pfn, and the output of the tunable pfn is connected to the sputtering cathode target on the magnetically enhanced sputtering source. the tunable pfn, in resonance mode, generates the high-power resonance asymmetrical ac voltage waveforms and provides hedp on the magnetically enhanced sputtering source. the magnetically enhanced high-power pulse resonance asymmetric ac hedp sputtering source may include a hollow cathode magnetron with a hollow cathode sputtering target, a second magnet assembly positioned around the side walls of the hollow cathode target, an electrical switch positioned between the tunable pfn and hollow cathode magnetron with a flat sputtering target rather than a hollow cathode shape, and a magnetic array with permanent magnets, electromagnets, or a combination thereof. the magnetically enhanced high-power pulse resonance asymmetric ac hedp sputtering apparatus includes a magnetically enhanced hedp sputtering source, a vacuum chamber, a substrate holder, a substrate, a feed gas mass flow controller, and a vacuum pump. the magnetically enhanced high-power pulse resonance asymmetric ac hedp sputtering apparatus may include one or more electrically and magnetically enhanced hedp sputtering sources, substrate heater, controller, computer, gas activation source, substrate bias power supply, matching network, electrical switch positioned between the tunable pfn and magnetically enhanced hedp sputtering source, and a plurality of electrical switches connected with a plurality of magnetically enhanced high-power pulse resonance asymmetric ac hedp sputtering sources and output of the tunable pfn. a method of providing high-power pulse resonance asymmetric ac hedp film sputtering includes positioning a magnetically enhanced sputtering source inside a vacuum chamber, connecting the cathode target to the output of the tunable pfn that, in resonance mode, generating the high-power asymmetrical ac waveform, positioning a substrate on a substrate holder, providing feed gas, programming voltage pulses frequency and duration, adjusting pulse voltage amplitude of the programmed voltage pulses with fixed frequency and duration feeding the tunable pfn, generating the output high voltage asymmetrical ac waveform with a negative voltage amplitude that exceeds the negative voltage amplitude of the voltage pulses in the resonance mode, thereby resulting in a high-power pulse resonance asymmetric ac hedp discharge. the method of magnetically enhanced high-power pulse resonance asymmetric ac hedp film sputtering may include positioning an electrical switch between the hollow cathode magnetron and the tunable pfn that, in resonance mode, generates the high voltage asymmetrical ac waveform, applying heat to the substrate or cooling down the substrate, applying direct current (dc) or radio frequency (rf) continuously and/or using a pulse bias voltage to the substrate holder to generate a substrate bias, connecting the tunable pfn that, in resonance mode, generates the high voltage asymmetrical ac waveform simultaneously to the plurality of hollow cathode magnetrons or magnetrons with flat targets, and igniting and sustaining simultaneously hedp in the plurality of the hollow cathode magnetron. the disclosed embodiments include a method of sputtering a layer on a substrate using a high-power pulse resonance asymmetric ac hedp magnetron. the method includes configuring an anode and a cathode target magnet assembly to be positioned in a vacuum chamber with a sputtering cathode target and the substrate, applying high-power negative unipolar voltage pulses with regulated amplitude and programmable duration and frequency to a tunable pfn, wherein the tunable pfn includes a plurality of inductors and capacitors, and adjusting an amplitude associated with the unipolar voltage pulses with programmed duration and frequency to cause a resonance mode associated with the tunable pulse forming network to produce an output high-power pulse resonance asymmetric ac on the hedp sputtering source. the output high-power pulse resonance asymmetric ac voltage waveform from the tunable pfn is operatively coupled to the hedp sputtering cathode target, and the output high-power pulse resonance asymmetric ac voltage waveform includes a negative voltage exceeding or equal to the amplitude of the input unipolar voltage pulses coming to the tunable pfn during the resonance mode and sputtering discharge of the hedp magnetron. with all conditions fixed, any further increase of the amplitude of the unipolar voltage pulses causes only an increase in the duration of the maximum value of the negative voltage amplitude of the output high-power asymmetric ac voltage waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer on the substrate. the disclosed embodiments further include an apparatus that sputters a layer on a substrate using a high-power pulse resonance asymmetric ac hedp magnetron. the apparatus includes an anode, cathode target magnet assembly, regulated high voltage source with variable power, high-power pulse power supply with programmable voltage pulse duration and frequency power supply, and a tunable pfn. the anode and cathode target magnet assembly are configured to be positioned in a vacuum chamber with a sputtering cathode target and the substrate. the high-power pulse power supply generates programmable unipolar negative voltage pulses with defined amplitude, frequency, and duration. the tunable pulse forming network includes a plurality of inductors and capacitors, and the amplitude of the voltage pulses are adjusted to be in the resonance mode associated with the tunable pfn and magnetically enhanced sputtering source for specific programmed pulse parameters, such as amplitude, frequency and duration of the unipolar voltage pulses. the output of the tunable pfn is operatively coupled to the sputtering cathode target, and the output of the tunable pfn in the resonance mode generates a high-power resonance asymmetric ac voltage waveform that includes a negative voltage exceeding the amplitude of the input to tunable pfn unipolar voltage pulses. an ac voltage waveform sustains plasma and forms high-power pulse resonance asymmetric ac hedp magnetron sputtering discharge, thereby causing the hedp magnetron sputtering discharge to form the layer of the sputtered target material on the substrate. the disclosed embodiments also include a computer-readable medium storing instructions that, when executed by a processing device, perform a method of sputtering a layer on a substrate using a high energy density plasma (hedp) magnetron, wherein the operations include configuring an anode and a cathode target magnet assembly to be positioned in a vacuum chamber with a sputtering cathode target and the substrate, applying regulated amplitude unipolar voltage pulses with programmed frequency and duration to the tunable pfn, wherein the pulse forming network includes a plurality of inductors and capacitors, and adjusting a pulse voltage for programmed voltage pulses frequency and duration to cause a resonance mode associated with the tunable pfn. the output asymmetric ac voltage waveform is operatively coupled to the sputtering cathode target, and the output asymmetric ac voltage waveform includes a negative voltage exceeding the amplitude of the regulated unipolar voltage pulses amplitude with programmed frequency and duration during sputtering discharge of the hedp magnetron. a further increase in the amplitude of the regulated unipolar voltage pulses with programmed frequency and duration causes a constant amplitude of the negative voltage of the output ac waveform in response to the pulse forming network being in the resonance mode, thereby causing the hedp magnetron sputtering discharge to form the layer on the substrate. other embodiments will become apparent from the following detailed description considered in conjunction with the accompanying drawings. it is to be understood, however, that the drawings are designed as an illustration only and not as a definition of the limits of any of the embodiments. brief description of the drawings the following drawings are provided by way of example only and without limitation, wherein like reference numerals (when used) indicate corresponding elements throughout the several views, and wherein: fig. 1 (a) shows an illustrative view of a train of output negative unipolar voltage pulses with amplitude v 1 and frequency f 1 from a high-power pulse supply with programmable pulse voltage duration and pulse voltage frequency; fig. 1 (b) shows an illustrative view of an output resonance asymmetrical ac voltage waveform with a duration of negative voltage τ 1 from a tunable pulse forming network (pfn); fig. 1 (c) shows an illustrative view of a train of output negative unipolar voltage pulses with amplitude v 2 and frequency f 1 from a high-power pulse supply with programmable pulse voltage duration and pulse voltage frequency; fig. 1 (d) shows an illustrative view of the output resonance asymmetrical ac voltage waveform with a duration of negative voltage τ 2 from the tunable pfn; fig. 1 (e) shows an illustrative view of the output resonance asymmetrical ac voltage waveform with three oscillations from the tunable pfn; fig. 1 (f) shows an illustrative view of the output resonance asymmetrical ac current waveform with three oscillations from the pfn; fig. 1 (g) shows an illustrative cross-sectional view of components and magnetic field lines of a magnetically enhanced hedp sputtering source with a stationary cathode target magnetic array; fig. 1 (h) shows an illustrative cross-sectional view of a hollow cathode target; fig. 2 (a) shows an illustrative circuit diagram of the high-power pulse resonance ac power supply; fig. 2 (b) shows an illustrative view of a train of unipolar voltage pulses with frequency f 3 and amplitude v 3 applied to the tunable pfn, and an output voltage waveform from the tunable pfn without a resonance mode in the tunable pfn; fig. 2 (c) shows an illustrative view of a train of unipolar voltage pulses with frequency f 4 and amplitude v 4 applied to the tunable pfn, and an output voltage waveform from the tunable pfn in a partial resonance mode; fig. 2 (d) shows an illustrative view of a train of unipolar voltage pulses with frequency f 5 and amplitude v 5 applied to the tunable pfn, and an output resonance asymmetrical ac voltage waveform from the tunable pfn in the resonance mode. fig. 2 (e) shows an illustrative circuit diagram of the tunable pfn when the plurality of inductors and capacitors are connected in series; fig. 2 (f) shows an illustrative circuit diagram of the tunable pfn when inductors and capacitors are connected in parallel; fig. 3 (a) shows an illustrative view of a train of input unipolar negative voltage pulses with two different voltage amplitudes applied to the tunable pfn. fig. 3 (b) shows an illustrative view of output resonance asymmetrical ac voltage waveform pulses with two different voltage amplitudes generated at resonance conditions in the tunable pfn; fig. 4(a) shows an illustrative circuit diagram of the tunable pfn and a plurality of electrical switches; fig. 4 (b) shows a train of resonance asymmetrical ac waveforms applied to different magnetically enhanced sputtering sources; fig. 5 (a) shows an illustrative view of the magnetically enhanced hedp sputtering apparatus; fig. 5 (b) shows different voltage pulse shapes that can be generated by a substrate bias power supply; fig. 5 (c) shows an illustrative view of a via in the semiconductor wafer; fig. 6 (a) shows a train of resonance asymmetrical ac voltage waveforms; fig. 6 (b) shows a plurality of unipolar voltage pulses generated by a pulse dc power supply; fig. 6 (c) shows a plurality of unipolar rf voltage pulses generated by a pulse rf power supply; fig. 7 shows a block diagram of at least a portion of an exemplary machine in the form of a computing system that performs methods according to one or more embodiments disclosed herein; fig. 8 (a) shows an illustrative circuit diagram of a high-power pulse resonance ac power supply with an additional high-frequency power supply; figs. 8 ( b, c, d ) show illustrative views of trains of oscillatory unipolar voltage pulses applied to the tunable pfn, and an output voltage waveform from the tunable pfn without a resonance mode in the tunable pfn; figs. 9 (a, b) show a hollow cathode target combined from two pieces; fig. 10 (a) shows a hollow cathode target combined from two pieces and connected to two different power supplies; fig. 10 (b) shows the voltage output from two high-power pulse resonance ac power supplies; fig. 11 shows an illustrative circuit diagram of the high-power pulse resonance ac power supply that includes a pulse forming network having a transformer and diodes; figs. 12 (a)-(g) show different ac voltage waveforms; fig. 13 shows arc resonance ac discharge current and arc resonance ac discharge voltage waveforms; and figs. 14 (a, b) show output voltage waveforms from the high-power pulse resonance ac power supply when connected to the hedp magnetron and generating hedp discharge. it is to be appreciated that elements in the figures are illustrated for simplicity and clarity. common but well-understood elements that are useful or necessary in a commercially feasible embodiment are not shown in order to facilitate a less hindered view of the illustrated embodiments. detailed description a high energy density plasma (hedp) magnetically enhanced sputtering source includes a hollow cathode magnetron, pulse power supply, and tunable pulse forming network (pfn). the tunable pfn, in resonance mode, generates a high voltage asymmetrical alternating current (ac) waveform with a frequency in the range of 400 hz to 400 khz. the resonance mode of the tunable pfn, as used herein, is a mode in which input negative unipolar voltage pulses with adjusted amplitude, and programmed duration, and frequency generate an output high-power resonance pulse asymmetric ac voltage waveform with negative amplitude that exceeds or is equal to the negative amplitude of the input negative unipolar voltage pulses. further increase of the amplitude of the input negative unipolar voltage pulses from the high-power pulse power supply does not increases the negative amplitude of the output high resonance asymmetric ac voltage waveform, but increases the duration of the maximum value of the negative resonance ac voltage waveform as shown in figs. 1 (a, b, c, d). in some embodiments a further increase of the amplitude of the input negative unipolar voltage pulses from the high-power pulse power supply increases the negative amplitude of the output high resonance asymmetric ac voltage waveform. when the amplitude of the input unipolar negative voltage pulses equals v 1 as shown in fig. 1 (a) at the output of the tunable pfn during the hedp discharge, there is an asymmetrical resonance ac voltage waveform as shown in fig. 1 (b) . the resonance asymmetrical ac voltage waveform has a negative portion v + with a duration τ 1 , and positive portions v 1 + and v 2 + . when the amplitude voltage becomes v 2 and v 2 >v 1 , the amplitude of the resonance negative ac voltage waveform is the same as v 3 , but the duration is τ 2 and τ 2 >τ 1 . a negative portion of the resonance asymmetrical ac voltage waveform generates ac discharge current i 1 and positive voltage generates discharge current i 2 as shown in figs. 1 (e, f) . a negative portion of the high-power asymmetrical resonance ac voltage waveform generates hedp magnetron discharge from feed gas and sputtering target material atoms inside a hollow cathode target due to high discharge voltage and improved electron confinement. during the sputtering process, the hollow cathode target power density is in the range of 0.1 to 20 kw/cm 2 . a positive portion of the high voltage asymmetrical ac voltage waveform provides absorption of electrons from the hedp by the hollow cathode magnetron surface and, therefore, generates a positive plasma potential that causes ions to accelerate towards the hollow cathode target walls and a substrate. the ion energy is a function of the amplitude and duration of the positive voltage. the duration of the maximum absolute value of the negative voltage from the high voltage asymmetrical ac voltage waveform is in the range of 0.001-to 100 ms. the discharge current during the positive voltage of the asymmetrical resonance ac voltage waveform can be in the range of 5-50% of the discharge current during the negative voltage from the ac voltage waveform. the high-power pulse resonance asymmetric ac hedp magnetron sputtering process is substantially different from high-power impulse magnetron sputtering (hipims) due to the resonance ac nature of the discharge generated by the tunable pfn and hedp magnetron discharge. the resonance asymmetrical high-power ac discharge is substantially more stable when compared with hipims discharge. in the resonance mode, the high-power ac voltage waveform can be symmetrical or asymmetrical. for example, for a carbon hollow cathode magnetron, a sputtering process with stable ac discharge current density of about 6 a/cm 2 is obtained. the disclosed embodiments relate to ionized physical vapor deposition (i-pvd) with an hedp sputtering apparatus and method. a sputtering process can be performed with a hollow cathode magnetron sputtering source and direct current (dc) power supply. an example of such an apparatus and sputtering process is described in zhehui wang and samuel a. cohen, hollow cathode magnetron, j. vac. sci. technol., vol. 17, january/february 1999, which is incorporated herein by reference in its entirety. however, these techniques do not address operation of a hollow cathode magnetron sputtering source with a high voltage resonance asymmetrical ac voltage waveform, a method of accelerating ions from the feed gas and sputtering target material atoms by controlling a positive voltage portion of a high-power asymmetrical resonance ac voltage waveform applied to an entirely hollow cathode magnetron, or operation of a pulse power supply and tunable pfn when the tunable pfn is in a resonant mode and generating a high-power resonance asymmetrical ac voltage waveform on a hollow cathode magnetron sputtering source. a magnetically and electrically enhanced hedp sputtering source 100 shown in fig. 1(g) includes a hollow cathode magnetron 101 and a high-power pulse resonance ac power supply 102 , which includes a high-power voltage source 119 , a high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 , and tunable pfn 124 . this tunable pfn, in resonance mode, generates a high-power resonance asymmetrical ac waveform. the hollow cathode magnetron 101 includes a hollow cathode target 103 . the hollow cathode target 103 has side walls 104 and a bottom part 105 as shown in figs. 1 (g), (h) . an anode 106 is positioned around the side walls 104 . magnets 107 , 108 , and magnetic pole piece 109 are positioned inside a water jacket 110 . the water jacket 110 is positioned inside a housing 111 . the hollow cathode target 103 is bonded to a copper backing plate 112 . magnets 107 , 108 and magnetic pole piece 109 generate magnetic field lines 113 , 114 that terminate on the bottom part 105 and form a magnetron configuration. magnetic pole piece 109 is positioned on a supporter 124 . magnetic field lines 115 , 116 terminate on the side walls 104 . water jacket 110 has a water inlet 117 and a water outlet 118 . the water inlet 117 and water outlet 118 are isolated from housing 111 by isolators 121 . water jacket 110 and, therefore, hollow cathode target 101 are connected to a high-power pulse resonance ac power supply 102 . the following chemical elements, or a combination of any two or more of these elements, can be used as a cathode material: b, c, al, si, p, s, ga, ge, as, se, in, sn, sb, te, i, tl, pb, bi, sc, ti, cr, mn, fe, co, ni, cu, zn, y, zr, nb, mo, tc, ru, rh, pd, ag, cd, lu, hf, ta, w, re, os, ir, pt, au, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, be, mg, ca, sr, and/or ba. a combination of these chemical elements with the gases o 2 , n 2 , f, cl, and/or h 2 can also be used as the cathode material. the hollow cathode target magnetic array may have electromagnets rather than permanent magnets. in some embodiments, the electromagnets are positioned around the side walls 104 of the hollow cathode target. these side electromagnets can balance and unbalance the hollow cathode target magnetic array. in some embodiments, the hollow cathode target, during the sputtering process, has a temperature between 20 c and 1000 c. a high target temperature in the range of 0.5-0.7 of the melting target temperature increases the deposition rate since the sputtering yield is a function of the temperature in this temperature range. in some embodiments, a portion of the target material atoms arriving on the substrate is evaporated from the target surface. in some embodiments, the sputtering yield is increased due to high target temperature. the high-power pulse resonance ac power supply 102 includes a regulated voltage source with variable power feeding 119 , a high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 and tunable pfn 124 as shown in fig. 2 (a) . a high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 has a computer 123 and controller 122 . a regulated voltage source with variable power feeding 119 supplies voltage in the range of 400-5000 v to the high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 . the high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 generates a train of unipolar negative voltage pulses to the tunable pfn 124 . the amplitude of the unipolar negative voltage pulses is in the range of 400 to 5000 v, the duration of each of the voltage pulses is in the range of 1 to 100 μs. the distance between voltages pulses can be in the range of 0.4 to 1000 μs, thus controlling the frequency to be between 0.1 to 400 khz. in some embodiments, there is a step-up transformer between the high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 and the tunable pfn 124 . in this case, the high-power pulsed power supply with programmable voltage pulse frequency and amplitude 120 generates a train of ac voltage waveforms coming to the step-up transformer. in some embodiments, there is a diode bridge between the step-up transformer and tunable pfn. the tunable pfn includes a plurality of specialized variable inductors l 1 -l 4 and a plurality of specialized variable capacitors c 1 -c 2 for high-power pulse applications. the value of the inductors and capacitors can be controlled by computer 123 and/or controller 122 . in some embodiments, at least one inductor and/or one capacitor are variable and their values can be computer controlled. the inductors l 1 , l 2 , l 3 , l 4 values can be in the range of 0 to 1000 μh each. capacitors c 1 , c 2 , c 3 , and c 4 have values in the range of 0 to 1000 μf each. the high-power pulse programmable power supply 120 is connected to controller 122 and/or computer 123 . controller 122 and/or computer 123 control output values and timing of the power supply 102 . power supply 102 can operate as a standalone unit without connection to the controller 122 and/or computer 123 . a high-power pulse resonance ac power supply 102 shown in fig. 2(a) includes output current and voltage monitors 125 , 126 , respectively. the current and voltage monitors 125 , 126 are connected to an arc suppression circuit 127 . if the current monitor 125 detects a high current and the voltage monitor 126 detects a low voltage, the arc suppression circuit 127 is activated. it is to be noted that the voltage monitor 126 is connected to an output of the tunable pfn. the arc suppression circuit sends a signal to stop generating incoming voltage pulses to the tunable pfn 124 and connects the output of the tunable pfn through switch 131 to the positive electrical potential generated by power supply 130 in order to eliminate arcing as shown in fig. 2 (a) . the hollow cathode is shown as a c-shaped structure coupled to the output of the tunable pfn 124 . the train of unipolar negative voltage pulses from the high-power pulse programmable power supply 120 is provided to the tunable pfn 124 . depending on the amplitude, duration, and frequency of the input unipolar negative voltage pulses in the train, the output train from the tunable pfn 124 of the unipolar negative voltage pulses can have a different shape and amplitude when compared with input unipolar negative voltage pulses. in non-resonant mode, in the tunable pfn 124 , the input train of negative unipolar pulses forms one negative voltage pulse with an amplitude equivalent to the amplitude of the negative unipolar voltage pulses and a duration equivalent to the duration of the input train of unipolar negative voltage pulses. when connected with the magnetically enhanced sputtering source, this voltage pulse can generate a quasi-static pulse dc discharge. in partial resonance mode, in the tunable pfn 124 , the input train of negative unipolar pulses forms one negative pulse with an amplitude and duration, but with voltage oscillations. the amplitude of these oscillations can be 30-80% of the total voltage amplitude. the frequency of the voltage oscillations is substantially equivalent to the frequency of the input unipolar negative voltage pulses. this mode of operation is beneficial to maintaining a high deposition rate, which is greater than that obtained in full resonance mode, and a high ionization of sputtered target material atoms. in resonance mode, the input train of unipolar negative voltage pulses forms asymmetrical ac voltage waveforms with a maximum negative voltage amplitude that can significantly exceed the voltage amplitude of the input unipolar negative voltage pulses. in some embodiments, in resonance mode, the input train of unipolar negative voltage pulses forms asymmetrical ac voltage waveforms with a maximum negative voltage amplitude that does not exceed the voltage amplitude of the input unipolar negative voltage pulses. the positive amplitude of the ac voltage waveform can reach the absolute value of the negative amplitude and form a symmetrical ac voltage waveform. in fig. 2 (b) , the pulsing unit generates, during time t 1 , a train of unipolar negative voltage pulses with a frequency f 1 and amplitude v 1 . in fig. 2 (c) , the high-power pulse programmable power supply 119 generates, during time t 2 , a train of unipolar negative voltage pulses with a frequency f 2 and amplitude v 2 . in this case, the partial resonance mode exists. the amplitude a of the voltage oscillations is about 30-80% of the voltage amplitude v 2 . at the end of the pulse, the positive voltage pulse 130 can be added by activating a positive voltage power supply connected to the output of the tunable pfn. if the high-power pulse programmable power supply 120 generates unipolar voltage pulses with a frequency f 3 and amplitude v 4 during time t 3 , the resonance mode exists in the pfn 124 . the resonance mode generates asymmetrical ac voltage waveform. the negative voltage amplitude v 5 exceeds the amplitude of the input voltage pulses v 4 as shown in fig. 2 (d) . in some embodiments, the amplitude of the voltage pulses v 4 is −1200 v, amplitude of the negative voltage v 5 is −1720 v. and the amplitude of the positive voltage v 6 is +280 v. in some embodiments, the amplitude of the voltage pulses v 4 is −1500 v, and amplitude of the negative voltage v 5 is −1720 v. the amplitude of the output positive voltage v 6 is +780 v. different tunable pfn that can be used to generate asymmetrical ac voltage waveforms are shown in figs. 2 (e, f) . in some embodiments, the high-power pulse programmable power supply pulsing 120 can generate a train of unipolar negative voltage pulses with different amplitudes v 7 , v 8 and frequencies f 4 , f 5 as shown in fig. 3 (a) . there is a resonance mode in the tunable pfn 124 when the output negative voltage amplitudes v 9 , v 10 exceed the amplitude of the input voltage pulses v 7 , v 8 as shown in fig. 3 (b) . during a negative portion of the asymmetrical ac discharge, a surface of the hollow cathode target 103 emits secondary electrons due to ion bombardment, and during the positive portion of the asymmetrical ac discharge the hollow cathode 103 absorbs electrons. the reduced amount of electrons in the plasma generates a positive plasma potential. this plasma potential accelerates ions towards the substrate. during a reactive sputtering process, positive electrical charge is formed on the hollow cathode target surface 107 due to reactive feed gas interaction with the hollow cathode target surface 107 . the positive voltage of the asymmetrical high voltage ac waveform attracts electrons to the hollow cathode target surface. these electrons discharge a positive charge on top of the cathode target surface 107 and significantly reduce or completely eliminate the probability of arcing. since the electrons are absorbed by the hollow cathode target surface 107 , it is possible to generate positive space charge in the plasma. the positive space charge provides additional energy to the ions in the plasma and leads the ions toward the substrate and hollow cathode target walls. the positive voltage applied to the cathode target surface can attract negative ions that were formed when the negative voltage was applied to the target surface and, therefore, reduce substrate ion bombardment. the tunable pfn 124 can be connected with a plurality of electrical switches 140 - 142 . the switches 140 , 141 , 142 are connected to separate magnetron sputtering sources 150 , 151 , 152 as shown in fig. 4 (a) . for example, during operation, the train 1 of pulses of high voltage ac waveform is directed to the sputtering source 150 , and the train 2 of pulses of high voltage ac waveform is directed to the sputtering source 151 as shown in fig. 4 (b) . in this approach, small size sputtering sources can provide large area sputtering. the hollow cathode magnetron 101 from the magnetically and electrically enhanced hedp sputtering source 100 is mounted inside a vacuum chamber 401 to construct the magnetically and electrically enhanced hedp sputtering apparatus 400 shown in fig. 5 (a) . the vacuum chamber 401 contains feed gas and plasma, and is coupled to ground. the vacuum chamber 401 is positioned in fluid communication with a vacuum pump 402 , which can evacuate the feed gas from the vacuum chamber 401 . typical baseline pressure in the vacuum chamber 401 is in a range of 10 −6 to 10 −9 torr. a feed gas is introduced into the vacuum chamber 401 through a gas inlet 404 from feed gas sources. a mass flow controller 404 controls gas flow to the vacuum chamber 401 . in an embodiment, the vacuum chamber 401 has a plurality of gas inlets and mass flow controllers. the gas flow is in a range of 1 to 1000 sccm depending on plasma operating conditions, pumping speed of a vacuum pump 403 , process conditions, and the like. typical gas pressure in the vacuum chamber 401 during a sputtering process is in a range of 0.5 to 50 mtorr. in some embodiments, a plurality of gas inlets and a plurality of mass flow controllers sustain a desired gas pressure during the sputtering process. the plurality of gas inlets and plurality of mass flow controllers may be positioned in the vacuum chamber 401 at different locations. the feed gas can be a noble gas, such as ar, ne, kr, xe; a reactive gas, such as n 2 , o 2 ; or any other gas suitable for sputtering or reactive sputtering processes. the feed gas can also be a mixture of noble and reactive gases. the magnetically enhanced hedp sputtering apparatus 400 includes a substrate support 408 that holds a substrate 407 or other work piece for plasma processing. the substrate support 408 is electrically connected to a bias voltage power supply 409 . the bias voltage power supply 409 can include a radio frequency (rf) power supply, alternating current (ac) power supply, very high frequency (vhf) power supply, and/or direct current (dc) power supply. the bias power supply 409 can operate in continuous mode or pulsed mode. the bias power supply 409 can be a combination of different power supplies that can provide different frequencies. the negative bias voltage on the substrate is in a range of 0 to −2000 v. in some embodiments, the bias power supply generates a pulse bias with different voltage pulse frequency, amplitude, and shape as shown in fig. 4 (b) . in some embodiments, the voltage is a pulse voltage. the negative substrate bias voltage can attract positive ions to the substrate. the substrate support 408 can include a heater 414 that is connected to a temperature controller 421 . the temperature controller 421 regulates the temperature of the substrate 407 . in an embodiment, the temperature controller 420 controls the temperature of the substrate 407 to be in a range of −100 c to (+1000) c. in some embodiments, the hollow cathode target material is copper and the substrate is a semiconductor wafer that has at least one via or trench. the semiconductor wafer diameter is in the range of 25 to 450 mm. the depth of the via can be between 100 å and 400 μm. the via can have an adhesion layer, barrier layer, and seed layer. typically, the seed layer is a copper layer. the copper layer can be sputtered with the hedp magnetron discharge as shown in fig. 5 (c) . a method of sputtering films, such as hard carbon, includes the following conditions. the feed gas pressure can be in the range of 0.5 to 50 mtorr. the substrate bias can be between 0 v and −120 v. the substrate bias voltage can be continuous or pulsed. the frequency of the pulsed bias can be in the range of 1 hz and 400 khz. the substrate bias can be generated by rf power supply and matching network. the rf frequency can be in the range of 500 khz and 27 mhz. the rf bias can be continuous or pulsed. in embodiment during the deposition the substrate can have a floating potential. the high-power pulse power supply 120 generates a train of negative unipolar voltage pulses with frequency and amplitude that provide a resonance mode in the tunable pfn 124 . in this case, tunable pfn 124 generates the high voltage asymmetrical ac waveform and, therefore, generates hedp discharge. the negative ac voltage can be in the range of −1000 to −10000 v. the duration of the pulse high voltage asymmetrical ac waveforms can be in the range of 1 to 20 msec. the substrate temperature during the sputtering process can be in the range of −100 c and +200 c. the hardness of the diamond like coating formed on the substrate can be in the range of 5 to 70 gpa. the concentration of sp3 bonds in the carbon film can be in the range of 10-80%. in some embodiments, the concentration of sp2 bonds in the carbon film can be in the range of 80 and 100%. in some embodiments, the feed gas is a noble gas such as ar, he, ne, and kr. in some embodiments, the feed gas is a mixture of a noble gas and hydrogen. in some embodiments, the feed gas is a mixture of a noble gas and a gas that contains carbon atoms. in some embodiments, the feed gas is a mixture of a noble gas and oxygen in order to sputter oxygenated carbon films co x for non-volatile memory devices or any other devices. the oxygen gas flow can be in the range of 1-100 sccm. the discharge current density during the sputtering process can be 0.2-20 a/cm 2 . in some embodiments, the amorphous carbon films are sputtered for non-volatile memory semiconductor based devices or for any other semiconductor based devices. in some embodiments, the hollow cathode target material is aluminum. the feed gas can also be a mixture of argon and oxygen, or argon and nitrogen. the feed gases pass through a gas activation source. in some embodiments, feed gasses pass directly to the vacuum chamber. pfn 124 generates the asymmetrical high voltage ac waveform to provide hedp magnetron discharge to sputter hard α-al 2 o 3 or γ-al 2 o 3 coating on the substrate. the substrate temperature during the sputtering process is in the range of 350 to 800 c. hedp magnetron discharge can be used for sputter etching the substrate with ions from sputtering target material atoms and gas atoms. a method of sputter etch processing with argon ions and sputtered target material ions uses high negative substrate bias voltage in the range of −900 to −1200 v. the gas pressure can be in the range of 1 to 50 mtorr. the pulse power supply generates a train of negative unipolar voltage pulses with frequency and amplitude that provide resonance mode in the tunable pfn 124 . in this case, the pfn 124 generates the high voltage asymmetrical ac voltage waveform that provides hedp discharge. for example, a sputter etch process can be used to sharpen or form an edge on a substrate for cutting applications, such as surgical tools, knives, inserts for cutting tools or razor blade for hair removal applications, or for cleaning a substrate by removing impurities to enhance adhesion. hedp magnetron discharge also can be used for ion implantation of ions from sputtered target material atoms into a substrate. for ion implantation, the negative bias voltage on the substrate can be in the range −900-15000 v. an ion implantation example includes the doping of a silicon based device or ion implantation to enhance thin film adhesion to the substrate where the layer is forming. in some embodiments, the electrically enhanced hedp magnetron sputtering source can be used for chemically enhanced i-pvd deposition (ce-ipvd) of metal containing or non-metal films. for example, in order to sputter carbon films with different concentrations of sp3 bonds in the film, the cathode target may be made from carbon material. the feed gas can be a noble gas and carbon atoms containing gas, such as c 2 h 2 , ch 4 , or any other gases. the feed gas can also contain h 2 . carbon films on the substrate are formed by carbon atoms from the feed gas and from carbon atoms from the cathode target. the carbon films on the substrate are formed by carbon atoms from the feed gas. the carbon films sputtered with the electrically enhanced hedp magnetron sputtering source with noble gas, such as argon, neon, helium and the like, or reactive gas, such as hydrogen, nitrogen, oxygen, and the like can be used for hard mask applications in etch processes, such as 3 d nand; for protectively coating parts, such as bearings, camshafts, gears, fuel injectors, cutting tools, inserts for cutting tools, carbide inserts, drill bits, broaches, reamers, razor blades for surgical applications and hair removal, hard drives, solar panels, optical filters, flat panel displays, thin film batteries, batteries for storage, hydrogen fuel cell, cutleries, jewelry, wrist watch cases and parts, coating metal on plastic parts such as lamps, air vents in cars, aerospace applications, such as turbine blades and jet engine parts, jewelry, plumbing parts, pipes, and tubes; medical implants, such as stents, joints, cell phone, mobile phone, iphone, ipod, touch screen, hand held computing devices, application specific integration circuits and the like. the carbon films sputtered with the electrically enhanced hedp magnetron sputtering source can be used to sputter thin ta-c and co x films for carbon based resistive memory devices. in some embodiments, the hedp magnetron discharge with a carbon target is used to grow carbon nanotubes. in some embodiments, these nanotubes are used to build memory devices. during the hedp sputtering process, when the high-power pulse asymmetric ac voltage waveform is applied to the magnetically enhanced sputtering source, a pulse bias voltage can be applied to the substrate to control ion bombardment of the growing film. in some embodiments, during the hedp sputtering process, when the high-power pulse asymmetric ac voltage waveform is applied to the magnetically enhanced sputtering source, a pulse bias voltage can be applied to the substrate to control ion bombardment of the growing film. the amplitude of the negative voltage can be in the range of −10 v and −200 v. trains of asymmetrical ac voltage waveforms 602 are shown in fig. 6 (a) . trains of negative voltage pulses 603 applied to the substrate are shown in fig. 6 (b) . in order to control time t 1 when bias voltage pulse is applied to the substrate, the high-power pulse resonance ac power supply and bias power supply are synchronized. in this case, the controller from the high-power pulse resonance ac power supply sends synchronization pulses that correspond to the trains of asymmetrical ac voltage waveforms to the controller from the bias power supply. the bias power supply controller can set time δt 1 in the range of 0-1000 μs. in some embodiments, the bias power supply includes an rf power supply. fig. 6 (c) shows a train of rf pulses 604 generated by the rf bias power supply. the method of generating resonance ac voltage waveforms for the magnetically enhanced sputtering source can also be used to generate resonance ac waveforms for the cathodic arc evaporation sources that have widespread applications in the coating industry. resonance ac voltage wave waveforms, when connected with a magnetically enhanced sputtering source, generate volume discharge. resonance ac voltage waveforms, when connected with an arc evaporation source, generate point arc discharge. dc power supplies generate and sustain continuous arc discharge on an arc evaporation source with a carbon target. the arc current can be in the range of 40-100 a. the arc discharge voltage can be in the range of 20-120 v. a regulated voltage with a variable power source feeds the high-power pulse programmable power supply. specifically, the high-power pulse asymmetric ac voltage waveform is generated by having the regulated voltage source with variable power feeding a regulated voltage to the high-power pulse supply with programmable pulse voltage duration and pulse voltage frequency producing at its output a train of regulated amplitude unipolar negative voltage pulses with programmed pulse frequency and duration, and supplying these pulses to a tunable pulse forming network (pfn) including a plurality of specialized inductors and capacitors designed for pulse applications connected in a specific configuration coupled to an arc evaporation source. the resonance occurs in the pfn and in the already existing arc discharge generated by the dc power supply. by adjusting the pulse voltage amplitude, duration, and frequency of the unipolar negative voltage pulses and tuning the values of the inductors and capacitors in the pfn coupled to an arc evaporation source, a resonance pulsed asymmetric ac arc discharge can be achieved. another method of producing a resonance pulsed asymmetric ac arc discharge is to have fixed unipolar pulse power supply parameters (amplitude, frequency, and duration) feeding a pulsed forming network, in which the numerical values of the inductors and capacitors, as well as their configurations are tuned to achieve the desired resonance values on the arc evaporation source to form a layer on the substrate. the tuning of the pfn can be performed manually with test equipment, such as an oscilloscope, voltmeter, and current meter or other analytical equipment; or electronically with a built-in software algorithm, variable inductors, variable capacitors, and data acquisition circuitry. the negative voltage from the pulse asymmetric ac voltage waveform generates high density plasma from the evaporated target material atoms between the cathode target and the anode of the arc evaporation source. the positive voltage from the pulse asymmetrical ac voltage waveform attracts plasma electrons to the cathode area and generates positive plasma potential. the positive plasma potential accelerates evaporated target material ions from the cathode target area towards the substrate that improve deposition rate and ion bombardment on the substrate. the reverse electron current can be up to 50% from the discharge current during the negative voltage. in some embodiments, the arc evaporation source may have one of a rotatable magnetic field, movable magnetic field, or stationary magnetic field. the tunable pfn includes a plurality of capacitors and inductors. the resonance mode associated with the tunable pfn is a function of the input unipolar voltage pulse amplitude, duration, and frequency generated by the high-power pulse power supply; inductance, resistance, and capacitance of the arc evaporation source, or any other magnetically enhanced arc evaporation source; the inductance, capacitance, and resistance of the cables between the tunable pfn and arc evaporation source; and a plasma impedance of the arc evaporation source itself as well as the evaporated material. in the resonance mode, the output negative voltage amplitude of the high-power pulse voltage mode asymmetrical ac waveform on the arc evaporation source exceeds the negative voltage amplitude of the input unipolar voltage pulses into the tunable pfn by 1.1-5 times. the unipolar negative high-power voltage output can be in the range of 400v-5000v. in the resonance mode, the absolute value of the negative voltage amplitude of the asymmetrical ac waveform can be in the range of 750-5000 v. in the resonance mode, the output positive voltage amplitude of the asymmetrical ac waveform can be in the range of 100-2500 v. in the resonance mode, the negative voltage amplitude of the output ac waveform can reach a maximum absolute value at which point a further increase of the input voltage to the tunable pfn will not result in a voltage amplitude increase, but rather an increase in duration of the negative pulse in the asymmetric ac waveform. in some embodiments, in the resonance mode, the negative voltage amplitude of the output ac waveform can reach a maximum absolute value, at which point a further increase of the input voltage to the tunable pfn will result in a positive voltage amplitude increase. in some embodiments, the frequency of the unipolar voltage pulses is in the range of 1 khz and 10 khz. in some embodiments, the duration of the unipolar voltage pulses is in the range of 3-20 μs. asymmetrical ac voltage waveforms significantly influence the size on of the cathode arc spot and velocity. in some embodiments, generation of the resonance ac voltage waveforms reduce the formation of macro particles from evaporated cathode target material. the arc discharge current during the negative portion of the ac voltage can be in the range of 200-3000 a. the arc discharge current during the positive portion of the ac voltage has a lower value and can be in the range of 10-500 a. the arc ac discharge current and arc discharge ac voltage waveforms are shown in fig. 13 . in an embodiment, a high-power pulse resonance ac power supply 700 , as compared with the high-power pulse resonance ac power supply 102 shown in fig. 1(g) , includes a high frequency high-power pulsed power supply 701 with a programmable voltage pulse frequency and amplitude as shown in fig. 8 (a) . the high frequency high-power pulsed power supply 701 generates pulse negative, unipolar oscillatory voltage waveforms with a frequency in the range of 100 khz to 5 mhz and a duration t 1 in a range of 5 μs to 20 μs. the absolute value of the voltage of these waveforms is in a range of 500 v to 5000 v. the frequency of these pulses with negative unipolar voltage waveforms is in a range of 5 hz to 200 khz. pulse negative unipolar oscillatory voltage waveforms 800 are shown in fig. 8 (b) . the tunable pfn 124 , which is in resonance mode for these pulses, generates a high-power resonance asymmetrical ac waveform. the resonance mode can be achieved by adjusting the values of inductors l 1 , l 2 , l 3 , and l 4 , and by adjusting the values of capacitors c 1 and c 2 for a particular shape of the pulse negative unipolar oscillatory voltage waveforms, their frequency, type of process gas, target material, and magnetic field strength of the hollow cathode sputtering source 702 . the resonance mode is defined as the prevailing conditions when the adjustment of the frequency and amplitude of the plurality of negative unipolar oscillatory voltage waveforms 800 generate the plurality of asymmetrical ac voltage waveforms 801 with positive v+ and negative v− voltages shown in figs. 8 (b, c) . further increase of the oscillatory voltage waveform amplitude causes an increase in the value of the positive portion of the ac voltage waveform. by adjusting time t 1 , rt 2 , or both t 1 and t 2 , double negative peak asymmetrical ac voltage waveforms 802 can be achieved as shown in fig. 8 (d) . in an embodiment, a magnetically and electrically enhanced hedp sputtering source 100 shown in fig. 1(g) has a hollow cathode target 103 that includes two parts as shown in fig. 9 (a) and fig. 9 (b) . fig. 9 (a) shows the hollow cathode target 103 that includes pieces 703 and 705 . these two pieces are attached to a copper baking plate by a clamp 704 . fig. 9 (b) shows the hollow cathode target that includes pieces 707 and 708 . these two pieces are bonded to a copper baking plate 706 . the magnetically and electrically enhanced hedp sputtering source can have a diameter in the range of 1 cm to 100 cm. the peak power density can be in the range of 100 w/cm 2 to 20 kw/cm 2 . the average power density can be in the range of 50 w/cm 2 to 150 w/cm 2 . in an embodiment, the hollow cathode target 103 includes two pieces 710 and 709 as shown in fig. 10 (a) . the piece 709 has magnetic field lines 715 and the piece 710 has magnetic field lines 714 . each of these pieces is connected to different high-power pulse resonance ac power supplies 711 and 712 . the block diagram of these high-power pulse resonance ac power supplies is shown in fig. 8 (a) . the high-power pulse resonance ac power supplies 711 and 712 generate ac voltage waveforms 715 and 716 shown in figs. 10 (a) and 10 ( b ). a time shift between negative voltage peaks 717 and 718 is controlled by controller 719 . in an embodiment, the power supply 711 sends a synchro pulse to power supply 712 to initiate the start of power supply 712 . in an embodiment, the power supply 712 sends a synchro pulse to power supply 711 to initiate the start of power supply 711 . in an embodiment, a magnetically enhanced hedp sputtering source that is shown in fig. 1 (g) includes an additional magnetic assembly positioned adjacent to the side walls 104 as shown in fig. 1 (h) . the magnetic assembly may have permanent magnets, electromagnets, or a combination of permanent magnets and electromagnetics. the method of generating resonance ac voltage waveforms for the magnetically enhanced sputtering source and high-power pulse resonance ac power supply 700 can also be used to generate resonance ac waveforms for cathodic arc evaporation sources. high-power pulse resonance ac power supply 700 can be used for all applications in which the high-power pulse resonance ac power supply 102 can be used. in an embodiment, a high-power pulse resonance ac power supply 810 includes an ac power supply 811 and pfn 812 as shown in fig. 11 . high-power ac power supply 811 can generate different ac voltage waveforms at the output as shown in figs. 12 (a, b, c, d, e, f). the frequency of these voltage waveforms can be in the range of 3 khz to 100 khz. the peak voltage amplitude can be in the range of 100 v to 1000 v. the pfn includes a step-up transformer 813 , a diode bridge 814 , a plurality of inductors 815 , 816 , 817 , 818 and a plurality of capacitors 819 and 820 . this pfn converts ac voltage waveforms to an asymmetrical complex ac voltage waveform during the resonance mode as shown in fig. 11 . ac voltage waveforms and frequencies that correspond to this particular ac voltage waveform are associated with specific values of inductors ( 815 , 816 , 817 and 818 ) and capacitors ( 819 , 820 ) in order to generate the resonance mode and form, at the output, the asymmetrical ac voltage waveform. in an embodiment, the pfn does not have a diode bridge. in an embodiment, the high-power pulse resonance ac power supply can be connected to the hedp magnetron sputtering source and rf power supply simultaneously. the frequency of the rf power supply can be in the range of 500 khz to 30 mhz. the rf power supply can operate in continuous mode or pulsed mode. in an embodiment, the rf power supply turns on before on the high-power pulse resonance ac power supply turns on (roman, is this correct? yes) in order to provide stable plasma ignition for plasma that will be generated with the high-power pulse resonance ac power supply. the rf power supply can be turned off after the high-density plasma is generated. in an embodiment, the rf power supply operates in continuous mode together with the high-power pulse resonance ac power supply. this operation reduces parasitic arcs during the reactive sputtering process. this operation is beneficial for sputtering ceramic target materials and target materials with low electrical conductivity such as those containing b, si, and the like. the output voltage waveforms from the high-power pulse resonance ac power supply are shown in fig. 14s ( a, b ). the second negative peak 812 can be generated by controlling parameters of the pfn, such as inductors, capacitors and the transformer (if applicable) as shown in fig. 14 (a) . the peak 812 has a significant influence on the probability of generating arcs during reactive sputtering. the plasma that is generated during this peak helps to ignite high density plasma during the first negative peak 811 . the second peak 812 may be triangular, sinusoidal or rectangular in shape. the rectangular shape of the second negative peak 814 is shown in fig. 14 (b) . the value and duration of the peak 812 helps to control the energy of ions coming to the substrate. the duration t s can be in the range of 2 μs to 50 μs. the amplitude v s can be in the range of 200 v to 1000 v. the greater the amplitude and/or duration of the second peak is, the less the ion energy will be. this arrangement is of particular importance for sputtering ta-c films when high ion energy can affect the structure of the growing film. one or more embodiments disclosed herein, or a portion thereof, may make use of software running on a computer or workstation. by way of example, only and without limitation, fig. 7 is a block diagram of an embodiment of a machine in the form of a computing system 900 , within which is a set of instructions 902 that, when executed, cause the machine to perform any one or more of the methodologies according to embodiments of the invention. in one or more embodiments, the machine operates as a standalone device; in one or more other embodiments, the machine is connected (e.g., via a network 922 ) to other machines. in a networked implementation, the machine operates in the capacity of a server or a client user machine in a server-client user network environment. exemplary implementations of the machine as contemplated by embodiments of the invention include, but are not limited to, a server computer, client user computer, personal computer (pc), tablet pc, personal digital assistant (pda), cellular telephone, mobile device, palmtop computer, laptop computer, desktop computer, communication device, personal trusted device, web appliance, network router, switch or bridge, or any machine capable of executing a set of instructions (sequential or otherwise) that specify actions to be taken by that machine. the computing system 900 includes a processing device(s) 904 (e.g., a central processing unit (cpu), a graphics processing unit (gpu), or both), program memory device(s) 906 , and data memory device(s) 908 , which communicate with each other via a bus 910 . the computing system 900 further includes display device(s) 912 (e.g., liquid crystal display (lcd), flat panel, solid state display, or cathode ray tube (crt)). the computing system 900 includes input device(s) 914 (e.g., a keyboard), cursor control device(s) 916 (e.g., a mouse), disk drive unit(s) 918 , signal generation device(s) 920 (e.g., a speaker or remote control), and network interface device(s) 924 , operatively coupled together, and/or with other functional blocks, via bus 910 . the disk drive unit(s) 918 includes machine-readable medium(s) 926 , on which is stored one or more sets of instructions 902 (e.g., software) embodying any one or more of the methodologies or functions herein, including those methods illustrated herein. the instructions 902 may also reside, completely or at least partially, within the program memory device(s) 906 , the data memory device(s) 908 , and/or the processing device(s) 904 during execution thereof by the computing system 900 . the program memory device(s) 906 and the processing device(s) 904 also constitute machine-readable media. dedicated hardware implementations, such as but not limited to asics, programmable logic arrays, and other hardware devices can likewise be constructed to implement methods described herein. applications that include the apparatus and systems of various embodiments broadly comprise a variety of electronic and computer systems. some embodiments implement functions in two or more specific interconnected hardware modules or devices with related control and data signals communicated between and through the modules, or as portions of an asic. thus, the example system is applicable to software, firmware, and/or hardware implementations. the term “processing device” as used herein is intended to include any processor, such as, for example, one that includes a cpu (central processing unit) and/or other forms of processing circuitry. further, the term “processing device” may refer to more than one individual processor. the term “memory” is intended to include memory associated with a processor or cpu, such as, for example, ram (random access memory), rom (read only memory), a fixed memory device (for example, hard drive), a removable memory device (for example, diskette), a flash memory and the like. in addition, the display device(s) 912 , input device(s) 914 , cursor control device(s) 916 , signal generation device(s) 920 , etc., can be collectively referred to as an “input/output interface,” and is intended to include one or more mechanisms for inputting data to the processing device(s) 904 , and one or more mechanisms for providing results associated with the processing device(s). input/output or i/o devices (including but not limited to keyboards (e.g., alpha-numeric input device(s) 914 , display device(s) 912 , and the like) can be coupled to the system either directly (such as via bus 910 ) or through intervening input/output controllers (omitted for clarity). in an integrated circuit implementation of one or more embodiments of the invention, multiple identical die are typically fabricated in a repeated pattern on a surface of a semiconductor wafer. each such die may include a device described herein, and may include other structures and/or circuits. the individual dies are cut or diced from the wafer, then packaged as integrated circuits. one skilled in the art would know how to dice wafers and package die to produce integrated circuits. any of the exemplary circuits or method illustrated in the accompanying figures, or portions thereof, may be part of an integrated circuit. integrated circuits so manufactured are considered part of this invention. an integrated circuit in accordance with the embodiments of the present invention can be employed in essentially any application and/or electronic system in which buffers are utilized. suitable systems for implementing one or more embodiments of the invention include, but are not limited, to personal computers, interface devices (e.g., interface networks, high-speed memory interfaces (e.g., ddr3, ddr4), etc.), data storage systems (e.g., raid system), data servers, etc. systems incorporating such integrated circuits are considered part of embodiments of the invention. given the teachings provided herein, one of ordinary skill in the art will be able to contemplate other implementations and applications. in accordance with various embodiments, the methods, functions or logic described herein is implemented as one or more software programs running on a computer processor. dedicated hardware implementations including, but not limited to, application specific integrated circuits, programmable logic arrays and other hardware devices can likewise be constructed to implement the methods described herein. further, alternative software implementations including, but not limited to, distributed processing or component/object distributed processing, parallel processing, or virtual machine processing can also be constructed to implement the methods, functions or logic described herein. the embodiment contemplates a machine-readable medium or computer-readable medium containing instructions 902 , or that which receives and executes instructions 902 from a propagated signal so that a device connected to a network environment 922 can send or receive voice, video or data, and to communicate over the network 922 using the instructions 902 . the instructions 902 are further transmitted or received over the network 922 via the network interface device(s) 924 . the machine-readable medium also contains a data structure for storing data useful in providing a functional relationship between the data and a machine or computer in an illustrative embodiment of the systems and methods herein. while the machine-readable medium 902 is shown in an example embodiment to be a single medium, the term “machine-readable medium” should be taken to include a single medium or multiple media (e.g., a centralized or distributed database, and/or associated caches and servers) that store the one or more sets of instructions. the term “machine-readable medium” shall also be taken to include any medium that is capable of storing, encoding, or carrying a set of instructions for execution by the machine and that cause the machine to perform anyone or more of the methodologies of the embodiment. the term “machine-readable medium” shall accordingly be taken to include, but not be limited to: solid-state memory (e.g., solid-state drive (ssd), flash memory, etc.); read-only memory (rom), or other non-volatile memory; random access memory (ram), or other re-writable (volatile) memory; magneto-optical or optical medium, such as a disk or tape; and/or a digital file attachment to e-mail or other self-contained information archive or set of archives is considered a distribution medium equivalent to a tangible storage medium. accordingly, the embodiment is considered to include anyone or more of a tangible machine-readable medium or a tangible distribution medium, as listed herein and including art-recognized equivalents and successor media, in which the software implementations herein are stored. it should also be noted that software, which implements the methods, functions and/or logic herein, are optionally stored on a tangible storage medium, such as: a magnetic medium, such as a disk or tape; a magneto-optical or optical medium, such as a disk; or a solid-state medium, such as a memory automobile or other package that houses one or more read-only (non-volatile) memories, random access memories, or other re-writable (volatile) memories. a digital file attachment to e-mail or other self-contained information archive or set of archives is considered a distribution medium equivalent to a tangible storage medium. accordingly, the disclosure is considered to include a tangible storage medium or distribution medium as listed herein and other equivalents and successor media, in which the software implementations herein are stored. although the specification describes components and functions implemented in the embodiments with reference to particular standards and protocols, the embodiments are not limited to such standards and protocols. the illustrations of embodiments described herein are intended to provide a general understanding of the structure of various embodiments, and they are not intended to serve as a complete description of all the elements and features of apparatus and systems that might make use of the structures described herein. many other embodiments will be apparent to those of skill in the art upon reviewing the above description. other embodiments are utilized and derived therefrom, such that structural and logical substitutions and changes are made without departing from the scope of this disclosure. figures are also merely representational and are not drawn to scale. certain proportions thereof are exaggerated, while others are decreased. accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense. such embodiments are referred to herein, individually and/or collectively, by the term “embodiment” merely for convenience and without intending to voluntarily limit the scope of this application to any single embodiment or inventive concept if more than one is in fact shown. thus, although specific embodiments have been illustrated and described herein, it should be appreciated that any arrangement calculated to achieve the same purpose are substituted for the specific embodiments shown. this disclosure is intended to cover any and all adaptations or variations of various embodiments. combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description. in the foregoing description of the embodiments, various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. this method of disclosure is not to be interpreted as reflecting that the claimed embodiments have more features than are expressly recited in each claim. rather, as the following claims reflect, inventive subject matter lies in less than all features of a single embodiment. thus, the following claims are hereby incorporated into the detailed description, with each claim standing on its own as a separate example embodiment. the abstract is provided to comply with 37 c.f.r. § 1.72(b), which requires an abstract that will allow the reader to quickly ascertain the nature of the technical disclosure. it is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. in addition, in the foregoing detailed description, it can be seen that various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. this method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. rather, as the following claims reflect, inventive subject matter lies in less than all features of a single embodiment. thus, the following claims are hereby incorporated into the detailed description, with each claim standing on its own as separately claimed subject matter. although specific example embodiments have been described, it will be evident that various modifications and changes are made to these embodiments without departing from the broader scope of the inventive subject matter described herein. accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense. the accompanying drawings that form a part hereof, show by way of illustration, and without limitation, specific embodiments in which the subject matter are practiced. the embodiments illustrated are described in sufficient detail to enable those skilled in the art to practice the teachings herein. other embodiments are utilized and derived therefrom, such that structural and logical substitutions and changes are made without departing from the scope of this disclosure. this detailed description, therefore, is not to be taken in a limiting sense, and the scope of various embodiments is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled. given the teachings provided herein, one of ordinary skill in the art will be able to contemplate other implementations and applications of the techniques of the disclosed embodiments. although illustrative embodiments have been described herein with reference to the accompanying drawings, it is to be understood that these embodiments are not limited to the disclosed embodiments, and that various other changes and modifications are made therein by one skilled in the art without departing from the scope of the appended claims.
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069-080-562-128-142
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US
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[
"US"
] |
G01N33/26,G01N33/28,G01F1/56,G01N25/00,G01N27/22
| 2014-08-12T00:00:00 |
2014
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[
"G01"
] |
system and method for measuring separation rate of water from water-in-crude oil emulsions
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system and method relates to measuring separation rate of water from water-in-crude oil emulsions at elevated temperature. the system includes an electrolytic interface (conductivity) cell comprising a plurality of capacitance/conductance probes disposed at different heights in a fluid stream disposed within the interface cell and an analyzer. logic of the analyzer determines the separation rate based on signals received from the plurality of capacitance/conductance probes in the interface cell that are coupled to monitor the fluid stream. methods for making and using the system are also disclosed.
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1. a method, comprising: measuring electrolytic conductivity of two or more capacitance/conductance probes disposed in a fluid stream at different heights from an inner bottom surface of an interface cell having a known geometry; determining an approximate location of an oil-water interface based on conductivity data from the two or more capacitance/conductance probes; determining separation data for the fluid stream based on the approximate location of the oil-water interface and the known geometry of the interface cell; and determining a separation rate based on a slope of the separation data for the fluid stream. 2. the method of claim 1 , wherein determining an approximate location comprises determining a time at which an oil-water interface passes a tip of each of the two or more capacitance/conductance probes. 3. the method of claim 2 , wherein determining separation data comprises determining the separation data based on the approximate location of the oil-water interface at discrete times and the known geometry of the interface cell. 4. the method of claim 1 , further comprising directing at least part of a water-in-crude-oil emulsion flow from an inlet to a desalter to provide the fluid stream or sample. 5. the method of claim 1 , further comprising directing at least part of a water-in-crude-oil emulsion flow from an analyzer loop coupled in fluid communication with flow at a desalter to provide the fluid stream within the analyzer loop. 6. the method of claim 1 , further comprising initiating conductivity measurements from the two or more capacitance/conductance probes when temperature of the fluid stream or sample is above a threshold value. 7. the method of claim 1 , further comprising tagging the separation rate if pressure of the fluid stream or sample is above a threshold value. 8. the method of claim 1 , further comprising tagging the separation rate if flow rate of the fluid stream is below a threshold value. 9. the method of claim 1 , further comprising outputting the separation rate to a display. 10. the method of claim 1 , wherein the interface cell comprises: an interface chamber having a first base shape and a first height, wherein the first base shape is selected from the group consisting of square, rectangular, circular and ellipse; and a first interface cell cover having a same first base shape as the interface cell chamber and a second height, wherein one or more holes extend through the first interface cover, wherein the first interface cell cover is fastened to the interface cell chamber; the two or more capacitance/conductance probes are disposed through the one or more holes in the first interface cell cover; the fluid stream comprises a water-in-crude oil emulsion, and further comprising a computer for determining the separation rate of water from the water-in-crude-oil emulsion based on one or more signals received from the two or more capacitance/conductance probes disposed at different heights from an inner bottom surface of the interface cell. 11. the method of claim 10 , wherein the interface chamber comprises: an interface sleeve having a first end and a second end, wherein the first end has the same base shape as the first interface cover, the second end has a second base shape and a third height, wherein the second base shape is selected from the group consisting of square, rectangular, circular and ellipse; and a second interface cell cover having the same second base shape as the second end of the interface cell sleeve and a fourth height, wherein the second interface cell cover is fastened to the second end of the interface cell sleeve. 12. the method of claim 11 , wherein the second base shape is smaller than the first base shape such that the sides of the interface cell taper towards the second base shape. 13. the method of claim 10 , wherein the interface cell chamber and the first interface cell cover are constructed from a metal, a plastic or a combination thereof. 14. the method of claim 10 , wherein the interface cell chamber and the first interface cell cover are constructed from a metal selected from the group consisting of carbon steel, stainless steel, stainless steel alloys and combinations thereof. 15. the method of claim 10 , wherein the interface cell chamber and the first interface cell cover are constructed of a plastic selected from the group consisting of polyether ketone (peek), polymethylene, polytetrafluorethylene (ptfe), other high-temperature polymers and combinations thereof. 16. the method of claim 10 , wherein the interface cell chamber and the first interface cell cover are constructed from carbon steel pipe and fittings. 17. the method of claim 1 , wherein the capacitance/conductance probes are constructed from a conductive metal. 18. the method of claim 17 , wherein the conductive metal is selected from the group consisting of aluminum, copper, nickel, silver, tungsten, zinc, and combinations thereof. 19. the method of claim 1 , wherein the capacitance/conductance probes are constructed from 1 mm tungsten welding rods. 20. the method of claim 1 , wherein the capacitance/conductance probes are spaced at about 0.1-inch (0.254 cm) apart. 21. the method of claim 10 , wherein a first hole extends into the interface cell chamber from an outer, upper surface, a second hole opposing the first hole extends into the interface cell chamber from an outer, lower surface; wherein the first hole is fluidically connected to an inlet, and the second hole is fluidically connected to an outlet. 22. the method of claim 10 , wherein the two or more capacitance/conductance probes are held in place with a metal fitting, a plastic fitting or a combination thereof. 23. the method of claim 10 , wherein the two or more capacitance/conductance probes are held in place with a gland fitting. 24. the method of claim 10 , wherein the two or more capacitance/conductance probes are held in place using an adhesive. 25. the method of claim 10 , wherein the interface cell is disposed along an inlet to a desalter such that the fluid stream or sample contains at least a part of the water-in-crude-oil emulsion. 26. the method of claim 10 , wherein the interface cell is disposed along an analyzer loop coupled in fluid communication with flow of a water-in-crude oil emulsion to produce the fluid stream within the analyzer loop. 27. the method of claim 10 , further comprising a temperature sensor coupled to measure temperature of the fluid stream or sample, wherein the analyzer initiates a separation rate determination when the measured fluid stream or sample temperature reaches a target value. 28. the method of claim 10 , further comprising a pressure sensor coupled to measure pressure of the fluid stream or sample, wherein the analyzer tags any determination of the separation rate in which the measured pressure is above a threshold value. 29. the method of claim 10 , further comprising a flow meter coupled to measure flow rate of the fluid stream, wherein the analyzer tags any determination of the separation rate in which the measured flow rate is below a threshold value. 30. the method of claim 10 , wherein the analyzer outputs the separation rate to a display.
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prior related applications this application claims benefit of u.s. provisional patent application ser. no. 62/036,301, filed on aug. 12, 2014. federally sponsored research statement n/a reference to microfiche appendix n/a field of invention the invention relates to an automated system and method for measuring oil/water separation rate, and, in particular, to a system and method for measuring separation rate of water from water-in-crude oil emulsions at elevated temperatures and/or pressures. background of the invention measurement of the separation rate of water from water-in-crude oil emulsions is critical for evaluating performance of a chemical demulsifier used for desalting and dehydration of crude oils in the refining industry. for successful operation of desalting and dehydration processes in a refinery, the best demulsifier chemical must be chosen from a pool of candidate chemicals, often from different supplier companies. evaluation of demusifiers is further complicated due to relatively low experimental conditions (i.e., below about 195° f. (90° c.)) of most laboratory methods compared to the much higher operating conditions (i.e., about 230° f. (110° c.) to about 300° f. (149° c.)) of most commercial desalters and dehydrators. therefore, real-world performance of candidate demulsifiers cannot be reliably predicted based on laboratory results at experimental conditions (i.e., below about 195° f.) and must be determined through expensive field trials at commercial operating conditions (i.e., about 230° f. to about 300° f.). the industry standard for laboratory evaluation of demulsifiers is commonly referred to as a “bottle test.” the bottle test (and its variants) involves monitoring the amounts of water separated from a chemically treated emulsion as a function of time. such measurements are made in glass bottles/tubes with volumetric markings. the separated water settles at the bottom of the glass bottle/tube and forms an interface with the emulsion on top. the amount of water that has separated is estimated periodically by visual inspection of the interface against the volumetric marks. the demulsifier that causes the fastest water separation at experimental conditions (i.e., below about 195° f.) is assumed to be a good candidate for an expensive field trial at operating conditions (i.e., about 230° f. to about 300° f.), which is much higher than the experimental conditions (i.e., below about 195° f.). the bottle test has at least three disadvantages: 1) it cannot be performed safely at temperatures above about 195° f. due to resulting high pressures, 2) it requires determination of real-world performance of candidate demulsifiers through expensive field trials at commercial operating conditions (i.e., about 230° f. to about 300° f.), and 3) it cannot be automated. in another laboratory method, a single immersed capacitance/conductance probe is used to measure emulsion stability by measuring the amount of water that has separated from oil indirectly. 1 basically, a water layer is carefully laid down at the bottom of a vessel and an emulsion is carefully spread on top of the bottom water layer. the probe level is set so that conductance is measured in the bottom water layer. as water separates, the separated water becomes part of the bottom water layer. if the salt content of the emulsified water is different than salt content of the initial water, then the electrical properties of the bottom water layer change as the water separates from the emulsion and such change in conductivity is measured by the probe. this method has at least three disadvantages: 1) it is extremely difficult to spread the emulsion on top of the bottom water layer, 2) because it is also limited to lower experimental temperatures, it requires expensive field trials at commercial operating conditions, and 3) it cannot be automated to introduce emulsions. another laboratory test that has been developed cannot be used for water-in-crude oil emulsions. ring electrodes, on the outside of the vessel, are arranged at different depths and used to measure capacitance/conductance of an oil-in-water emulsion. 2 although the principals of this test may initially seem similar to the present invention, as discussed below, there are critical, non-obvious differences. first, for the ring electrodes, a non-conductive vessel is required, which means the vessel must be fabricated of glass, ceramic or polymer. none of these materials can be safely adapted for elevated temperatures (i.e., about 230° f. to about 300° f.) and the resulting elevated pressures. second, the ring electrodes must be sized for a larger vessel to provide the necessary resolution. third, the method requires the water phase to be continuous and the measured conductivity to be correlated with the oil volume fraction (and, thus, is similar to methods used to measure water-drop size). similar to the other laboratory methods, this method has at least two disadvantages: 1) because it is also limited to lower experimental temperatures, it requires expensive field trials at commercial operating conditions, and 2) it cannot be automated to introduce emulsions at temperatures above the boiling point of water (i.e., above about 212° f. (100° c.)). other industrially-used methods are not suitable for the laboratory setting. for example, radar is used industrially to measure separation rate by measuring the interface location; however, its high cost and relative large circular cross-sections makes it difficult (if not impossible) to use in a laboratory setting. microwave (i.e., agar probes) and gamma radiation (i.e., tracerco profiler) are other industrially-used methods that may (or may not) work on a laboratory scale, and, further, they are cost prohibitive for a laboratory setting. a mechanical float would not be robust enough for measuring separation rate of water from water-in-crude oil emulsions in the laboratory. therefore, there is a need for an accurate laboratory and/or online system and method for measuring separation rate of water from water-in-crude oil emulsions at elevated temperatures. summary of the invention the present invention provides an automated system and method for measuring oil/water separation rates, and, in particular, to a system and method for measuring separation rates of water from water-in-crude oil emulsions at elevated temperatures. in some embodiments, a system for measuring separation rate in a fluid stream or sample includes an interface (conductivity) cell, an oven or a bath and an analyzer. in an embodiment, the interface cell includes two or more capacitance/conductance probes disposed at different heights from the bottom of the cell. in an embodiment, the oven or bath includes a temperature sensor. the interface cell measures electrolytic conductivity of the fluid stream or sample disposed within the cell at elevated temperatures. the separation rate is determined based on signals received from the interface cell coupled to measure separation rate of the fluid stream or sample. in particular, the system measures the approximate location of the oil/water interface as a function of time. as the emulsion separates, a continuous water phase forms on the bottom of the interface cell and grows with time. a volume of separated water as function of time can be calculated based on a location of the oil/water interface as a function of time and interface cell dimensions. for some embodiments, a computer-readable storage-medium contains a program for measuring separation rate in a fluid stream or sample. the program, when executed, performs a method that includes receiving a signal indicative of electrolytic conductivity for the fluid stream or sample from two or more conductance/conductance probes disposed at different heights from the bottom of the interface cell. in addition, the method performed by the program includes determining the separation rate based on the signal and the height of the conductance/conductance probe from the bottom of the interface cell. the present invention has at least three advantages over current laboratory methods: 1) the present invention can measure separation rate at elevated temperatures and/or pressures, 2) because the present invention can measure separation rate at commercial operating temperatures, it reduces the risk of expensive field trials, and 3) it can be automated. these and other objects, features and advantages will become apparent as reference is made to the following detailed description, preferred embodiments, and examples, given for the purpose of disclosure, and taken in conjunction with the accompanying drawings and appended claims. brief description of the drawings for a further understanding of the nature and objects of the present invention, reference should be made to the following detailed disclosure, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals, and wherein: fig. 1a illustrates a schematic diagram of an exemplary laboratory separation rate analyzer system according to an embodiment of the present invention; fig. 1b illustrates a schematic diagram of an exemplary automated laboratory separation rate analyzer system according to an embodiment of the present invention; fig. 1c illustrates a schematic diagram of an exemplary online separation rate analyzer system according to an embodiment of the present invention; fig. 2 illustrates a detailed schematic of an interface cell for a separation rate analyzer system according to an embodiment of the present invention; fig. 3 illustrates a schematic of a computing device for a separation rate analyzer according to an embodiment of the present invention; fig. 4 illustrates a photograph of a prototype interface cell with eight (8) conductivity probes, showing the capacitance/conductance probes mounted at different heights from the bottom of the cell according to an embodiment of the present invention; fig. 5 illustrates a photograph of the assembled prototype interface cell in fig. 4 showing the probe electrical leads exiting the top of the interface cell according to an embodiment of the present invention; fig. 6 illustrates a photograph of five (5) assembled prototype cells, showing the interface cell disposed in an oven and connected to a computer according to an embodiment of the present invention; fig. 7 illustrates a flow chart for a method of measuring separation rate of water from water-in-crude oil emulsion according to an embodiment of the present invention; fig. 8a illustrates a chart of time (seconds) versus voltage (v) for a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8b illustrates a chart of time (seconds) versus voltage (v) for channel 1 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8c illustrates a chart of time (seconds) versus voltage (v) for channel 2 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8d illustrates a chart of time (seconds) versus voltage (v) for channel 3 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8e illustrates a chart of time (seconds) versus voltage (v) for channel 4 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8f illustrates a chart of time (seconds) versus voltage (v) for channel 5 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8g illustrates a chart of time (seconds) versus voltage (v) for channel 6 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8h illustrates a chart of time (seconds) versus voltage (v) for channel 7 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 8i illustrates a chart of time (seconds) versus voltage (v) for channel 8 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in low api crude oil emulsion according to an embodiment of the present invention; fig. 9a illustrates a chart of time (seconds) versus voltage (v) for a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9b illustrates a chart of time (seconds) versus voltage (v) for channel 1 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9c illustrates a chart of time (seconds) versus voltage (v) for channel 2 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9d illustrates a chart of time (seconds) versus voltage (v) for channel 3 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9e illustrates a chart of time (seconds) versus voltage (v) for channel 4 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9f illustrates a chart of time (seconds) versus voltage (v) for channel 5 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9g illustrates a chart of time (seconds) versus voltage (v) for channel 6 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9h illustrates a chart of time (seconds) versus voltage (v) for channel 7 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 9i illustrates a chart of time (seconds) versus voltage (v) for channel 8 of a prototype interface cell with eight (8) capacitance/conductance probes for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 10 illustrates a chart of time (seconds) versus water fraction for four (4) prototype interface cells operated in parallel at about 255° f. (i.e., about 125° c.) for a 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; fig. 11a illustrates a chart of slope of electrical conductivity tests (per minute) versus slope of bottle tests (per minute) for about two (2) (circles) or eight (8) (filled circles) hour separation of 20% deionized water in heavy api crude oil emulsion, showing a dotted line representing results if the slopes agreed with one another according to an embodiment of the present invention; fig. 11b illustrates a chart of slope of electrical conductivity tests (per minute) versus slope of bottle tests (per minute) for about eight (8) (filled circles) or twelve (12) (circles) hour separation of 20% deionized water in heavy api crude oil emulsion, showing a dotted line representing results if the slopes agreed with one another according to an embodiment of the present invention; fig. 11c illustrates a chart of time (minutes) versus temperature (° c.), showing electrical conductivity tests and bottle tests for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention; and fig. 12 illustrates a chart of time (minutes) versus water fraction for four (4) prototype interface cells operated in parallel at about 255° f. (i.e., about 125° c.) for 20% deionized water in heavy api crude oil emulsion according to an embodiment of the present invention. detailed description of embodiments of the invention the following detailed description of various embodiments of the present invention references the accompanying drawings, which illustrate specific embodiments in which the invention can be practiced. while the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains. therefore, the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled. embodiments of the invention relate to a system and method for measuring separation rate in a fluid stream or sample, such as water from water-in-crude oil emulsions. as illustrated in figs. 1a, 1b and 1c , a system 100 includes an interface cell 112 , an oven, bath or heater 118 and an analyzer 114 . although certain sample handling techniques for an exemplary laboratory separation rate analyzer system 100 , an exemplary automated laboratory system 100 and an exemplary on-line system 100 are depicted in figs. 1a, 1b and 1c and discussed in detail below, a person of ordinary skill in the art (posita) could easily combine and adapt these teachings to arrive at other sample handling techniques for the system 100 . accordingly, although certain sample handling techniques are discussed in detail below, this discussion should not be interpreted to exclude other combinations and/or adaptations of these techniques. the use of such sample handling techniques is well known in the art. in an embodiment, the interface cell 112 includes two or more capacitance/conductance probes 206 disposed at different heights from an inner bottom surface of the interface cell 112 . in an embodiment, the interface cell 112 includes a plurality of probes 206 disposed at different heights from the inner bottom surface of the cell 112 . in embodiments of the present invention, the number of probes 206 may range from just a few to many. as shown in fig. 2 , six (6) probes 206 may be used in the cell 112 ; and as shown in fig. 4 , eight (8) probes 206 , 404 were used in a prototype interface cell 112 , 500 . the total number (n) of probes 206 is determined by the desired resolution of the cell 112 and the geometry of the cell 112 . the probes may be spaced closer together for better resolution or further apart for less resolution. for example, in a prototype cell 112 , 500 , the probes 206 , 404 were spaced at about 0.1-inch (0.254 cm) apart as shown in fig. 4 . in an embodiment, the analyzer 114 may be a computer or a computing device as discussed below. in an embodiment, a person may determine a separation rate using a computer based on signals received from two or more capacitance/conductance probes 206 in the interface cell 112 that are coupled to monitor a fluid stream 104 . in an embodiment, logic of the analyzer 114 may determine a water separation rate based on signals received from two or more capacitance/conductance probes 206 in the interface cell 112 that are coupled to monitor a fluid stream 104 . in an embodiment, the stream 104 is diverted to the cell 112 for analysis. further, the analyzer 114 may also monitor signals received from an optional temperature sensor 116 , an optional pressure sensor 124 and/or an optional flow meter 126 . fig. 1a illustrates a schematic diagram of an exemplary laboratory system 100 according to an embodiment of the present invention. as shown in fig. 1a , the system 100 includes an interface cell 112 , an oven, bath or heater 118 and an analyzer 114 . in an embodiment, the temperature of the oven, bath or heater 118 may be monitored with an optional temperature sensor 116 . in an embodiment, the system 100 includes an optional pump 108 and an optional pressure gauge 110 . suitable pumps 108 include low shear pumps including peristaltic pumps to avoid additional, uncontrolled emulsification. in an embodiment, the pump 108 is a peristaltic pump. in operation of the exemplary laboratory system 100 , a source 102 may be an inlet to a crude oil desalter and/or dehydrator in a refinery. in an embodiment, the source 102 may be downstream of a mixer for the desalter and/or dehydrator. at least part of the source 102 enters a fluid stream or sample 104 . in an embodiment, the fluid stream or sample 104 may be extracted into a sample vessel or into a sample pipe/tube. if the stream or sample 104 is collected in a sample vessel, the stream or sample 104 should be heated and prepared as an emulsion before transferring the stream or sample 104 in the interface cell 112 . in an embodiment, the emulsion of fluid stream or sample 104 may be prepared at the same temperature as the cell 112 , and then transferred to the cell 112 . in an embodiment, the emulsion of stream or sample 104 may be prepared at lower temperature and heated to a desired temperature en route to or in the cell 112 before beginning an analysis. for example, the stream or sample 104 may be heated with an oven or bath or heater 118 . in an embodiment, the stream or sample 104 may be heated with an in-line heater 118 en route to the cell 112 . if the fluid stream or sample 104 is collected into a sample pipe/tube, the stream or sample 104 may need to be heated to maintain a desired temperature before transferring the stream or sample 104 into the interface cell 112 . in an embodiment, the stream or sample 104 may be heated with heat tracing 118 of the sample pipe/tube from the source 102 to the cell 112 . in an embodiment, the fluid stream or sample 104 may be transferred by pouring, piping/tubing and/or pumping the stream or sample 104 into the interface cell 112 . in an embodiment, the stream or sample 104 may be manually poured into the cell 112 , or, optionally, the stream or sample 104 may be piped/tubed to the cell 112 , or, optionally, the stream or sample 104 may be pumped to the cell 112 through pipe/tube that feeds the cell 112 . for example, an inlet pipe/tube may be connected at or near the top of the cell 112 and an outlet pipe/tube could be connected at or near the bottom of the cell 112 . such configuration of inlet and outlet would permit the cell 112 to be flushed with stream or sample 104 between analyses. in an embodiment, the sample piping/tubing may include an optional valve to divert the fluid stream or sample 104 to or around the interface cell 112 . in an embodiment, the valves may be manual- or computer-controlled. in an embodiment, a plurality of interface cells 112 may be piped/tubed in parallel to allow simultaneous measure of multiple samples. as illustrated in fig. 6 , five (5) prototype interface cells 112 , 600 were disposed in an oven 118 in parallel to simultaneously measure multiple samples. as illustrated in figs. 10 & 12 , four (4) prototype cells 112 were used in parallel to simultaneously collect data from multiple samples. in an embodiment, the sample piping/tubing may include an optional plurality of valves as part of a manifold to allow simultaneous measurement of multiple samples. fig. 1b illustrates a schematic diagram of an exemplary automated laboratory system 100 according to an embodiment of the present invention. as shown in fig. 1b , the system 100 includes an interface cell 112 , an oven, bath or heater 118 and an analyzer 114 . in an embodiment, the temperature of the oven, bath or heater 118 may be monitored with an optional temperature sensor 116 . if present, the temperature sensor 116 may be disposed within a fluid stream 104 or in an oven, bath or heater 118 disposed around the interface cell 112 . suitable temperature sensors 116 include heat probes, resistance temperature detectors (rtds), thermocouples, thermometers, and the like. in an embodiment, the system 100 includes an optional pump 108 and an optional pressure gauge 110 . suitable pumps 108 include low shear pumps including peristaltic pumps to avoid additional, uncontrolled emulsification. in an embodiment, the pump 108 is a peristaltic pump. in an embodiment, the system includes an optional flow loop 106 and an optional waste outlet 120 . in operation of the exemplary automated laboratory system 100 , a source 102 may be an inlet to a crude oil desalter and/or dehydrator in a refinery. in an embodiment, the source 102 may be downstream of a mixer for the desalter and/or dehydrator. at least part of the source 102 enters a fluid stream 104 . in an embodiment, the fluid stream 104 may be extracted into a sample pipe/tube. if only a portion of the source 102 is diverted into the flow loop 106 , a sufficient pressure differential between entry of fluid stream 104 and exit of the optional flow loop 106 (e.g., optional waste outlet) may ensure flow of the source 102 through the flow loop 106 . in an embodiment, the system 100 includes an optional pump 108 and an optional pressure gauge 110 to provide the sufficient pressure differential between entry of the fluid stream 104 and exit of the optional flow loop 106 (e.g., optional waste outlet 120 ). in an embodiment, the fluid stream 104 may need to be heated to maintain a desired temperature before transferring the stream 104 into the interface cell 112 . in an embodiment, the stream 104 may be heated with heat tracing 118 of the sample/tube from the source 102 to the interface cell 112 . in an embodiment, the stream 104 may be heated to a desired temperature en route to or in the cell 112 before beginning an analysis. for example, the stream 104 may be heated with an oven or bath or heater 118 . in an embodiment, the stream 104 may be heated with an in-line heater 118 en route to the cell 112 . in an embodiment, the fluid stream 104 may be transferred by piping/tubing and/or pumping the stream 104 into the interface cell 112 . in an embodiment, the fluid stream 104 may be piped/tubed to the cell 112 , or, optionally, the stream 104 may be pumped to the cell 112 through a pipe/tube that feeds the cell 112 . for example, an inlet pipe/tube may be connected at or near the top of the cell 112 and an outlet pipe/tube could be connected at or near the bottom of the cell 112 . such configuration of inlet and outlet would permit the cell 112 to be flushed with stream 104 between analyses. in an embodiment, the fluid stream 104 flows to or is pumped to the cell 112 under pressure through a pipe/tube that feeds the cell 112 . after the cell 112 is flushed with steam 104 , a sample shut off valve 122 would close to stop the flow of the stream 104 . after the flow is stopped, the stream 104 in the cell 112 may be allowed to settle for a brief period of time before beginning an analysis. after the analysis is complete, the sample shut-off 122 would open to allow flow of stream 104 to flush the cell 112 again. in an embodiment, the sample shut-off valve 122 may be upstream and/or downstream of the cell 112 as shown in fig. 3 . in an embodiment, the sample shut-off valve 122 may be computer controlled. in an embodiment, the sample piping/tubing may include an optional valve to divert the fluid stream 104 to or around the interface cell 112 . in an embodiment, the valves may be computer-controlled. in an embodiment, a plurality of interface cells 112 may be piped/tubed in parallel to allow simultaneous measure of multiple samples. as illustrated in fig. 6 , five (5) prototype interface cells 112 , 600 were disposed in an oven 118 in parallel to simultaneously measure multiple samples. as illustrated in figs. 10 & 12 , four (4) prototype cells 112 , 500 were used in parallel to simultaneously collect data from multiple samples. in an embodiment, the sample piping/tubing may include an optional plurality of valves as part of a manifold to allow simultaneous measurement of multiple samples. fig. 1c illustrates a schematic diagram of an exemplary online system 100 according to an embodiment of the present invention. as shown in fig. 1c , the system 100 includes an interface cell 112 , an oven, bath or heater 118 and an analyzer 114 . in an embodiment, the temperature of the oven, bath or heater 118 may be monitored with an optional temperature sensor 116 . if present, the temperature sensor 116 may be disposed within a fluid stream 104 or in an oven, bath or heater 118 disposed around the interface cell 112 . suitable temperature sensors 116 include heat probes, resistance temperature detectors (rtds), thermocouples, thermometers, and the like. in an embodiment, the system 100 includes an optional pump 108 and an optional pressure gauge 110 . suitable pumps 108 include low shear pumps including peristaltic pumps to avoid additional, uncontrolled emulsification. in an embodiment, the pump 108 is a peristaltic pump. in an embodiment, the system 100 includes an optional flow loop 106 and an optional waste outlet 120 . in an embodiment, the system 100 includes an optional pressure gauge 124 and an optional flow meter 126 . if present, the optional pressure sensor 124 may be disposed within the fluid stream 104 . in operation of the exemplary on-line system 100 , a source 102 may be an inlet to a crude oil desalter and/or dehydrator in a refinery. in an embodiment, the source 102 may be downstream of a mixer for the desalter and/or dehydrator. at least part of the source 102 enters a fluid stream 104 . in an embodiment, the stream 104 may be extracted into a sample pipe/tube. if only a portion of the source 102 is diverted into the flow loop 106 , a sufficient pressure differential between entry of fluid stream 104 and exit of the optional flow loop 106 (e.g., optional waste outlet) may ensure flow of the source 102 through the flow loop 106 . in an embodiment, the system 100 includes an optional pump 108 and an optional pressure gauge 110 to provide the sufficient pressure differential between entry of the fluid stream 104 and exit of the optional flow loop 106 (e.g., optional waste outlet 120 ). in an embodiment, the interface cell 112 , an oven, bath or heater 118 , and an optional temperature sensor 116 are disposed along a crude oil desalter and/or dehydrator of a refinery such that the fluid stream 104 contains at least part of the water-in-crude oil emulsion of source 102 . in an embodiment, the fluid stream 104 may need to be heated to maintain a desired temperature before transferring the stream 104 into the interface cell 112 . in an embodiment, the stream 104 may be heated with heat tracing 118 of the sample/tube from the source 102 to the cell 112 . in an embodiment, the stream 104 may be heated to a desired temperature en route to or in the cell 112 before beginning an analysis. for example, the stream 104 may be heated with an oven, bath or heater 118 . in an embodiment, the stream 104 may be heated with an in-line heater 118 en route to the cell 112 . in an embodiment, the fluid stream 104 may be transferred by piping/tubing and/or pumping the stream 104 into the interface cell 112 . in an embodiment, the fluid stream 104 may be piped/tubed to the cell 112 , or, optionally, the stream 104 may be pumped to the cell 112 through pipe/tube that feeds the cell 112 . for example, an inlet pipe/tube may be connected at or near the top of the cell 112 and an outlet pipe/tube could be connected at or near the bottom of the cell 112 . such configuration of inlet and outlet would permit the cell 112 to be flushed with stream 104 between analyses. in an embodiment, the fluid stream 104 flows to or is pumped to the cell 112 under pressure through a pipe/tube that feeds the cell 112 . after the cell 112 is flushed with steam 104 , a sample shut off valve 122 would close to stop the flow of the stream 104 . after the flow is stopped, the stream 104 in the cell 112 may be allowed to settle for a brief period of time before beginning an analysis. after the analysis is complete, the sample shut-off 122 would open to allow flow of stream 104 to flush the cell 112 again. in an embodiment, the sample shut-off valve 122 may be upstream and/or downstream of the cell 112 as shown in fig. 3 . in an embodiment, the sample shut-off valve 122 may be computer controlled. in an embodiment, the sample piping/tubing may include an optional valve to divert the fluid stream 104 to or around the interface cell 112 . in an embodiment, the valves may be computer-controlled. in an embodiment, a plurality of interface cells 112 may be piped/tubed in parallel to allow simultaneous measure of multiple samples. as illustrated in fig. 6 , five (5) prototype cells 112 , 600 were disposed in an oven 118 in parallel to simultaneously measure multiple samples. as illustrated in figs. 10 & 12 , four (4) prototype cells 112 , 500 were used in parallel to simultaneously collect data from multiple samples. in an embodiment, the sample piping/tubing may include an optional plurality of valves as part of a manifold to allow simultaneous measurement of multiple samples. interface cell as illustrated in figs. 1-2 & 4-6 , the interface cell 112 represents any device capable of measuring electrolytic conductivity in a fluid stream 104 at different heights from the inner, bottom surface of the cell 112 . the cell 112 of the present invention may be cubic-, rectangular-, circular- or circular-like shaped (e.g., elliptical base), and the like. in an embodiment, the interface cell 112 may be a combination of shapes as discussed below. in an embodiment, an interface cell chamber 202 may be fabricated to have a first base shape and a first height. in an embodiment, a first interface cell cover 204 may be fabricated to have the same base shape as the interface chamber 202 and a second height. in an embodiment, the first base shape may be selected from the group consisting of square, rectangular, circular and ellipse. in an embodiment, the interface cell chamber 202 includes an interface cell sleeve having a first end and a second end, and a third height. in an embodiment, the first end of the interface cell sleeve may be fabricated to have the same shape as the first interface cell cover 204 and the second end may be fabricated to have a second base shape. in an embodiment, a second interface cell cover may be fabricated to have the same base shape as the second end of the interface cell sleeve and a fourth height. in an embodiment, the second base shape may be selected from the group consisting of square, rectangular, circular and ellipse. in an embodiment, the first base shape may be different than the second base shape. in an embodiment, the second base shape may be smaller than the first than the base shape such that the sides of the interface cell 112 taper towards the second base shape. the tapered shape has advantages for low-water content emulsions. suitable materials for the interface cell chamber 202 and/or cover 204 include any metal compatible with water-in-crude oil emulsions, any plastic compatible with water-in-crude oil emulsions and any combination thereof. in an embodiment, the metal may be selected from the group consisting of carbon steel, stainless steel, stainless steel alloys such as monel® (special metals corp.) and hastalloy® (haynes international, inc.), and the like. in an embodiment, the plastic may be selected from the group consisting of polyether ketone (peek), polymethylene (e.g., delrin® (dupont co.)), polytetrafluorethylene (ptfe) (e.g., teflon® (dupont co.)) and other high-temperature polymers, and the like. in an embodiment, carbon steel pipe and pipe fittings were used to fabricate a prototype interface cell chamber 202 , 502 and cover 204 , 504 . importantly, when an electrically conductive material (e.g., metal) is used for the interface cell chamber 202 and/or cover 204 , the two or more capacitance/conductance probes 206 may need to be isolated from the chamber 202 and/or cover 204 . in fact, if the chamber 202 is fabricated from an electrically conductive material, the chamber 202 may be used as a required ground for the probes 206 ; otherwise one of the probes 206 may be used as the ground. techniques for isolating and sealing the probes 206 in a conductive cover 204 are discussed below. although a cylindrical interface chamber 202 and cover 204 are depicted in figs. 2 & 4-6 , a posita could easily adapt these teachings to cubic, rectangular and cylindrical-like interface cell chambers and covers. accordingly, although the cylindrical interface cell chamber 202 and cover 204 are discussed in detail below, this discussion should not be interpreted to exclude cubic, rectangular and cylindrical-like interface cell chambers and covers. although the prototype interface cell chamber 202 , 502 and cover 204 , 504 were fabricated from pipe and pipe fittings, a posita could easily adapt these teachings to other suitable methods of fabricating/machining parts. in an embodiment, the fabrication method may be selected from machining, molding, printing and combinations thereof. for example, if a plastic material is used, the reactor module and cover may be molded by compression or injection molding techniques or printed on a 3-d printer as customary in the art. accordingly, although machining is discussed in detail below, this discussion should not be interpreted to exclude molding and printing techniques. an exploded view of an interface cell 200 is depicted in fig. 2 . as shown in fig. 2 , the interface cell chamber 202 has a diameter 208 , a height 210 and a thickness 212 . the interface chamber 202 may be constructed from a metal or a plastic as discussed above. in an embodiment, the interface cell 200 was constructed from carbon steel. in an embodiment, the interface cell 200 may have an optional temperature sensor (not shown). when a temperature sensor is used, the interface cell chamber 202 may have an optional temperature probe chamber (not shown) with a temperature probe diameter (not shown) and a temperature probe depth (not shown) extending into the interface cell 200 from an outer surface. suitable temperature sensors (not shown) include heat probes, resistance temperature detectors (rtds), thermocouples, thermometers, and the like. in an embodiment, the interface cell 200 may have a plurality of holes (not shown) extending into the interface cell chamber 202 material from an upper surface 214 and/or lower surface 216 to attach the first interface cell cover 204 . in an embodiment, if the temperature probe chamber extends into the interface cell chamber 202 from an upper surface 214 or lower surface 216 , the first interface cell cover 204 will have a temperature probe hole with a temperature probe diameter extending through the first cover 204 and aligning with the temperature probe diameter of the temperature probe chamber in the chamber 202 . the first interface cell cover 204 may be constructed from a metal or a plastic as discussed above. in an embodiment, the first interface cell cover 204 was constructed from carbon steel. for example, a prototype interface cell chamber 202 , 502 was constructed from a cylindrical carbon steel pipe with a diameter 208 of about 1-inch (2.54 cm), a length 210 of about 3-inches (7.5 cm) and a thickness 212 of about ⅛-inch (0.3 cm) as depicted in figs. 4-6 . a plurality of threaded holes (not shown) may be machined into the upper surface 214 and/or a lower surface 216 of the interface cell chamber 202 to receive a plurality of screws. although screws may be used to secure the first interface cell cover 204 to the interface cell chamber 202 , a posita could easily adapt this teaching to other fasteners (e.g., compression fitting). in general, any fitting system that provides a leak-free seal between the interface cell chamber 202 and the interface cell cover 204 , and maintains the capacitance/conductance probes 206 at a constant height from the inner, bottom surface of the interface cell chamber 202 may be used. in an embodiment, the interface cell 112 , 200 is connected to an inlet and an outlet of fluid stream 104 . in an embodiment, a first hole may be machined into the interface cell chamber 202 from an outer surface extending into the chamber 202 , and a second hole opposing the first hole may be machined into the chamber 202 from an outer surface extending into the chamber 202 . in an embodiment, the first hole may be machined into the interface cell chamber 202 from an outer, upper surface extending into the chamber 202 , and the second hole opposing the first hole may be machined into the chamber 202 from an outer, lower surface extending into the chamber 202 . in an embodiment, the first hole is fluidically connected to the inlet of fluid stream 104 , and the second hole is fluidically connected to the outlet of fluid stream 104 . such configuration of inlet and outlet would permit the cell 112 , 200 to be flushed with stream 104 between analyses. a cylindrical disk may be used to fabricate the first interface cell cover 204 . an exploded view of an interface chamber 202 and cover 204 is depicted in fig. 2 . as shown in fig. 2 , the first interface cell cover 204 has a diameter 218 , and a height 220 . a plurality of holes (not shown) may be machined in the first interface cell cover 204 extending through the cover 204 and aligning with the diameters of the threaded holes in the interface cell chamber 202 . for example, a prototype first interface cell cover 204 , 504 a was constructed from a carbon steel pipe fitting sized to fit a 1-inch (2.54 cm) pipe as depicted in figs. 4-6 . similarly, a cylindrical disk may be used to fabricate the second interface cell cover. the second interface cell cover has a diameter and a height. a plurality of holes may be machined in the second interface cell cover extending through the cover and aligning with the diameters of the threaded holes in the interface cell sleeve. for example, a prototype second interface cell cover 504 b was constructed from a carbon steel pipe fitting sized to fit a 1-inch (2.54 cm) pipe as depicted in figs. 4-6 . an assembled view of an interface cell chamber 202 and a cover 204 is depicted in figs. 4-6 . in an embodiment, the interface cell cover 204 was constructed from a pipe fitting. an assembled view of an interface cell chamber 202 including an interface cell sleeve and a second cover is depicted in figs. 4-6 . in an embodiment, the interface cell sleeve was constructed from a pipe. in an embodiment, the second interface cell cover was constructed from a pipe fitting. a temperature probe hole (not shown) may be machined in the first interface cell cover 204 extending through the cover 204 and aligning with the temperature probe diameter of the temperature probe chamber in the interface chamber 202 . suitable temperature probes (not shown) include heat probes, resistance temperature detectors (rtds), thermocouples, thermometers, and the like. the first interface cell cover 204 may provide a flange-seal by tightening the cover 204 onto the interface cell chamber 202 via a plurality of screws. in an embodiment, an o-ring may be used between the interface cell chamber 202 and cover 204 . similarly, the second interface cell cover may provide a flange-seal by tightening the cover onto the interface cell sleeve via a plurality of screws. in an embodiment, an o-ring may be used between the interface cell sleeve and cover. alternatively, when the first base shape is circular, the interface cell chamber 202 and first cover 204 may be machined to screw together. for example, when the interface cell chamber 202 was a pipe and pipe fitting, and the cover 204 was a pipe fitting, the cover 204 was screwed onto the interface cell chamber 202 . similarly, when the second base shape is circular, the interface cell interface sleeve and second cover may be machined to screw together. for example, when the interface cell sleeve was a pipe and the second cover was a pipe fitting, the cover was screwed onto the interface cell sleeve. as discussed above, the interface cell 112 includes two or more of capacitance/conductance probes 206 disposed at different heights from the inner bottom surface of the interface cell 112 . in an embodiment, a plurality of conductance/conductance probes 206 disposed at different heights from the inner bottom surface of the interface cell 112 . the number (n) of capacitance/conductance probes may range from just a few to many. as shown in fig. 2 , six (6) capacitance/conductance probes may be used in the interface cell 112 ; and as shown in fig. 4 , eight (8) capacitance/conductance probes were used in a prototype interface cell 112 , 404 . the total number of capacitance/conductance probes is determined by the desired resolution of the interface cell 112 and the geometry of the cell 112 . in an embodiment, two or more capacitance/conductance probes 206 may be disposed at different heights from the inner bottom surface of the interface cell 112 . in an embodiment, the two or more capacitance/conductance probes 206 may be a welding rod. in an embodiment the capacitance/conductance probes may be any conductive metal. in an embodiment, the conductive metal may be selected from the group consisting of aluminum, copper, nickel, silver, tungsten, zinc, and the like. for example, in the prototype interface cell 112 , 500 , the capacitance/conductance probes 206 , 404 were 1 mm tungsten welding rods for metal inert gas (mig) welding applications. one or more holes (not shown) may be machined in the first interface cell cover 204 extending through the cover 204 . in an embodiment, the one or more capacitance/conductance probes 206 may be disposed individually through the one or more holes in the first interface cell cover 204 as shown in fig. 2 , or, optionally, as a bundle through the one hole in the first cover 204 as illustrated by figs. 4-6 . in an embodiment, the individual probes 206 may be secured in place using a metal fitting, a plastic fitting or a combination thereof. in an embodiment, the individual probes 206 may be secured in place using or adhesive. in an embodiment, the plastic may be selected from the group consisting of polytetrafluorethylene (ptfe) (e.g., teflon® (dupont co.)) and other high-temperature polymers, and the like. in an embodiment, the adhesive may be selected from the group consisting of epoxy resins, and the like. for example, in the prototype interface cell 112 , 500 , the capacitance/conductance probes 206 , 404 were secured into place using a teflon® gland seal fitting 506 . after the two or more probes 206 are positioned to a desired height from the inner, bottom surface of the interface cell 112 , 500 , the gland seal fitting 506 was screwed into an upper prototype cover 504 a and tightened to compress an inner teflon® seal. in the prototype cell 112 , 500 , the capacitance/conductance probes 206 , 404 were spaced at about 0.1-inch (0.254 cm) apart. as shown in fig. 4 , teflon® tape was used on the threads of the gland seal fitting 506 . although a gland seal may be used to secure the capacitance/conductance probes 206 , 404 in place in the interface cell cover 204 , 504 a , a posita could easily adapt this teaching to other fasteners. in general, any fitting system that provides a leak-free seal between the capacitance/conductance probes 206 , 404 and the interface cell cover 204 , 504 a at elevated pressures (e.g., about 100 psig (about 790.8 kilopascals)), and maintains the capacitance/conductance probes 206 , 404 at a constant, known heights from the bottom surface of the interface cell chamber 202 may be used. the upper cover 504 a (assembly) and the lower cover 504 b were screwed onto the interface cell chamber 502 . as shown in fig. 5 , teflon® tape was used on the threads of the interface cell chamber 502 . computing device for separation rate analyzer fig. 3 illustrates a schematic diagram of a computing device for a separation rate analyzer system according to an embodiment of the present invention. referring to the drawings in general, and initially to figs. 1 and 3 in particular, an exemplary operating environment for implementing embodiments of the present invention is shown and designated generally as a computing device 300 for the analyzer 114 . the computing device 300 is but one example of a suitable computing environment and is not intended to suggest any limitation as to the scope of use or functionality of the invention. neither should the computing device 300 be interpreted as having any dependency or requirement relating to any one or combination of components illustrated. embodiments of the invention may be described in the general context of computer code or machine-executable instructions stored as program modules or objects and executable by one or more computing devices, such as a laptop, server, mobile device, tablet, etc. generally, program modules including routines, programs, objects, components, data structures, etc., refer to code that perform particular tasks or implement particular abstract data types. embodiments of the invention may be practiced in a variety of system configurations, including handheld devices, consumer electronics, general-purpose computers, more specialty computing devices, and the like. embodiments of the invention may also be practiced in distributed computing environments where tasks may be performed by remote-processing devices that may be linked through a communications network. with continued reference to fig. 3 , the computing device 300 of the analyzer 114 includes a bus 310 that directly or indirectly couples the following devices: memory 312 , one or more processors 314 , one or more presentation components 316 , one or more input/output (i/o) ports 318 , i/o components 320 , a user interface 322 and an illustrative power supply 324 . in an embodiment, the two or more capacitance/conductance probes 206 couple directly or indirectly to a signal conditioning device because the probe's raw signal must be processed to provide a suitable signal for an i/o system. the bus 310 represents what may be one or more busses (such as an address bus, data bus, or combination thereof). although the various blocks of fig. 3 are shown with lines for the sake of clarity, in reality, delineating various components is not so clear, and metaphorically, the lines would more accurately be fuzzy. for example, one may consider a presentation component such as a display device to be an i/o component. additionally, many processors have memory. the inventors recognize that such is the nature of the art, and reiterate that the diagram of fig. 3 is merely illustrative of an exemplary computing device that can be used in connection with one or more embodiments of the present invention. further, a distinction is not made between such categories as “workstation,” “server,” “laptop,” “mobile device,” etc., as all are contemplated within the scope of fig. 3 and reference to “computing device.” the computing device 300 of the analyzer 114 typically includes a variety of computer-readable media. computer-readable media can be any available media that can be accessed by the computing device 300 and includes both volatile and nonvolatile media, removable and non-removable media. by way of example, and not limitation, computer-readable media may comprise computer-storage media and communication media. the computer-storage media includes volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer-readable instructions, data structures, program modules or other data. computer-storage media includes, but is not limited to, random access memory (ram), read only memory (rom), electronically erasable programmable read only memory (eeprom), flash memory or other memory technology, cd-rom, digital versatile disks (dvd) or other holographic memory, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium that can be used to encode desired information and which can be accessed by the computing device 300 . the memory 312 includes computer-storage media in the form of volatile and/or nonvolatile memory. the memory 312 may be removable, non-removable, or a combination thereof. suitable hardware devices include solid-state memory, hard drives, optical-disc drives, etc. the computing device 300 of the analyzer 114 includes one or more processors 314 that read data from various entities such as the memory 312 or the i/o components 320 . the presentation component(s) 316 present data indications to a user or other device. in an embodiment, the computing device 300 outputs present data indications including separation rate, temperature, pressure and/or the like to a presentation component 316 . suitable presentation components 316 include a display device, speaker, printing component, vibrating component, and the like. the user interface 322 allows the user to input/output information to/from the computing device 300 . suitable user interfaces 322 include keyboards, key pads, touch pads, graphical touch screens, and the like. for example, the user may input a type of signal profile into the computing device 300 or output a separation rate to the presentation component 316 such as a display. in some embodiments, the user interface 322 may be combined with the presentation component 316 , such as a display and a graphical touch screen. in some embodiments, the user interface 322 may be a portable hand-held device. the use of such devices is well-known in the art. the one or more i/o ports 318 allow the computing device 300 to be logically coupled to other devices including the interface cell 112 , the optional temperature sensor 116 , the optional pressure sensor 124 , the optional flow meter 126 , and other i/o components 320 , some of which may be built in. examples of other i/o components 320 include a printer, scanner, wireless device, and the like. in operation, a capacitance/conductance probe 206 of the interface cell 112 sends a signal indicative of the electrolytic conductivity to the computing device 300 of analyzer 114 via a first i/o port 318 a . each capacitance/conductance probe 206 must be connected to the first i/o port 318 a . for example, if a plurality of probes 206 are used, the first probe 206 - 1 will be connected to the first i/o port 318 a - 1 , the second probe 206 - 2 will be connected to the first i/o port 318 a - 2 , etc. the analyzer 114 includes logic for determining the separation rate of water from water-in-crude oil emulsions based on the signals received from two or more capacitance/conductance probes 206 of the interface cell 112 . the stream 104 may consist of, or consist essentially of, water and crude oil in solution. in some embodiments, the analyzer 114 outputs the separation rate of water from water-in-crude oil emulsions to a presentation component 316 onsite with the interface cell 112 and/or to a remote presentation component 316 , such as a display in a control room or offsite monitoring location. the interface cell 112 , optionally, temperature sensor 116 , optionally, pressure sensor 126 or the analyzer 114 may include a cellular modem or wireless device for this output of the separation rate of water from water-in-crude oil emulsions to the remote location from the interface cell 112 . in an embodiment, the presentation component 316 may show present data indications including a separation rate (e.g. water fraction/minute) of the stream 104 , optionally, temperature of the stream 104 in degree fahrenheit (° f.) or in degree celsius (° c.), and, optionally, pressure of the stream 104 in pounds per square inch gauge (psig) or in kilopascals (kpa). in an embodiment, the analyzer 114 operates at temperatures between about 150 to 350° f. (i.e., about 65.5 to about 176.7° c.) or an upper limit defined by component temperature ratings. in an embodiment, the analyzer 114 may operate at temperatures higher than about 350° f. some embodiments include the temperature sensor 116 , which can provide assurance that the temperature is in an acceptable range. in these embodiments, the computing device 300 receives a second signal from the pressure sensor 116 via a second i/o port 318 b , as discussed above. the temperature sensor represents any device capable of measuring temperature of the fluid stream 104 . the temperature sensor 116 represents any device capable of measuring temperature of the fluid stream 104 . examples of temperature sensors 116 include heat probes, resistance temperature detectors (rtd), thermocouples, thermometers, and the like. the temperature sensor 116 enables determining temperature of the stream 104 when passing through the interface cell 112 and, thus, the temperature sensor 116 may be disposed at or near the interface cell 112 . some embodiments utilize the temperature sensor 116 located directly in contact with the fluid stream 104 . in other words, the temperature sensor 116 may be inserted directly into the stream 104 . for other embodiments, the temperature sensor 116 operates as part of a temperature-regulating device such as an oven, bath or heater 118 that controls temperature of the stream 104 such that the stream temperature remains constant when passing through the conductivity cell 112 . if the second signal representing temperature of the fluid stream 104 decreases below a first threshold value or increases above a second threshold value, the computing device 300 of analyzer 114 may, thus, indicate an error or otherwise tag the separation rate that is determined and output. in an embodiment, the computing device 300 may initiate a separation rate determination when the second signal reaches a first threshold value. in an embodiment, the analyzer 114 operates at pressures between about 0 to 100 psig (i.e., about 101.4 to about 790.8 kilopascal) or an upper limit defined by component pressure ratings. some embodiments include the pressure sensor 110 or 124 , which can provide assurance that the pressure is in an acceptable range. the pressure sensor 110 , 124 represents any device capable of measuring pressure of the fluid stream 104 . in these embodiments, the computing device 300 receives a third signal from the pressure sensor 110 or 124 via a third i/o port 318 c , as discussed above. if the third signal representing pressure of fluid stream 104 increases above a threshold value, the computing device 300 of analyzer 114 may, thus, indicate an error or otherwise tag the separation rate that is determined and output. in some embodiments, a flow meter 126 disposed along the flow loop 106 confirms that the fluid stream 104 is flowing through the interface cell 112 since the fully-automated system 100 can provide real-time online measurements as separation rates are determined. the flow meter 126 represents any device capable of measuring flow rate of the fluid stream 104 . the separation rate would fail to be updated over time in the absence of the stream 104 moving through the flow loop 106 . if flow stops or slows below a threshold value, the computing device 300 of analyzer 114 may, thus, indicate an error or otherwise tag the separation rate that is determined and output. in these embodiments, the computing device 300 receives a fourth signal from the flow meter 126 via a fourth i/o port 318 d. in some embodiments, the analyzer 114 may output the separation rate at specified intervals, such as every two to eight hours. continuous automatic monitoring by the analyzer 114 permits integration of the analyzer 114 with other process controls that can adjust levels of the temperature, pressure and/or flow rate in the stream 104 based on the separation rate that is determined. for some embodiments, the analyzer 114 may output an alarm signal if the separation rate falls below a minimum value. the stream 104 exits the flow loop 106 and is sent as a waste output 120 for treatment or reuse. the waste output 120 may include any of the stream 104 not diverted through the flow loop 106 . in some embodiments, at least about 7 psig (i.e., about 50 kilopascal) pressure differential between where part of the stream 104 enters the flow loop 106 and combines back to form the waste output 120 maintains desired flow. method of measuring separation rate of water from water-in-crude oil emulsions fig. 7 shows a flow chart for a method of measuring separation rate of water from water-in-crude oil emulsions 700 in a fluid stream. a first step 701 of the method includes measuring conductivity of two or more capacitance/conductance probes 206 disposed at different heights from the inner bottom surface of the interface cell 112 . in an embodiment, the computing device 300 of the analyzer 114 receives a first signal indicative of conductivity from two or more probes 206 of the interface cell 112 . for example, figs. 8a through 8i and 9a through 9i represent raw data (e.g., time vs. voltage) from eight (8) capacitance/conductance probes 206 disposed in an interface cell 112 at different heights from the inner bottom surface of the cell 112 . the geometry of the cell 112 and the height of each probe 206 from the inner bottom surface of the cell 112 are known and can be used to determine the separation as an actual volume or as a fraction. for comparisons to bottle tests, a fractional value would be preferred. in figs. 8a through 8i and 9a through 9i , the lower channel numbers represent a position closer to the bottom of the cell 112 , and a more conductive water layer. obviously, the details of a signal and its relationship to conductance depend on configuration of the electronics. a second step 702 of the method includes determining an approximate location of an oil-water interface based on conductivity data (e.g., time vs. voltage) from the capacitance/conductance probes 206 disposed in the interface cell 112 at different heights from the inner bottom surface of the cell 112 . in an embodiment, the computing device 300 of the analyzer 114 determines an approximate location of an oil-water interface based on conductivity data (e.g., time vs. voltage) from the probes 206 disposed in the cell 112 at different heights from the inner bottom surface of the cell 112 . in an embodiment, the computing device 300 of the analyzer 114 determines a time at which an oil-water interface passes a tip of a capacitance/conductance probe 206 based on conductivity data from the probe 206 . for example, two qualitatively different signal profiles relating to a location of an oil-water interface are possible depending on water conductivities for deionized water and two crude oils with different api gravities, as shown in figs. 8a through 8i and 9a through 9i . figs. 8a through 8i show a lower viscosity, more quickly separating emulsion with deionized water and high api crude oil; and figs. 9a through 9i show a higher viscosity more slowly separating emulsion with deionized water and low api crude oil. assuming that a tip of a capacitance/conductance probe 206 in an interface cell 112 is initially immersed in a spatial region corresponding to an emulsion, its conductivity signal will be initially constant with time followed by a rapid decrease in voltage when the probe is immersed in water. this rapid decrease is followed either by a relative minimum or a plateau. for the emulsion shown in figs. 8a through 8i , the time when the relative minimum in signal was reached was the time used to determine the interface location. the plateau is observed when the water is conductive, (e.g., salt water) because water is the most conductive component in the interface cell 112 . for the emulsion shown in figs. 9a through 9i , the time when the signal starts to rapidly decrease represents the time that is used to determine the interface location. the choice of which feature to use is strictly based on convenience. in figs. 8a through 8i , if the time when the signal starts to rapidly decrease were used, then some capacitance/conductance probes 206 would be eliminated from consideration because the emulsion separated at a faster rate than the test could be started, and, thus, the bottom probes (i.e., lower channel numbers) were already in water. in figs. 9a through 9i , using the time when the relative minimum in signal is reached would be less precise because the relative minimum is spread out over a long time interval and also some of the probes had not reached the minimum. clearly neither technique represents exactly where the oil-water interface is located; however the separation rate depends only on the slope from the data of time vs. water separation. accordingly, as long as a consistent measure is chosen for a particular emulsion, the exact interface location is not important because the rate of separation is being measured. a third step 703 includes determining separation data (e.g., time vs. water volume or water fraction) based on an approximate location of an oil-water interface and the geometry of the interface cell 112 . in an embodiment, the computing device 300 determines separation data based on the approximate location of the oil-water interface and the geometry of the cell 112 . in an embodiment, the computing device 300 determines separation data based on the approximate location of the oil-water interface at discrete times and the geometry of the cell 112 . as shown in figs. 10 and 12 , separation data can be determined based on the time when the conductance changes as determined in the second step 702 and knowing the geometry of the cell 112 and the height of the tip of the probe 206 from the inner bottom surface of the cell 112 . time vs. water separation data is typically described by a sigmoidal type of relationship—an induction period with little to no change in separation volume followed by an increase in separation volume that is reasonably approximated as being linear with time, followed by a plateau as the separation approaches completion. figs. 10 and 12 show little to no evidence of an induction period for the emulsion tested (i.e., deionized water and high api crude oil). in fig. 10 , the separation data was collected at a temperature of 195° f. (91° c.), and, in fig. 12 , the data was collected at a temperature of 255° f. (124° c.). a fourth step 704 includes determining separation rate (i.e., slope) based on separation data (e.g., time vs. water volume or water fraction) for the fluid stream 104 . in an embodiment, the computing device 300 determines separation rate (i.e., slope) based on separation data (e.g., time vs. water volume or water fraction) for the stream 104 . as shown in figs. 10 and 12 , separation rate can be determined based on the slope of the separation data (e.g., time vs. water volume or water fraction) as determined in the third step 703 for the stream 104 . fig. 11 shows a comparison of the slopes of the lines for two types of data sets (slope of electrical conductivity tests vs. slope of bottle tests) for the heavy crude oil emulsion. a line x=y would indicate perfect agreement. as shown in fig. 11 , the agreement between the electrical conductivity tests (present invention) and the bottle tests is excellent. the data shown in fig. 11 was collected at a temperature of 195° f. (91° c.). in an embodiment, the method 700 optionally includes outputting conductivity data (e.g., time vs. voltage), separation data (time vs. water volume or water fraction), and/or the separation rate (e.g., slope) for the fluid stream 104 to the presentation component 316 , such as a display. in an embodiment, the method 700 optionally includes outputting a time at relative minimum in conductivity signal and/or a time at rapid decrease in conductivity signal for the stream 104 to the presentation component 316 , such as a display. in an embodiment, the method 700 optionally includes the step of measuring temperature of the fluid stream 104 . in an embodiment, the temperature sensor 116 may be inserted directly into the fluid stream 104 , as discussed above. in an embodiment, the computing device 300 receives a second signal indicative of temperature from the temperature sensor 116 for the stream 104 , as discussed above. in an embodiment, the method 700 optionally includes outputting the temperature measured for the stream 104 to the presentation component 316 , such as a display. in an embodiment, the method 700 optionally includes the step of measuring pressure of the fluid stream 104 . in an embodiment, the pressure sensor 124 may be inserted directly into the stream 104 , as discussed above. in an embodiment, the computing device 300 receives a third signal indicative of pressure from the pressure sensor 124 for the stream 104 , as discussed above. in an embodiment, the method 700 optionally includes outputting the pressure measured for the stream 104 to the presentation component 316 , such as a display. in an embodiment, the method 700 optionally includes the step of measuring flow rate of the fluid stream 104 . in an embodiment, the flow meter 126 may be inserted directly into the stream 104 , as discussed above. in an embodiment, the computing device 300 receives a fourth signal indicative of flow rate from the flow meter 126 for the stream 104 , as discussed above. in an embodiment, the method 700 optionally includes outputting the flow rate measured for the stream 104 to the presentation component 316 , such as a display. in an embodiment, the method 700 includes a step of directing at least part of a water-in-crude oil emulsion source 102 to provide the fluid stream 104 . in an embodiment, the method 700 optionally includes the step of tagging the separation rate if flow rate of the fluid stream 104 is below a threshold value. laboratory testing of prototype separation rate analyzer a prototype system 100 including an interface cell 112 , 500 , an oven 118 and a computer 114 was constructed to evaluate the system 100 for measuring separation rate of water from water-in-crude oil emulsions and to compare those measured separation results to bottle tests used in a refinery. a prototype interface cell 112 , 500 was fabricated from carbon steel pipe and fittings. as shown in fig. 4 , eight (8) capacitance/conductance probes 206 , 508 were used in the prototype interface cell 112 , 500 . in the prototype cell 112 , 500 , the probes 206 , 508 were 1 mm tungsten welding rods for metal inert gas (mig) welding applications. the probes 206 , 508 were secured into place using a teflon® gland seal 506 . after the two or more probes 206 , 508 were positioned to a desired height from the inner surface of the cell 112 , 500 , the gland fitting 506 was screwed into a first prototype cover 504 a and tightened to compress an inner teflon® seal. as shown in fig. 4 , teflon® tape was used on the threads. the first cover 504 a (assembly) and the second cover 504 b were screwed onto the chamber 502 . as shown in fig. 5 , teflon® tape was used on the threads. the prototype interface chamber 502 was constructed from carbon steel pipe with a diameter of about 1-inch (2.54 cm), a length of about 3-inches (7.5 cm) and a thickness of about ⅛-inch (0.3 cm) as depicted in figs. 4-6 . the prototype cover 504 was constructed from a carbon steel pipe fitting sized to fit a 1-inch (2.54 cm) pipe. in an embodiment, a plurality of interface cells 112 , 500 may be piped/tubed in parallel to allow simultaneous measure of multiple samples. as illustrated in fig. 6 , five (5) prototype interface cells 112 , 600 were disposed in an oven 118 in parallel to simultaneously measure multiple samples. as illustrated in figs. 10 & 12 , four (4) prototype cells 112 , 500 were used in parallel to simultaneously collect data from multiple samples. for the laboratory evaluations of the interface cell 112 , 500 , mixtures of deionized water and crude oil used were prepared in a heated blender as the emulsions. the blender, deionized water and crude oil were pre-heated to about 70° c. about 20% deionized water in low api crude oil or about 20% deionized water in high api crude oil was blended at a reproducible, controlled speed. the interface cell 112 , 500 , namely the interface cell chamber 202 , 502 and cover 204 , 504 , was also pre-heated to about 70° c. the pre-heated emulsion was poured or pumped into the pre-heated interface chamber 202 , 502 . the cover 504 was screwed onto the emulsion-filled interface chamber 502 , taking care not to short the capacitance/conductance probes 206 , 404 against the carbon steel chamber 502 . the emulsion-filled interface cell 112 , 500 was placed in an oven 118 and connected to a computing device 300 as discussed above. the cell 112 , 500 was heated to a desired temperature. typically, it takes about eighteen (18) minutes for about 195° f. (90° c.) and about forty-five (45) minutes for about 255° f. (125° c.) for the cell 112 , 500 to reach the desired temperature. during heating to 255° f., the pressure inside the cell 112 , 500 increased from about 0 psig to about 100 psig (i.e., about 101.4 kilopascals to about 790.8 kilopascals). the electrical conductivity tests were started when the oven 118 reached the desired temperature (i.e., time=0). typically, it takes about three and half (3.5) minutes for about 195° f. (90° c.) and about eleven (11) minutes for about 255° f. (125° c.). the evaluations covered a range of conditions as follows: 1) about 195° f. to about 255° f. (i.e., about 90° c. to about 125° c.);2) about 0 to about 100 psig (i.e., about 101.4 to about 790.8 kilopascals);3) about 20% deionized water in low api crude oil (light crude oil emulsion) and about 20% deionized water in high api crude oil (heavy crude oil emulsion). the inventors have shown that the conductance changes when an interface passes by a tip of a capacitance/conductance probe 206 , 404 . by using the time when the conductance changes in one of two predetermined manners (depends on the crude oil being used) and knowing the geometry of an interface cell 112 , 500 and height of the tip of a capacitance/conductance probe 206 , 404 from the bottom of the cell 112 , 500 , an approximate interface location can be determined. the resolution of the method relative to the interface height is determined by the number of capacitance/conductance probes 206 , 404 ; six (6) are shown in fig. 2 and eight (8) are shown in fig. 4 . the total number of probes 206 , 404 is simply a function of the desired resolution and the geometry (size) of the cell. a cylindrical interface cell 200 , 500 is shown in figs. 2 & 4-6 . as illustrated in fig. 6 , five (5) prototype interface cells 112 , 600 were disposed in an oven 118 in parallel to simultaneously measure multiple samples. as illustrated in figs. 10 & 12 , four (4) prototype interface cells 112 , 500 were used in parallel to simultaneously collect data from multiple samples. the non-obviousness of the system 100 arises from a number of issues. first, it was not clear whether the probes 206 , 404 would become coated with debris from crude oil and, thus, render the readings unreliable. however, the comparison data shows that the bottle tests and the present invention agree at lower temperatures. second, it was not obvious whether the small differences in height (e.g., about 0.1-inch (0.254 cm) apart as shown in fig. 4 ) would allow for sufficient resolution. although the present invention has some scatter, the interfacial levels vs. time approximate the bottle tests. third, it was not obvious that a feature in the conductance vs. time signal could be used to reliably determine when the interface passed by a particular probe tip. again, agreement with bottle tests suggests that the present invention would be reliable. figs. 8a through 8i and 9a through 9i represent raw data from eight (8) capacitance/conductance probes 206 , 404 disposed in an interface cell 112 , 500 at different heights from the bottom of the cell 112 , 500 . the height of each capacitance/conductance probe is known in the interface cell 112 , 500 and can be used to determine the separation as an actual volume or as a fraction. for comparison to bottle tests, a fractional value is preferred. in these figures, the lower channel numbers represent a position closer to the bottom of the cell 112 , 500 , and a more conductive water layer. obviously, the details of a signal and its relationship to conductance depend on configuration of the electronics. as shown in figs. 8a through 8i and 9a through 9i , two qualitatively different signal profiles relating to a location of an oil-water interface are possible depending on water conductivities for deionized water and two crude oils with different api gravities. figs. 8a through 8i show a lower viscosity, more quickly separating emulsion with deionized water and high api crude oil; and figs. 9a through 9i shows a higher viscosity, more slowly separating emulsion with deionized water and low api crude oil. assuming that a tip of a capacitance/conductance probe 206 , 404 in an interface cell 112 , 500 is initially immersed in a spatial region corresponding to an emulsion, its conductivity signal will be initially constant with time followed by a rapid decrease in voltage when the probe is immersed in water. this rapid decrease is followed either by a relative minimum or a plateau. the minimum will be observed if the oil-water interface will be the highest conductive component (e.g., higher than pure water, pure oil or water-in-oil emulsion) in the cell. for the emulsion shown in figs. 8a through 8i , the time when the relative minimum signal was reached was the time used to determine the interface location. for the emulsion shown in figs. 9a through 9i , the time when the signal starts to rapidly decrease represents the time that is used to determine the interface location. the choice of which feature to use is strictly based on convenience. in figs. 8a through 8i , if the time when the signal starts to rapidly decrease was used, then some capacitance/conductance probes 206 , 404 would be eliminated from consideration because the emulsion separated at a faster rate than the test could be started, and, thus, the bottom probes (i.e., lower channel numbers) were already in water. in figs. 9a through 9i , using the time when the relative minimum in signal is reached would be less precise because the relative minimum is spread out over a long time interval and also some of the probes had not reached the minimum. clearly neither technique represents exactly where the oil-water interface is located; however, the separation rate depends only on the slope from the data of fractional separation vs. time. accordingly, as long as a consistent measure is chosen for a particular emulsion, the exact interface location is not important. time vs. water separation data is typically described by a sigmoidal type of relationship—an induction period with little-to-no change in separation volume followed by an increase in separation volume that is reasonably approximated as being linear with time, followed by a plateau as the separation approaches completion. fig. 10 shows little to no evidence of an induction period for the emulsion tested (i.e., deionized water and high api crude oil). similar to bottle tests, the water separation data shown in fig. 10 was collected at a temperature of 195° f. (91° c.). however, the emulsifying conditions were adjusted so that oil-water separation took no longer than about eight (8) hours for comparison of electrical conductivity tests to bottle tests which are typically performed by a person during an eight hour shift. fig. 11 shows a comparison of the slopes of the lines for the two types of data sets (slope of electrical conductivity tests vs. slope of bottle tests) for the heavy crude oil emulsion. a line x=y would indicate perfect agreement. as shown in fig. 11 , the agreement between the electrical conductivity tests and the bottle tests is excellent. the data shown in fig. 11 was collected at a temperature of 195° f. (91° c.). similar to fig. 10 , fig. 12 shows little to no evidence of an induction period for the heavy crude oil. however, unlike fig. 10 , the water separation data shown in fig. 12 was collected at a temperature of 255° f. (124° c.). as compared to fig. 10 , fig. 12 shows no degradation in the quality of the data. because bottle tests cannot be performed safely at temperatures above 195° f. (91° c.), corresponding bottle test data could not be obtained at a temperature of 255° f. (124° c.). depending on materials of construction for the interface cell 112 , 500 , elevated temperatures of hundreds of degrees fahrenheit should be possible with the present invention. the embodiments and examples set forth herein are presented to best explain the present invention and its practical application and to thereby enable those skilled in the art to make and utilize the invention. however, those skilled in the art will recognize that the foregoing description and examples have been presented for the purpose of illustration and example only. the description as set forth is not intended to be exhaustive or to limit the invention to the precise form disclosed. many modifications and variations are possible in light of the above teaching without departing from the spirit and scope of the following claims. the invention is specifically intended to be as broad as the claims below and their equivalents. definitions as used herein, the terms “a,” “an,” “the,” and “said” means one or more, unless the context dictates otherwise. as used herein, the term “about” means the stated value plus or minus a margin of error or plus or minus 10% if no method of measurement is indicated. as used herein, the term “or” means “and/or” unless explicitly indicated to refer to alternatives only or if the alternatives are mutually exclusive. as used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject. as used herein, the terms “containing,” “contains,” and “contain” have the same open-ended meaning as “comprising,” “comprises,” and “comprise,” provided above. as used herein, the terms “having,” “has,” and “have” have the same open-ended meaning as “comprising,” “comprises,” and “comprise,” provided above. as used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise,” provided above. as used herein, the phrase “consisting of” is a closed transition term used to transition from a subject recited before the term to one or more material elements recited after the term, where the material element or elements listed after the transition term are the only material elements that make up the subject. as used herein, the term “simultaneously” means occurring at the same time or about the same time, including concurrently. incorporation by reference all patents and patent applications, articles, reports, and other documents cited herein are fully incorporated by reference to the extent they are not inconsistent with this invention, as follows: 1) j. van dijk, et al., monitoring the demulsification of crude oil emulsions by using conductivity measurements , e mulsions and e mulsion s tability ; s urfactant s cience vol. 132 (crc press, 2d ed. nov. 21, 2005); and2) m. kostoglou, et al., evolution of volume fractions and droplet sizes by analysis of electrical conductance curves during destabilization of oil - in - water emulsions, 349(1) j. c olloid i nterface s ci . (2010) 408-416.
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069-831-253-356-293
|
KR
|
[
"EP",
"KR",
"CN",
"JP",
"US"
] |
G11C7/10,G06F12/1009,G11C29/42,G06F12/02,G06F3/06,G06F12/06,G06F12/00
| 2016-11-24T00:00:00 |
2016
|
[
"G11",
"G06"
] |
method and apparatus for managing memory
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a method of managing memory includes generating a page pool by aligning a plurality of pages of a memory; when a request to store first data is received, allocating a destination page corresponding to the first data using a page pool; and updating a page table using information about the allocated destination page.
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a method of managing memory, the method comprising: generating a page pool by aligning a plurality of pages of a memory; when a request to store first data is received, allocating a destination page corresponding to the first data using the page pool; and updating a page table using information about the allocated destination page. the method of claim 1, wherein the destination page is a page to which the first data is copied. the method of claim 1, wherein the destination page is allocated so that the destination page and a page in which the first data is stored are included either in a same rank or in a same channel. the method of claim 1, wherein the page pool is generated by aligning the plurality of pages according to ranks included in the memory. the method of claim 1, wherein the page table is updated by mapping a physical address corresponding to the destination page to a continuous logical address. the method of claim 1, further comprising generating a chuck pool using a space other than a space occupied by the first data in the memory. a computer-readable recording medium having embodied thereon a program for executing the method of claim 1 in a computer. an apparatus for managing memory, the apparatus comprising a controller configured to: generate a page pool by aligning a plurality of pages of a memory; when a request to store first data is received, allocate a destination page corresponding to the first data using the page pool; and update a page table using information about the allocated destination page. the apparatus of claim 8, wherein the destination page comprises a page to which the first data is copied. the apparatus of claim 8, wherein the controller is further configured to allocate the destination page so that the destination page and a page in which the first data is stored are included either in a same rank or in a same channel. the apparatus of claim 8, wherein the controller is further configured to generate the page pool by aligning the plurality of pages according to ranks included in the memory. the apparatus of claim 8, wherein the controller is further configured to update the page table by mapping a physical address corresponding to the destination page to a continuous logical address. the apparatus of claim 8, wherein the controller is further configured to generate a chunk pool using a space other than a space occupied by the first data in the memory. the apparatus of claim 13, wherein when a request to store second data is received, the controller is further configured to allocate a destination chunk corresponding to the second data using the chunk pool. the apparatus of claim 13, wherein the controller is further configured to allocate the destination page so that the destination chunk and a chunk in which the second data is stored are included in a same rank. the apparatus of claim 13, wherein the second data comprises data occupying a storage space smaller than a storage space corresponding to at least one of the pages. the apparatus of claim 8, wherein the apparatus is included in a dynamic random-access memory (dram).
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technical field the inventive concept relates to a method and apparatus for managing memory. discussion of related art application programs may include any program designed to perform a specific function directly for a user or, in some cases, for another application program. application programs typically require data processing systems having high performance. therefore, various in-memory data copying methods for avoiding memory latency overhead have been used. in a dynamic random-access memory (dram), data copying refers to a process of copying data from one area of the dram to another area of the dram. when data is copied in the dram and a central processing unit (cpu) intervenes in this process, the performance of the dram may deteriorate. summary according to an exemplary embodiment of the inventive concept, there is provided a method of managing memory, the method including: generating a page pool by aligning a plurality of pages of a memory; when a request to store first data is received, allocating a destination page corresponding to the first data using the page pool; and updating a page table using information about the allocated destination page. according to an exemplary embodiment of the inventive concept, there is provided an apparatus for managing memory, the apparatus including a controller configured to: generate a page pool by aligning a plurality of pages of a memory; when a request to store first data is received, allocate a destination page corresponding to the first data using the page pool; and update a page table using information about the allocated destination page. according to an exemplary embodiment of the inventive concept, there is provided a method of managing memory, the method including: dividing a memory into a plurality of pages and generating a page pool by aligning the pages; allocating a destination page to have a same rank as that of a source page, when a request for in-memory copying is received; and updating a page table by mapping a physical address corresponding to the destination page to a continuous logical address. brief description of the drawings exemplary embodiments of the inventive concept will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings in which: fig. 1 is a block diagram of a data processing system according to an exemplary embodiment of the inventive concept; fig. 2 is a block diagram for explaining a process of copying data according to an exemplary embodiment of the inventive concept; fig. 3 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept; fig. 4 is a block diagram of memory according to an exemplary embodiment of the inventive concept; fig. 5 is a diagram for explaining a process performed by a controller to align pages according to an exemplary embodiment of the inventive concept; fig. 6 is a diagram of a page pool according to an exemplary embodiment of the inventive concept; fig. 7 is a diagram for explaining a process performed by the controller to update a page cable according to an exemplary embodiment of the inventive concept; fig. 8 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept; fig. 9 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept; fig. 10 is a diagram for explaining a process performed by the controller to generate a chunk pool according to an exemplary embodiment of the inventive concept; fig. 11 is a diagram of a chunk pool according to an exemplary embodiment of the inventive concept; fig. 12 is a diagram of an application programming interface (api) for performing a method of managing memory according to an exemplary embodiment of the inventive concept; and figs. 13a and 13b are block diagrams illustrating an arrangement for managing memory according to an exemplary embodiment of the inventive concept. detailed description of the embodiments exemplary embodiments of the inventive concept will now be described more fully with reference to the accompanying drawings. fig. 1 is a block diagram of a data processing system 1 according to an exemplary embodiment of the inventive concept. referring to fig. 1 , the data processing system 1 includes a central processing unit (cpu) 10 and memory 30. in addition, the data processing system 1 includes a graphics processing unit (gpu) 20. the cpu 10 receives external information (e.g., data, commands, addresses, etc.), interprets and calculates instructions of a computer program, and outputs a calculation result. for example, the cpu 10 may interpret and execute instructions of a computer program provided in a machine language. the cpu 10 may control an overall operation of the data processing system 1 by exchanging information within the data processing system 1. when the data processing system 1 includes the gpu 20, the cpu 10 generates a draw call to be transmitted to the gpu 20 by using path data. the term 'path' used herein may refer to an element constituting an object to be rendered. in other words, the object may include a closed polygon or a closed path formed by connecting at least one path. for example, the path may correspond to a line or a curve. the gpu 20 receives the draw call and performs path rendering by using primitive data stored in the memory 30. in other words, the gpu 20 may calculate a color value of each of pixels included in a frame by using the primitive data. the term 'frame' used herein may refer to an image to be displayed on a screen, and one image is formed by setting a color to each of the pixels included in the frame. for example, one pixel may be set with a red color and another pixel may be set with a green color. for example, the gpu 20 may include a vertex shader, a rasterizer, a fragment shader, a pixel shader, and a frame buffer. the term 'primitive' used herein may refer to an element used in rendering. a result obtained after dividing a path may be referred to as a primitive, or a path and a primitive may be the same. the memory 30 stores information or data used to operate the cpu 10 and the gpu 20. the memory 30 also stores a result obtained after the cpu 10 and the gpu 20 process data. for example, the memory 30 may be a dynamic random-access memory (dram). data stored in the memory 30 may be copied to another area of the memory 30. in other words, data may be copied from a source area of the memory 30 to a destination area of the memory 30. for example, data may be copied from a first area of the memory 30 to a second area of the memory 30. a process of copying data from a source area of the memory 30 to a destination area of the memory 30 will now be explained with reference to fig. 2 . fig. 2 is a block diagram for explaining a process of copying data according to an exemplary embodiment of the inventive concept. referring to fig. 2 , a data processing system 2 includes the cpu 10, a plurality of gpus (e.g., first and second gpus 21 and 22), and the memory 30. although two gpus are illustrated in fig. 2 , exemplary embodiments of the inventive concept are not limited thereto. for example, more than two gpus may be provided in a data processing system of the inventive concept. the memory 30 is connected to the cpu 10 and the first and second gpus 21 and 22 and stores data. in this case, the memory 30 may be divided into a plurality of areas (e.g., first through third areas 31, 32, and 33). at least one area from among the first through third areas 31, 32, and 33 may be allocated to the cpu 10 and the first and second gpus 21 and 22. for example, the first area 31 may be allocated to the cpu 10, the second area 32 may be allocated to the first gpu 21, and the third area 33 may be allocated to the second gpu 22. accordingly, information or data used to operate the cpu 10 and a calculation result of the cpu 10 may be stored in the first area 31. when the first gpu 21 operates according to the calculation result of the cpu 10, data stored in the first area 31 (e.g., a source area) has to be copied to the second area 32 (e.g., a destination area). this is because since an area allocated to the first gpu 21 is the second area 32, the first gpu 21 may not access the data stored in the first area 31. accordingly, as the cpu 10 and the first and second gpus 21 and 22 operate, the memory 30 may perform a process of copying data stored in a source area to a destination area. referring back to fig. 1 , the cpu 10 may intervene in a process of copying data from a source area to a destination area. for example, the cpu 10 may read data stored in the source area, and then, may write the read data to the destination area. in this case, the performance of the memory 30 may deteriorate due to a bandwidth and a latency of a channel between the cpu 10 and the memory 30. an apparatus for managing memory according to an exemplary embodiment of the inventive concept may allocate a destination area so that the destination area is the same as a source area. for example, the apparatus for managing the memory may allocate the destination area so that the source area and the destination area are included in the same channel and in the same rank. each of the source area and the destination area may be, but not limited to, a page or a chunk of the memory 30. accordingly, as the apparatus for managing the memory operates, the performance of the memory 30 may increase. for example, the apparatus for managing the memory according to an exemplary embodiment of the inventive concept may be included in the memory 30, and may be included as an independent apparatus in the data processing system 1. in addition, the apparatus for managing the memory may include a controller, and the controller may control an overall operation of the apparatus for managing the memory. for convenience, the following description will be made on the assumption that the controller of the apparatus for managing the memory performs a method of managing a memory according to an exemplary embodiment of the inventive concept. fig. 3 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept. in operation 310, the controller generates a page pool by aligning a plurality of pages constituting the memory. for example, the controller may generate the page pool by aligning the plurality of pages according to ranks. the memory may be, but not limited to, a dram. the memory may include a plurality of ranks, and a plurality of pages may be included in one rank. the controller may align a plurality of pages included in the memory according to ranks. in operation 320, the when a request to store first data is received, a destination pace is allocated corresponding to the first data based on the page pool. in operation 330, a page table is updated based on information about the allocated destination page. a structure of the memory will now be explained with reference to fig. 4 . fig. 4 is a block diagram of the memory 30 according to an exemplary embodiment of the inventive concept. fig. 4 illustrates a structure of the memory 30 according to an exemplary embodiment of the inventive concept. in the memory 30, a plurality of banks 410 may be connected to one another and a plurality of ranks 420 may be included in each of the banks 410. for example, when the bank 410 is a module having a capacity of 128 megabytes (mb), eight ranks 420 each having a capacity of 16384*1024 bytes may be included in the bank 410. one rank 420 may be expressed as a matrix including a plurality of rows and a plurality of columns. accordingly, a row detector that writes/reads data to/from rows of the plurality of ranks 420 and a column detector that writes/reads data to/from columns of the plurality of ranks 420 may be connected to the bank 410. the same rows or the same columns in the plurality of ranks 420 included in the bank 410 refer to pages 430. for example, when eight ranks 420 each having a capacity of 16384*1024 bytes are included in the bank 410, the page 430 may have a storage capacity of at least one kilobyte (kb). data copy in the memory 30 may be performed in units of the pages 430. accordingly, the controller may generate a page pool by aligning the plurality of pages 430 constituting the memory 30. data copy in the memory 30 may be performed in units of chunks that are smaller than the pages 430. accordingly, the controller may generate a chunk pool by aligning chunks constituting the memory 30. a process performed by the controller to generate a page pool by aligning the pages 430 will now be explained with reference to figs. 5 and 6 . fig. 5 is a diagram for explaining a process performed by the controller to align pages according to an exemplary embodiment of the inventive concept. fig. 5 illustrates the memory 30 connected through a plurality of channels 511 and 512 to the cpu 10 according to an exemplary embodiment of the inventive concept. each of the channels 511 and 512 is a path through which data is transmitted/received between the cpu 10 and the memory 30. a plurality of ranks 521, 522, 523, and 524 may be connected to the channels 511 and 512. for example, n ranks 521 and 522 may be connected to the channel 511, and n ranks 523 and 524 may be connected to the channel 512. when a source area is the rank 521 and a destination area is the rank 522, data has to be read from the rank 521 and has to be written to the rank 522 through the channel 511. accordingly, since the channel 511 intervenes in a process of copying data, the performance of the memory 30 may deteriorate. in addition, when a source area is the rank 521 and a destination area is the rank 523, data has to be read from the rank 521 and has to be written to the rank 523 through the channels 511 and 512 and the cpu 10. accordingly, since the channels 511 and 512 and the cpu 10 intervene in a process of copying data, the performance of the memory 30 may deteriorate. when both a source area and a destination area are the rank 521, data may be rapidly and efficiently copied. for example, when a source area and a destination area are pages in the rank 521, data may be rapidly and efficiently copied. accordingly, when a source area and a destination area of data are allocated to pages in the same rank, power consumed when data is copied may be reduced and a time taken to copy the data may also be reduced. the controller generates a page pool by aligning a plurality of pages included in the memory 30 according to the ranks 521, 522, 523, and 524. when a request to store data is received, the controller may allocate a destination page so that a source page in which the data is stored and the destination page to which the data is to be copied are included in the same rank. fig. 6 is a diagram of a page pool 610 according to an exemplary embodiment of the inventive concept. fig. 6 illustrates the page pool 610 according to an exemplary embodiment of the inventive concept. for example, the page pool 610 may be a table in which pages 641 through 648 are aligned according to ranks 620 and 630. for example, the controller may recognize that the pages 641 through 644 are included in the same rank 620 and may perform a grouping so that the pages 641 through 644 correspond to the rank 620. similarly, the controller may perform a grouping so that the pages 645 through 648 correspond to the rank 630. as the controller generates the page pool 610, the controller may allocate a destination page so that a source page and the destination page are included in the same rank 620. referring back to fig. 3 , in the operation 320, when a request to store first data is received, the controller allocates a destination page corresponding to the first data based on the page pool. the first data may be, but not limited to, data having a size corresponding to a capacity of a page. for example, the controller may allocate the destination page so that the destination page and a page (e.g., a source page) in which the first data is stored are included in the same rank. alternatively, the controller may allocate the destination page so that the destination page and the source page are included in the same rank and the same channel. when the request to store the first data is received, the controller checks the page pool and searches for a page in which the first data may be stored. for example, the controller may search for a page that allows the source page and the destination page of the first data to be included in the same rank from among pages included in the page pool. alternatively, the controller may search for a page that allows the source page and the destination page of the first data to be included in the same rank and the same channel from among the pages included in the page pool. the controller allocates the found page to the destination page of the first data. in operation 330, the controller updates a page table based on information about the allocated destination page. the term 'page table' used herein may refer to a table in which a logical address and a physical address of a page are mapped to each other. for example, the controller may update the page table by mapping a physical address corresponding to the destination page to a continuous logical address. the controller may pre-allocate a data copy area (hereinafter, referred to as an 'iddc area') to an address space. the term 'address space' used herein may refer to a space in which a logical address of the memory 30 (or a page of the memory 30) is defined. for example, the cpu 10 (or the gpu 20) may determine a position at which data is stored in the memory 30 by referring to the logical address defined in the address space. the logical address defined in the address space and a physical address of the memory 30 (or the page of the memory 30) may be different from each other. accordingly, the cpu 10 (or the gpu 20) may determine a position at which data is stored in the memory 30 by referring to the logical address defined in the address space and the page table. a process performed by the controller to update the page table will now be explained with reference to fig. 7 . fig. 7 is a diagram for explaining a process performed by the controller to update a page table according to an exemplary embodiment of the inventive concept. fig. 7 illustrates an address space 710 including an iddc area 720 and a rank allocated to a page 730 according to an exemplary embodiment of the inventive concept. the page 730 may be a combination of parts allocated to at least one rank. in other words, parts constituting the page 730 may be respectively allocated to ranks, and types of the ranks may be various. for example, some parts of the page 730 may be included in 'ranks 0', and other parts of the page 730 may be included in 'ranks 1'. in addition, a physical address of each of the parts of the page 730 may be set. the address space 710 may be divided into a space in which settings of a system are recorded and a space in which settings of a user are recorded. the controller may allocate the iddc area 720 to the space in which the settings of the system are recorded. logical addresses of parts of the page 730 may be defined in the iddc area 720. a physical address and a logical address may be different from each other. accordingly, the controller generates a page table in which a physical address and a logical address of the same part of the page 730 are mapped to each other, and updates the page table as a destination page is allocated. for example, the controller may divide the memory in units of pages, and may allocate a free page having the same rank as that of a source page to a destination page. the controller may update the page table by mapping a physical address and a logical address of the destination page. fig. 8 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept. the method of fig. 8 includes operations performed by the controller of figs. 1 through 7 . accordingly, the descriptions made with reference to figs. 1 through 7 may apply to the method of fig. 8 . in operation 810, the controller divides the memory in units of pages. for example, the controller divides the memory into a plurality of pages and generates a page pool by aligning the pages. for example, the controller may generate the page pool by aligning the plurality of pages according to ranks. in operation 820, the controller allocates a destination page to a page having the same rank as that of a source page. for example, the controller may allocate the destination page so that the destination page and a page in which first data is stored (e.g., a source page) are included in the same rank. alternatively, the controller may allocate the destination page so that the destination page and the source page are included in the same rank and the same channel. in operation 830, the controller updates a page table. for example, the controller may update the page table by mapping a physical address corresponding to the destination page to a continuous logical address. the controller performs operations 820 and 830 on each of the source pages. for example, operations 820 and 830 may be performed on all of the source pages. in other words, whenever a request to store data is received, the controller repeatedly performs operations 820 and 830. data requested to be stored may be a chunk smaller than a page. accordingly, the controller may generate a chunk pool by aligning chunks constituting the memory 30. the controller may allocate a destination chunk of the data requested to be stored based on the chunk pool. a process performed by the controller to generate the chunk pool and allocate the destination chunk will now be explained with reference to figs. 9 through 11 . fig. 9 is a flowchart of a method of managing memory according to an exemplary embodiment of the inventive concept. the method of fig. 9 includes operations performed by the controller of figs. 1 through 8 . accordingly, the descriptions made with reference to figs. 1 through 8 may apply to the method of fig. 9 . operations 910 through 930 of fig. 9 are the same as operations 310 through 330 of fig. 3 . accordingly, a detailed explanation of operations 910 through 930 will not be given. in operation 940, the controller generates a chunk pool based on a space other than a space occupied by the first data in the memory. for example, the controller allocates the destination page of the first data and inserts a space other than the destination page allocated to the first page into the chuck pool. in operation 950, when a request to store second data is received, the controller allocates a destination chuck corresponding to the second data based on the chunk pool. a process performed by the controller to generate the chunk pool will now be explained with reference to figs. 10 and 11 . fig. 10 is a diagram for explaining a process performed by the controller to generate a chunk pool according to an exemplary embodiment of the inventive concept. fig. 10 illustrates a rank allocated to a page 1010. parts constituting the page 1010 may be respectively allocated to ranks, and types of the ranks may be various. for example, some parts of the page 1010 may be included in 'ranks 0', and other parts of the page 1010 may be included in 'ranks 1'. when a request to store first data is received, the controller allocates a destination page of the first data. for example, the destination page of the first data may be allocated to the 'rank 0'. in this case, a chunk 1020 that is a free storage space may be formed in parts 1012 and 1014 allocated to the destination page from among parts 1011, 1012, 1013, and 1014 constituting the page 1010. the controller inserts the parts 1012 and 1014 in which the chunk 1020 is formed into a chunk pool 1030. accordingly, when a request to store second data is received, the controller may allocate a destination chunk of the second data based on the chunk pool 1030. fig. 11 is a diagram of a chunk pool 1110 according to an exemplary embodiment of the inventive concept. fig. 11 illustrates the chunk pool 1110 according to an exemplary embodiment of the inventive concept. for example, the chunk pool 1110 may be a table in which parts 1141 through 1147 each including a chunk are aligned according to ranks 1120 and 1130. for example, the controller may recognize that the parts 1141 through 1143 are included in the same rank 1120 and may perform a grouping so that the parts 1141 through 1143 correspond to the rank 1120. similarly, the controller may perform a grouping so that the parts 1144 through 1147 correspond to the rank 1130. as the controller generates the chunk pool 1110, the controller may allocate a destination chunk so that a source chunk and the destination chunk of data are included in the same rank 1120 or 1130. referring back to fig. 9 , in the operation 950, when a request to store second data is received, the controller allocates a destination chunk corresponding to the second data based on the chunk pool. the term 'second data' used herein may refer to data occupying a storage space smaller than a storage space corresponding to a page. for example, the controller may allocate the destination chunk so that the destination chunk and a chunk (e.g., a source chunk) in which the second data is stored are included in the same rank. alternatively, the controller may allocate the destination chunk so that the destination chunk and the source chunk are included in the same rank and the same channel. in addition, the controller may update the page table based on information about the allocated destination chunk. for example, the controller may update the page table by mapping a physical address corresponding to the destination chunk to a continuous logical address. a process performed by the controller to update the page table is the same as or substantially similar to that described with reference to fig. 7 . fig. 12 is a diagram of an application programming interface (api) for performing a method of managing memory according to an exemplary embodiment of the inventive concept. when iddcopydstalloc(src, size) is input, the controller interprets a physical address of a source page/chunk (src), and allocates a page/chunk that is in the same channel and the same rank as those of the source page/chunk (src) as a destination page/chunk. when iddcopyset(dest, src, size) is input, the controller sets register values such as an address of the source page/chunk (src) and an address of a destination page/chunk (dest) in a data copy module located in the memory 30. when iddcopystart() is input, the controller commands the data copy module to copy data from the source page/chunk (src) to the destination page/chunk (dest). figs. 13a and 13b are block diagrams illustrating an apparatus for managing memory according to an exemplary embodiment of the inventive concept. data processing systems 3 and 4 of figs. 13a and 13b include the cpu 10, the gpu 20, memories 1320 and 1340, and apparatuses 1310 and 1330 for respectively managing the memories 1320 and 1340. in addition, each of the apparatuses 1310 and 1330 include the controller of figs. 1 through 12 . referring to fig. 13a , the apparatus 1310 may be included in the memory 1320. in this case, a method of managing memory according to an exemplary embodiment of the inventive concept may be performed without changing a hardware structure of the data processing system 3. referring to fig. 13b , the apparatus 1330 may be included as an independent apparatus in the data processing system 4. in this case, the apparatus 1330 may be connected to the cpu 10, the gpu 20, and the memory 1340 and may perform a method of managing memory according to an exemplary embodiment of the inventive concept. as described above, since data stored in a memory may be copied to another space of the memory without intervention of a cpu, a process of copying data in the memory may become more efficient. the afore-described method may be implemented as an executable program, and may be executed by a general-purpose digital computer that runs the program by using a computer-readable recording medium. in addition, a structure of data used in the method may be recorded by using various units on a computer-readable recording medium. examples of the computer-readable recording medium include storage media such as magnetic storage media (e.g., read only memories (roms), floppy discs, or hard discs), optically readable media (e.g., compact disk-read only memories (cd-roms), or digital versatile disks (dvds)), etc. while the inventive concept has been particularly shown and described with reference to embodiments thereof, the inventive concept should not be construed as limited to those embodiments. for example, it will be understood that various changes in form and details may be made thereto without departing from the spirit and scope of the inventive concept as defined by the claims.
|
074-546-419-906-864
|
JP
|
[
"JP",
"EP",
"US"
] |
G06F17/50,G06T17/00,G06F19/00,G06G7/48
| 2001-01-19T00:00:00 |
2001
|
[
"G06"
] |
design support system, and design support method
|
problem to be solved: to provide a design support system which can enhance reusability of historical data of design work of the past and to improve work efficiency. solution: while a historical design work data is segmented, based on the direction and unit work historical data, being a generated, an input job part by a working staff in the history is searched, the input for the design support information corresponding to the job is accepted, the inputted design support information is inserted in the work unit historical data and stored in a database 1. the working staff who reuses this unit work historical data executes the design work referring the design work historical data to be regenerated, in advance, in a design support window which is displayed on a display part 24 of a design support device 2 and the design support information which is included in the data.
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a design support system, comprising: a holding device which divides a history of design work for creating a shape model for each part of the shape model and holds a plurality of design work histories as unit work history data; a selection device which fetches at least two unit work history data selected from the plurality of unit work history data held by the holding device; and a combining device which combines the at least two selected unit work history data and outputs design work data for creating a combined shape model which is formed by joining part shape models corresponding to the respective unit work history data. a design support system which outputs work data for creating a shape model of a design target in order to create the shape model of the design target conforming to a standard shape, comprising: a holding device which holds a plurality of unit work history data which are obtained by dividing a history of a design work performed with reference to a first standard shape for each design work history corresponding to a shape model of a predetermined portion; a receiving device which accepts designation of data about a second standard shape; a selecting device which fetches multiple unit work history data selected from the multiple unit work history data held by the holding device; and an output device which combines each of the fetched unit work history data, reproduces design work with reference to the designated second standard shape for the design works performed with reference to the first standard shape among the design works contained in the unit work history data, and outputs work data corresponding to a combined shape model conforming to the second standard shape. the design support system according to claim 2, further comprising: a device which computes at least one technical characteristic value of a combined shape model which is created from the output work data. the design support system according to claim 3, wherein: the holding device accumulates technical conditions, which should be met by a part shape model to be created according to each unit work history data, in association with each unit work history data; and further comprising: a device which compares the computed technical characteristic value with the technical conditions related to unit work history data which is the origin of the work data. the design support system according to claim 2, further comprising: a device which receives designation of data about a third standard shape; wherein: the work data is converted by reproducing a design work with reference to the designated third standard shape for work included in the work contained in the output work data and performed with reference to the second standard shape, and conversion work data corresponding to a shape model conforming to the third standard shape is output. the design support system according to claim 1, further comprising: a device which analyzes a history of design work and extracts input work carried out by a person in charge of work when unit historical data is created; a device which shows the extracted input work to the person in charge of work to receive input of design support information; and a device which records the design support information in a history of the design work and divides into unit historical data when the design support information is input so to show when the design support information is reused. a design support system which holds a series of design work histories to reuse as work history data and creates a shape based on the work history data, comprising: a device which analyzes the work history data to extract input work carried out by a person in charge of work; a device which shows the extracted input work to the person in charge of work to receive input of design support information; and a device which records the design support information in the work history data when the design support information is input so to show when the design support information is reused. the design support system according to claim 7, further comprising: a device which generates unit work history data by dividing the work history data into predetermined work units for each design target. a design support system, comprising: a device which accumulates unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; a device which selectively shows the unit work history upon receiving designation of the design target; a device which creates a shape by sequentially reproducing the selected unit work history; and a device which provides design support information related to input work when the input work is demanded while the unit work history is being reproduced. the design support system according to claim 9, further comprising: a device which judges whether the work history to be reproduced agrees with predetermined guidance display conditions while the unit work history is being reproduced; and a device which implements a guidance display determined in connection with the guide display conditions if the work history agrees with the guidance display conditions. a design support system, comprising: a device which accumulates unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to an input work among the design work; a first display device which shows a shape of a design target obtained by sequentially reproducing a history of the design work with reference to the unit work history data; and a second display device which shows design support information contained in the unit work history data by reproducing a history of a design work prior to the reproduction at the first display device. a design support method using a computer, wherein: a series of design work histories is held in multiple quantities as work history data in a database in order to create a part shape model; at least two selected work history data are fetched from the held multiple work history data according to an instruction input to a processor; and design work data for creating a one-piece shape model by combining the at least two fetched work history data and connecting part shape models corresponding to the respective work history data is output. a design support method which uses a computer to create a shape model of a design target conforming to a desired standard shape according to input to its processor and outputs work data for creating the shape model of the design target, comprising the steps of: holding a plurality of histories of design work performed in the past with reference to the respective standard shapes in a database as work history data; accepting designation of data about a second standard shape, which is a desired standard shape, according to an instruction input to the processor; fetching the selected multiple work history data from the multiple work history data held in the database; and combining respective pieces of the fetched work history data, reproducing design work with reference to the designated second standard shape for the design work performed in the past with reference to the respective standard shapes among the design work contained in the work history data, and outputting work data corresponding to a combined shape model conforming to the second standard shape. a design support method which holds a series of design work histories as work history data in order for reuse and generates a shape by a computer according to the work history data according to an instruction input to a processor, comprising the steps of: analyzing the work history data upon input to the processor to extract the input work performed by a person in charge of work; and showing the extracted input work to the person in charge of work to receive input of design support information and, when the design support information is input, recording the design support information in the work history data so to show it at the time of reuse. a design support method, comprising the steps of: accumulating, using a computer, unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; showing the unit work history selectively upon receiving designation of a design target by the computer; creating a shape by sequentially reproducing the selected unit work history; and providing the design support information related to input work when the input work is demanded while the unit work history is being reproduced. the design support method according to claim 15, wherein it is judged whether the work history to be reproduced conforms to predetermined guidance display conditions while the unit work history data is being reproduced by the computer and, if it conforms to the guidance display conditions, a guidance display determined in connection with the guide display conditions is performed. a recording medium storing a design support program and being computer-readable, the design support program comprising: a module holding a series of design work histories as a plurality of work history data for creation of a part shape model; a module fetching at least two selected work history data from the held multiple work history data; and a module outputting design work data for creating a one-piece shape model by combining the at least two fetched work history data and connecting part shape models corresponding to the respective work history data. a recording medium storing a design support program and being computer-readable, the design support program comprising: a module outputting work data for creating a shape model of a design target in order to create the shape model of the design target conforming to a desired standard shape; a module holding a history of design work performed with reference to a first standard shape as a plurality of work history data; a module receiving designation of data about a second standard shape which is a desired standard shape; a module fetching the selected multiple work history data from the held multiple work history data; and a module combining each of the fetched work history data, reproducing design work with reference to the designated second standard shape for the design works performed with reference to the first standard shape among the design works contained in the work history data, and outputting work data corresponding to a one-piece shape model conforming to the second standard shape. a recording medium storing a design support program and being computer-readable, the design support program comprising: a module holding a series of design work histories to reuse as work history data; a module analyzing the work history data to extract input work performed by a person in charge of work; a module showing the extracted input work to the person in charge of work to receive input of design support information; and a module recording the design support information in the work history data when the design support information is input in order to show it when reused. a recording medium storing a design support program and being computer-readable, the design support program comprising: a module accumulating unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; a module selectively showing the unit work history upon receiving designation of the design target; a module creating a shape by sequentially reproducing the selected unit work history; and a module providing design support information related to an input work when the input work is demanded while the unit work history is being reproduced. the recording medium being computer-readable according to claim 20, wherein: the design support program stored in the recording medium further includes a module judging whether the work history to be reproduced agrees with predetermined guidance display conditions while the unit work history is being reproduced and, if the work history agrees with the guidance display conditions, implements a guidance display determined in connection with the conditions.
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background of the invention field of the invention the present invention relates to a design support system such as cad (computer aided design), and more particularly to an improvement in work efficiency. description of the related art recently, cad generally performs modeling of figures by combining basic figure elements called primitives, or by performing predetermined processing of the primitives as they are, or a combination thereof. specifically, when one edge of a cube is rounded to have a curved shape, a rounding process of that edge is performed with respect to a cube primitive to create a figure, or the same figure is created by extrusion processing of one quarter of a circle, for example. as a conventional cad system, there is known a cad system which records a history of work contents such as creation, arrangement, processing, etc. of a primitive as work history data and also relates data (figure data) of a figure itself created by the work history data to record and manage as a file, as shown in fig. 13. according to this cad system, the work history data can be traced back to change the contents of the past work. for example, histories of design work for parts elements such as a bolt and a nut have their designs and structures made common to some degree and their shapes are simple. they can therefore be readily reused to design another product. in an actual design situation, a design work of a single product is often conducted separately by a plurality of design teams at the same time in order to speed-up designing. division of the design work is carefully decided to prevent the design results from individual teams from disagreeing with the designs made by other teams. however, it is difficult to completely eliminate mutually dependency. for example, to design a single vehicle body, a design of its outside body shape (designed surface, which will be hereinafter called a reference surface) and a design of each component part of each body section are separately performed by different teams, but the shapes of the body parts cannot be decided unless the outside body shape is decided because they must conform to the outside body shape. for example, when the aforementioned conventional cad system is used to design body parts of a vehicle, their designs and structures are variable depending on design targets, and their shapes are also complex, increasing work history data up to 3000 to 7000 steps. therefore, it is not realistic to reuse the work history data in view of overhead costs for fetching a required shape from the work history data to know the meaning of work in each step etc. consequently, design work has to be carried out again from the beginning, and this is very inefficient. it is difficult to reuse certain work history data to actually carry out design unless information such as, for example, directions of drawn line segments, input coordinate values and the like of the work are known even if that work history data is comprised of steps which happen to be reusable. meanwhile, when a history of each design work is to be recorded and a shape is represented with reference to a reference surface at a time when the design work is performed, e.g., by designating an offset amount from a temporary reference surface which is used as a standard, a shape conforming to the reference surface, even if it is changed, can be created with ease by reproducing the shape with an offset amount from the changed reference surface. however, if a number of surfaces, a direction of a boundary line or the like, which is referenced between the temporary reference surface and the changed reference surface, is changed, a conforming shape cannot be created properly. summary of the invention the present invention was completed in view of the aforementioned circumstances, and, it is an object of the invention to provide a design support system which can improve work efficiency by enhancing reusability of past work history data. in order to remedy the aforementioned disadvantages, the present invention provides a design support system, comprising a holding device which divides a history of design work for creating a shape model for each part of the shape model and holds a plurality of design work histories as unit work history data; a selection device which fetches at least two unit work history data selected from the plurality of unit work history data held by the holding device; and a combining device which combines the at least two selected unit work history data and outputs design work data for creating a combined shape model which is formed by joining part shape models corresponding to the respective unit work history data. in order to remedy the aforementioned disadvantages, the present invention also provides a design support system which outputs work data for creating a shape model of a design target in order to create the shape model of the design target conforming to a standard shape, comprising a holding device which holds a plurality of unit work history data which are obtained by dividing a history of design work performed with reference to a first standard shape for each design work history corresponding to a shape model of a predetermined portion; a receiving device which accepts designation of data about a second standard shape; a selecting device which fetches multiple unit work history data selected from the multiple unit work history data held by the holding device; and an output device which combines each of the fetched unit work history data, reproduces design work with reference to the designated second standard shape for the design works performed with reference to the first standard shape among the design work contained in the unit work history data, and outputs work data corresponding to a combined shape model conforming to the second standard shape. it is also preferable to additionally have a device which computes at least one technical characteristic value of a combined shape model which is created from the output work data. it is also suitable for the holding device to accumulate technical conditions, which shall be met by a part shape model to be created according to each unit work history data, in association with each unit work history data; and there is further provided a device which compares the computed technical characteristic value with the technical conditions related to unit work history data which is the origin of the work data, so as to provide the compared results to predetermined design processing. it is also preferable to additionally have a device which receives designation of data about a third standard shape; and the work data is converted by reproducing design work with reference to the designated third standard shape for work which is included in the work contained in the output work data and performed with reference to the second standard shape, and conversion work data corresponding to a shape model conforming to the third standard shape is output. it is also preferable to further include a device which analyzes a history of design work and extracts input work made by a person in charge of work when unit history data is created; a device which shows the extracted input work to the person in charge of work to receive input of design support information; and a device which records the design support information in a history of the design work and divides into unit history data when the design support information is input, so as to show when the design support information is reused. in order to remedy the aforementioned disadvantages, the present invention also provides a design support system which holds a series of design work histories to reuse as work history data and creates a shape based on the work history data, comprising a device which analyzes the work history data to extract input work made by a person in charge of work; a device which shows the extracted input work to the person in charge of work to receive input of design support information; and a device which records the design support information in the work history data when the design support information is input so as to show when the design support information is reused. thus, an operator reusing the design support information can be provided with the design support information describing meanings of the respective work etc., and reusability and work efficiency are improved. it is preferable to further provide the design support system with a device which generates unit work history data by dividing the work history data into predetermined work units for each design target. thus, the work history data can be registered as predetermined divided elements and, for example, reuse of the work history data on side portions only is promoted. in order to remedy the aforementioned disadvantages, the present invention also provides a design support system, comprising a device which accumulates unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; a device which selectively shows the unit work history upon receiving designation of the design target; a device which creates a shape by sequentially reproducing the selected unit work history; and a device which provides design support information related to input work when the input work is demanded while the unit work history is being reproduced. it is also preferable that the design support system is further provided with a device which judges whether the work history to be reproduced agrees with predetermined guide display conditions while the unit work history is being reproduced; and a device which performs a guide display determined in connection with the guide display conditions if the work history agrees with the guide display conditions. besides, in order to remedy the aforementioned disadvantages, the present invention also provides a design support system, comprising a device which accumulates unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; a first display device which shows a shape of a design target obtained by sequentially reproducing a history of the design work with reference to the unit work history data; and a second display device which shows design support information contained in the unit work history data by reproducing a history of a design work ahead of the reproducing state by the first display device. besides, in order to remedy the aforementioned disadvantages, the present invention also provides a design support method which holds a series of design work histories as work history data for reuse and creates a shape based on the work history data, comprising the steps of analyzing the work history data to extract input work carried out by a person in charge of work, showing the extracted input work to the person in charge of work to receive input of design support information, and recording the design support information in the work history data when the design support information is input so as to show when the design support information is reused. in order to remedy the aforementioned disadvantages, the present invention also provides a design support method, comprising the steps of accumulating unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work among the design work; selectively showing the unit work history upon receiving designation of the design target; creating a shape by sequentially reproducing the selected unit work history; and providing design support information related to input work when the input work is demanded while the unit work history is being reproduced. it is also preferable for this design support method to judge whether the work history to be reproduced agrees with predetermined guide display conditions while the unit work history is being reproduced and to perform a guidance display determined in connection with the guidance display conditions if the work history agrees with the guidance display conditions. in order to remedy the aforementioned disadvantages, the present invention also provides a design support method using a computer, wherein a series of design work histories are held in multiple quantities as work history data in a database in order to create a part shape model; at least two selected work history data are fetched from the held multiple work history data according to an instruction input to a processor; and design work data for creating a one-piece shape model by combining the at least two fetched work history data and connecting part shape models corresponding to the respective work history data is output. in order to remedy the aforementioned disadvantages, the present invention also provides a design support method which uses a computer to create a shape model of a design target conforming to a desired standard shape according to input to its processor and outputs work data for creating the shape model of the design target, comprising the steps of holding a plurality of histories of design work performed in the past with reference to the respective standard shapes in a database as work history data; accepting designation of data about a second standard shape, which is a desired standard shape, according to an instruction input to the processor; fetching the selected multiple work history data from the multiple work history data held in the database; and combining respective pieces of the fetched work history data, reproducing design work with reference to the designated second standard shape for the design work performed in the past with reference to the respective standard shapes among the design works contained in the work history data, and outputting work data corresponding to a combined shape model conforming to the second standard shape. the respective design work histories subject to combination may be made with reference to different standard shapes (different first standard shapes). in order to remedy the aforementioned disadvantages, the present invention also provides a design support method which holds a series of design work histories as work history data for reuse and generates a shape by a computer according to the work history data according to an instruction input to a processor, comprising the steps of analyzing the work history data upon input to the processor to extract the input work performed by a person in charge of work; showing the extracted input work to the person in charge of work to receive input of design support information and, when the design support information is input, recording the design support information in the work history data so as to show it at reuse. in order to remedy the aforementioned disadvantages, the present invention also provides a design support method, comprising the steps of accumulating, by a computer, unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to an input work among the design work; showing the unit work history selectively upon receiving designation of a design target by the computer; creating a shape by sequentially reproducing the selected unit work history; and providing the design support information related to input work when the input work is demanded while the unit work history is being reproduced. here, it is preferable that it is judged whether the work history to be reproduced conforms to predetermined guidance display conditions while the unit work history data is being reproduced by the computer and, if it conforms to the guidance display conditions, a guidance display determined in connection with the guide display conditions is performed. brief description of the drawings fig. 1 is a structural block diagram of a design support system according to an embodiment of the present invention; fig. 2 is an explanatory diagram showing an example of work history data accumulated in a database 1; fig. 3 is a flow chart showing an example of an editing process; fig. 4 is a flow chart showing an example of a designing process; fig. 5a and fig. 5b is an explanatory diagram showing example selection screens; fig. 6 is a flow chart partly showing an example of an editing process; fig. 7a and fig. 7b and fig. 7c and fig. 7d and fig 7e and fig. 7g and fig. 7h is an explanatory diagram showing an example of a guidance display; fig. 8a is an explanatory diagram showing a relationship between a reference surface and work history data; fig. 8b is an explanatory diagram showing a relationship between a reference surface and work history data; fig. 9 is an explanatory diagram showing an example of an error situation caused when a design is replaced; fig. 10 is a diagram showing a design flow by a design support system of an embodiment; fig. 11 is an explanatory diagram showing an example of a screen display; fig. 12 is an explanatory diagram showing an example of a screen display; and fig. 13 is an explanatory diagram showing example contents of a design data file. description of the preferred embodiment an embodiment of the present invention will be described with reference to the accompanying drawings. the design support system according to the embodiment of the present invention is comprised of a database 1 as means for accumulating work history data and a design support device 2 as shown in fig. 1. the design support device 2 is basically configured of a control section 21 (processor), a storage section 22, an external storage device 23, a display section 24 and an operation section 25. the database 1 and the design support device 2 are mutually connected over a network or the like. the database 1 holds records of the past design work performed by the design support device 2 as design work history data. this embodiment has a feature that the design work history data held by the database 1 is divided and registered for each work unit which is previously determined for each design target. the work unit will be hereinafter called unit work history data. for example, body parts of a vehicle are previously determined to have units such as a "side" a "rib" and the like, and the design work history data is divided for each data about such parts and registered as unit design work history data in the database 1. specifically, this database 1 has a history of the past design work for each design target divided into a unit work history and registered together with its name (a) as shown in fig. 2. it is also desirable that a shape resulting from the execution of the unit work history is also registered (b). another feature of this embodiment is that the unit work history data includes design support information determined by a person in charge of work. setting of the design support information will be described in conjunction with the operation of the control section 21 later. the control section 21 of the design support device 2 basically performs processing (design processing) corresponding to the design work and processing (edit processing) for editing the contents of the design work. such processing will be described in detail later. the storage section 22 is a hard disk or the like and stores programs for design processing and edit processing executed by the control section 21. the external storage device 23 reads a program from a storage medium such as cd-rom or dvd and outputs to the control section 21. the read program is installed in the storage section 22 by the control section 21. the display section 24 is a display or the like which displays according to an instruction from the control section 21. the operation section 25 is a mouse, a keyboard or the like which outputs the contents operated by the person in charge of work to the control section 21. [processing by control section] here, design processing and edit processing by the control section 21 will be described specifically. in the design processing, the control section 21 shows a window screen for designing (main window) and performs the same design work as conventional parametric cad does. the contents of the design work are registered as work history data in the database 1. [edit processing] the control section 21 starts analyzing the registered work history data according to an instruction by the person in charge of work and starts the edit processing shown in fig. 3. the control section 21 reads the work history data subject to the processing (s1) and retrieves input work by the person in charge of work from the work history data (s2). the input work includes, for example, the designation of a primitive, the input of coordinate values, the instructions for a computation (instructions for the sum (combination) of a primitive a and a primitive b, their difference (clipping) or their product (taking out of a multiple part)), and their order (whether b is subtracted from a or a is subtracted from b). the control section 21 judges whether the input work is found by searching (s3), and if it is found (if yes), highlights the contents of the input work on the display section 24 (s4), and requests the person in charge of work to input design support information such as a comment and a meaning of the work (55). when the design support information is input or no input thereof is instructed, it is judged which one is made (s6), and if the design support information is input (an input is made), the input information is inserted in connection with the input work into the work history data (s7), and the procedure returns to the step s2 to continue processing. if the design support information is not input in the step s6 (no input), the procedure returns to the step s2 to continue processing. furthermore, if no additional input work is found by searching in the step s3 (when the steps s4 to s7 are completed for all the input work), the work history data after the processing is registered in the database 1, and the procedure is terminated. here, the highlighting in the step s4 is animated for example by alternately displaying the shapes before and after the work or by indicating a work command. the edit processing, means and procedures for extraction of the input work of the present invention, reception of the input of the design support information and recording in the work history data, are realized by software. [creation of unit work history data] the control section 21 extracts data ranging from a first position to a second position designated in the work history data, stores it with a name added thereto, and registers as unit work history data in the database 1. thus, means and procedures for generating unit work history data are realized. specifically, a procedure to design an l-shaped member, to divide it, and to generate unit work history data will be described. first, when the l-shaped member is designed, two sides configuring the l-shaped member can be separately designed and then put together. in other words, a first sectional shape is created, the created first sectional shape is extruded by a designing operation to create a pillar shape (a first side), a second sectional shape is separately created so as to cross at right angles with the first side, and the created second sectional shape is extruded by a designing operation to create another pillar shape (a second side). thus, the first and second sides are created and put together to design the l-shaped member. here, if the first sectional shape and the second sectional shape are different, both the sectional shapes are interpolated to form a joint part (joint block). the design work history of the l-shaped member designed as described above is divided to create unit work history data. division can be made into any unit, e.g., the first side, the second side and the joint block. the control section 21 receives from the person in charge of work the operation to fetch the data ranging from the instruction to create the first sectional shape (first position) to the instruction to create the pillar shape by extruding the first sectional shape as the unit work history data in the work history, inquires the person in charge of work about a name to be given to the fetched unit work history data, receives the input of the name, and registers the previously fetched unit work history data with the name into the database 1. it is then determined that an instruction to create the second sectional shape is a first position and the instruction to create the second shape by extruding the first position is a second position, and unit work history data is fetched and registered in the database 1 in the same way as above. this embodiment has a feature that the instruction to create the joint block extending from the first sectional shape to the second sectional shape can also be recorded as unit work history data in the database 1. the first sectional shape and its extrusion and the second sectional shape and its extrusion may be instructed as an offset value or the like from a predetermined design surface. in other words, individual corners of the sectional shape, the extruding direction, the extruding volume, etc. may be designated based on the coordinate values of surface elements forming a separately designated design surface. each instruction may be made including conditions (design requirements) such as size values necessary for the pertinent design part to exhibit necessary performance, conditions (production technology requirements) of values necessary for processing the pertinent part, etc. interpolation processing is made according to an interpolation parameter instructed by the person in charge of work, and the joint block has a shape which is slightly different depending on the interpolation parameter. the unit work history data registered in the database 1 as described above is used for actual designing. [design processing] design processing by the control section 21 of the design support device 2 of this embodiment will now be described. the design processing works to support the process to fetch the contents of the past design work for reuse. specifically, the control section 21 receives the input of the instruction to read the unit work history data from the database 1, starts the processing shown in fig. 4, reads a name (or a shape obtained by it) of the unit work history data related to the design target to be designed now, and performs selective display on the display section 24 (s11). this displaying embodiment may show a list of names as shown in fig. 5a or preferably may show a list of shapes as shown in fig. 5b. here, when one of the unit work history data is selected by manipulating the mouse of the operation section 25, the control section 21 reads the unit work history data from the database 1 (s12), shows the design support window (s13), processes to sequentially execute the unit work history data one by one (s14) and terminates the processing after completing the execution. thus, the database 1 having accumulated a plurality of unit work history data can be a "shelf" for the unit work history data, and the person in charge of work can fetch the unit work history data from the "shelf" to use it for designing. here, the step s14 for sequentially executing the unit work history data fetches the next single work procedure of the read unit work history data as shown in fig. 6 (s20) and checks whether. it is input work or not (s21). this input work includes, for example, instructions for designation of a primitive, input of coordinate values, a computation instruction, etc. if it is not input work (if no), the work is reproduced in the main window (s22) (i.e., a shape is created), and the procedure returns back to the step s20 to continue the processing. meanwhile, if the work procedure fetched in the step s21 is input work (if yes), it is judged whether there is design support information related to it (s23), and if there is design support information (if yes), it is shown on the design support window (s24), and an operation is awaited (s25). when the operation executed in the step s25 is an instruction to execute the unit work history data as it is (approval instruction), the procedure returns to the step s20 to continue the processing (b). however, if there is no design support information in the step s23 (if no), display is carried out to ask the person in charge of work whether the work procedure fetched in the step s20 may be executed as it is (s26), and the procedure moves to the step s25. when the operation executed in the step s25 is different from an operation for the unit work history data (another operation), the operation for the shape in the main window is executed accordingly (s27), the next input work is retrieved (namely, the present input work is skipped) (s28), the procedure returns back to the step s20, and the processing is continued from the retrieved input work. if the next work is not in the step s20 or the next input work cannot be retrieved in the step s28, the processing is terminated. here, when a display is made in the steps s24 and s26 and the work procedure fetched in the step s20 is executed, it is preferable to show in the design support window what shape is formed as a result. this is performed by reproducing the procedure until a command for the next input work in the design support window. in other words, the display in the design work window takes precedence and is also synchronized with the designing situation being performed in the main window, and even if a work procedure different from the one for the unit work history data being reused for the work shape on the way is performed, synchronization can be made again from the next input work. here, it is configured that when an operation different from the one for the unit work history data is executed, a corresponding operation is skipped (step s28). however, it may be configured to ask the person in charge of work whether this skipping operation shall be skipped or not, and the step s28 is executed only when it is instructed to skip it, but if not, the procedure may be repeated from the step s23. [support information not depending on input by person in charge of work] in the aforementioned description, design support information which is provided in accordance with the display effected in the step s24 or s26 is previously determined by a creator (or editor) of the unit work history data being reproduced. however, it is also preferable that a guide display condition related to information indicating the display mode is accumulated in the storage section 22 for a command indicating a particular operation, such as an input operation of line segments, an input operation to determine a single shape by a plurality of steps, an operation to move a given shape or the like, it is judged whether the command related to the work history being reproduced agrees with the guide display condition, and if it agrees, a predetermined guide display is made within the design support window according to the information about the display mode related to the command. for example, this guide display is effected by the embodiment as shown in fig. 7. specifically, when the input operation of a line segment is performed, the arrow (x) indicating a direction of the line segment is highlighted (fig. 7a), and if input of many steps is required, numerals indicating an input order are shown (y) in the proximity of the shape determined by each input (fig. 7b). besides, a moving direction of the figure is indicated by the arrow (z) (fig. 7c). highlight of the reproduced section (fig. 7d) and an input order of the shape elements at computing (fig. 7e) are also shown. when a shape (sketch) which is not created through a series of steps, but only defined by entering dimensions, is contained in the work history, an indication of the coordinate axes used to define the shape (fig. 7f), an indication of size conditions (constraint conditions) (fig. 7g) and an indication of the fetched sketch element (fig. 7h), are given as the guide indications. the input order of the shape elements at the time of computing is determined so as to prevent creation of a different shape element. for example, when a new shape element is created by subtracting a subsequent input shape element (subsequent shape element) from a previous input shape element (previous shape element), an erroneous reverse subtraction, namely the subtraction of the previous shape element from the subsequent shape element, can be prevented. thus, first display means of the present invention are realized by the above processing to show the main window, and second display means of the invention are realized by the processing to show the design support window. [reproduction based on the designated reference surface] in the design processing by the control section 21, the unit work history data is based on the reference surface (original reference surface (a first standard shape of the present invention)) used for the past designing, and, for example, the work history may be configured using an offset value from the reference surface. thus, it is possible to design while conforming to a specific reference surface as the shape elements (points, line segments, surfaces, etc.) to be a standard specify other shape elements (namely, the other shape elements refer to data on the shape elements to be standards). the unit work history data may be created using design work based on a different reference surface. in other words, there may be more than one first standard shape. in this case, a reference surface to which the design content shall conform is designated in advance of the design processing, and an offset value or the like included in the work history is used with reference to the designated reference surface (second standard shape of the invention) in the reproduction of the procedure shown in fig. 6 (step s22). here, the reference surface is generally designed by combining shape elements having a plurality of surfaces, and upon receiving the designation about which surface (or which surface group) is used as a standard for the reproduction procedure, the work history is reproduced based on the surface shape designated as the standard. thus, a member conforming to the designated reference surface can be designed according to the past design history. for the results of designing the member conforming to the designated reference surface, the control section 21 analyzes a strength according to a method such as a finite element method, computes a value (technical characteristic value) indicating technical characteristics, and shows the results to the person in charge of work. [use of design requirements and production technology requirements] the technical characteristic value is compared with the design requirement and production technology requirement contained in the work history, and the results are shown to the person in charge of work. thus, the person in charge of work is provided with the results of evaluating the design contents as required to know a change in the technical characteristic values involved in the shape change (edit of the design history) etc., and can readily design while keeping the technical characteristic values at an appropriate level. [combination of at least two unit work history data] the person in charge of work can also create a single combined shape by combining at least two unit work history data fetched by design processing. for example, a first unit work history which is a work history for designing a side portion and a second unit work history which is a work history of designing a rib portion are fetched, and it is instructed to connect the side portion and the rib portion at their designated ends. this instruction may be an instruction to interpolate by designating a new interpolation parameter for the shapes of the ends to be joined or an instruction to join by fetching a joint block registered as unit work history data in the database 1 and using an interpolation parameter included as the joint block. according to the latter, the past design history can be used to simplify the design work. the combined shape is created according to the history of a series of work procedures for combining a plurality of unit work data. it is also desirable to make the series of work procedures after the combination executable sequentially one by one. in this case, the next single work procedure is sequentially fetched from the series of work procedures obtained by combining, and the same procedure as the one shown in fig. 6 is executed. specifically, it is checked whether the fetched procedure is input work (instructions such as designation of a primitive, input of coordinate values, a computation instruction, etc.), and if it is not input work, the work is reproduced in the main window (namely, a shape is created), while if it is input work, it is judged whether there is design support information which is linked to the input work, and if there is design support information, the design support information is shown on the design support window, and an operation is awaited. also, if there is no design support information, the person in charge of work is asked whether the work procedure may be executed as it is, and an operation is waited for. here, the person in charge of work inputs an instruction (approval instruction) to execute as it is or performs a different operation (another operation). when the approval instruction is input, the work data is executed as it is, the procedure returns to a step to fetch the next procedure, and the processing is continued. when another operation is performed, the shape shown in the main window is operated according to the operation, the next input work is retrieved (namely, the present input work is skipped), the retrieved input work is fetched, and the processing is continued. if the next work is not present or the next input work cannot be retrieved, the processing is terminated. according to this embodiment, for the history of a series of work procedures obtained as a result of combining the unit work history data, the procedure is sequentially reproduced and the design support information is provided without causing the person in charge of work to notice the joint (combined point) of the respective pieces of unit historical data. [basic operation] a basic operation of the design support system of this embodiment will now be described. a plurality of histories of past design works are accumulated for the respective design targets as unit work history data in the database 1. the person in charge of work who designs a new product inputs the design target and design information to the design support device 2 to show the unit work history data linked to the design target on the display section 24. here, when the person in charge of work selects one piece of data from the unit work history data shown on the display section 24, the design support window is shown, and the reproduction of the selected unit work history data is started. when the person in charge of work refers to the shape to be reproduced in advance in the design support window to use as it is, the reproduction is approved, and when a change or addition is made, a design operation is performed instead of a part of the work history or in addition to the work history. when there is information (information about designation of a primitive, input of coordinate values and the like) to be input by the person in charge of work in the reproduction process and when design support information is contained in the unit work history data the design support device 2 of this embodiment displays the design support information. besides, when there is a guide display corresponding to a predetermined command, the guide display is performed. the person in charge of work can see the design support information to know information such as a meaning of each input work and can also know more detailed information about the contents of work from the guide display. thus, reuse of the work history data is promoted, and design work efficiency is improved. besides, for the historical data about the design work obtained as above, the input work contained in it is retrieved in this embodiment, and an interface for requesting each input work to input design support information is provided. thus, the person in charge of work is saved from inputting the design support information. [operation to design based on reference surface] an operation to design according to the reference surface by the design support system of this embodiment will now be described. a plurality of histories of past design works are accumulated in the database 1 as unit work history data for each design target. the accumulated unit work history data are designed on the basis of the reference surface (original reference surface) used for the past design works. the person in charge of work who designs a new member conforming to a new reference surface inputs information about the new reference surface to the design support device 2. then, the design support device 2 reproduces work history data based on the new reference surface. when the person in charge of work inputs the design target and the design, unit work history data linked to the design target is shown on the display section 24. when the person in charge of work operates to select one piece of data from the displayed unit work history data, the design support window is shown, and the reproduction of the selected unit work history data is started. when reproducing, the work performed with the original reference surface used as a standard is reproduced with the newly designated reference surface used as a standard. specifically, when the selected unit work history data is created by an operation using offset values (a1, a2, ...) with the original reference surface (d1) used as a standard and having a recessed shape on a plate along the reference surface as shown in fig. 8a, a minimum value is determined for a width l of the recess section as a design requirement with respect to the unit work history data, and minimum and maximum values are determined for an angle θ which is formed by the inside wall of the recess section and the plate parallel to the reference surface. to make it easier to understand, fig. 8a shows the reference surface which is cut away at a certain portion. when the reference surface (d2) shown in fig. 8b is newly designated on the basis of the unit work history data of fig. 8a, the offset values (a1, a2, ...) are reproduced, and a shape f having a recess section is designed with the reference surface d2 used as a standard. when the person in charge of work references the shape f which is reproduced in advance in the design support window and uses it as it is, the reproduction is approved, and when a change or addition is made, a design operation is performed instead of a part of the work history or in addition thereto. also, when there is information (information about designation of a primitive, input of coordinate values, etc.) to be input by the person in charge of work in the reproduction process and design support information is contained in the unit work history data, the design support device 2 of this embodiment shows that information. besides, when there is a guide display corresponding to the predetermined command, the design support device 2 performs the guide display. here, when the person in charge of work instructs to evaluate, technical characteristic values are computed by the finite element method or the like, the technical characteristic values are compared with the design requirements and the production technology requirements, and the results are shown to the person in charge of work. the person in charge of work can know information such as meanings of respective input work by seeing the design support information and the computed results of the technical characteristic values and also can know more detailed information about the contents of the work from the guide display. besides, an appropriate design is made according to the computed results of the technical characteristic values. thus, reuse of the work history data is promoted, and efficiency of the design work is improved. [conversion into formal design] as described above, the reference surface may be designed in parallel with the designing of a member which shall be made to conform to the reference surface. in this case, when the member is designed based on a temporary reference surface and a finally determined reference surface (formal reference surface) is completely designed, the design history which is previously performed based on the temporary reference surface (corresponding to the second standard shape of the present invention) is converted into a design history based on the formal reference surface, and a member conforming to the formal reference surface (corresponding to the third standard shape of the present invention) is designed. at this time, the following technical problems might arise. specifically, they are an error (1) involved in a change of the number of configuring surfaces, an error (2) resulting from a change in direction or quantity of border lines, an error (3) involved in reversing of the direction of a surface, and an error (4) due to folding of a surface. as shown in fig. 9, the error (1) involved in a change of the number of configuring surfaces means that when there is a surface 104, which is designed based on given surface elements a, b on a temporary reference surface 102 and conditioned to come into contact with the temporary reference surface 102, and a reference surface 102a corresponding to the temporary reference surface 102 consists of three surface elements c, d, e, it is not certain to which of the surfaces c, d, e the standard surface to be referenced corresponds, and the system cannot make a judgment. also, the error (2) resulting from a change in direction or a number of border lines is derived from the fact that a surface is indicated by a single loop specifying a border line. depending on whether the loop is clockwise or counterclockwise, e.g., when it is clockwise for the temporary design but becomes counterclockwise for the formal design, a created shape is different from an intended one due to the results of the work performed based on the border line. besides, the error (3) involved in reversing of the direction of a surface means that a shape specified in a "positive direction" (e.g., when a right-hand screw is turned in the direction of a loop specifying the surface, the forwarding direction of the screw is determined as positive) with respect to a certain surface is occasionally generated. this type of work results in a formed shape different from the intended shape when the surface direction is reversed. here, each surface element is internally generated by a cad system, and the direction of a corresponding surface might be reversed between the temporary design surface and the formal design surface before the designer of the reference surface knows it. besides, the error (4) due to folding of a surface means an error caused when a plurality of surface elements which are smoothly connected for the temporary design are not smoothly connected for the formal design. specifically, when a line is projected to a given curved surface to form a shape by cutting the surface by the projected line, other work may be conducted with reference to the projected line. at this time, the projected line selected from a group of smoothly connected surface elements forms a single smooth curve, so that other work conducted with reference to it corresponds to the single curve. however, when a group of surfaces corresponding to the projected line are not connected smoothly, the projected line becomes a zigzag line, which is formed of a plurality of line segments. therefore, the work performed with reference to a single curve cannot specify a projected line to be referenced and has an error. under the aforementioned circumstances, design support information may be shown in the same way as designing performed with unit work history data combined. however, because the temporary design and the formal design are not that different from each other, the surface groups can be made to correspond mutually between the surface elements contained in the temporary design and the surface elements contained in the formal design. therefore, the generating of correspondence is performed prior to the reproduction of the procedure based on the formal design. specifically, this generation of correspondence is performed as the person in charge of work shows the temporary reference surface and the formal reference surface to determine a surface group for both of them and allots an id to them. also, a corresponding surface group is designated. thus, the corresponding surface groups are determined and ids of the corresponding surface groups are registered as a pair. by generating correspondence as described above, it can be judged whether a direction of the loop specifying the corresponding surface is changed or not, and a direction of the surface can also be judged. therefore, the aforementioned problems (1) to (3) can be solved by previously generating correspondence. also, when a connected relation of the surface elements contained in the associated individual surface groups (the surface group of the temporary design and that of the formal design) is checked, and if one of them is smoothly connected while the other is not, this is notified to the person in charge of work to cause them to edit the design work of the member, to prevent a design surface from being folded or the like, thereby making it possible to prevent the error (4) from occurring. [execution of overall work] as described above, the design support system (this system) according to this embodiment can realize the designing flow shown in fig. 10. designing of a vehicle will be described below. first, the person in charge of work can divide a history of the design work performed based on a certain body shape design (first standard shape) into predetermined units and register as unit work history data in the database 1 (s31). the unit work history data registered as described above is arranged according to the units of each design target for future reuse to form a "shelf" (a). this system finds a procedure by which the person in charge of work inputs to register for future reuse, requests input of design support information and includes the input design support information in the procedure for registration. in this stage, the unit work history data to be registered in the database 1 is registered as a general-purpose procedure which does not depend on a particular design or a particular joint relationship. therefore, when a member conforming to a new body is designed, the above unit work history data can be used to design. in other words, the person in charge of work determines the new body shape based on the shape (second standard shape) presented as a temporary design by a body design department. the unit work history data is also fetched from the database 1 ("shelf"), and the design work is conducted (s32). in addition to a main window m reflecting the actual design contents, the unit work history data is reproduced prior to the actual design contents, a sub-window s for design support to indicate the results is shown (fig. 11), and if there is input design support information, it is shown in the sub-window s. thus, the person in charge of work can know the input contents to be designated at this time, and the reuse can be implemented smoothly. here, the person in charge of work may conduct new design work without using the unit work history data. the person in charge of work operates to utilize the unit work history data or to combine newly designed elements so to create a "joint" for connecting the respective elements to form a combined shape, and designs a member conforming to the second standard shape to create work history data on a temporary original design. here, data on the work history obtained by editing the unit work history data or performing the new design work is divided into predetermined units as required, and registered as unit work history data in the database 1 (s33). thus, reuse and registration are appropriately performed to enhance the contents of the database 1. furthermore, it is evaluated in this stage whether the technical character values based on the shape created according to the unit work history data to comply with the second standard shape have the predetermined design requirements and technical production requirements, and the results are shown (s34). after the results are shown, the person in charge of work further edits the work history data and changes the design so to meet the predetermined requirements. thus, part characteristics can be analyzed in a stage prior to the completion of a formal design, and the design work can be performed smoothly. when the body design department has completed the design of the formal design (formal design; the third standard shape), the standard shape (reference surface) referenced by the work history data about the temporary original design is replaced, and the work history data about the original design for the formal design is created (s35). also, the surface groups are made to correspond between the temporary design and the formal design prior to the creation of the work history data about the formal design, and the design can be replaced completely while considering the standard surface, line segment direction, surface direction and the like with reference to the correspondence of the respective surface groups. if the surface group has folding, the work history data for creating a shape conforming to the formal design can be obtained by editing the reference surface or the work history data. the obtained work history data is also used for subsequent processes such as a mold design step. in the aforementioned description, the design support information is determined to be shown in the sub-window s, but the window for showing design support information and the window for showing the actual design contents may be realized as an independent main window. such a configuration can be made by, for example, writing a program to separately manage the respective windows in a single design support application or by creating a separate application for each window and operating the applications on a multitask os. in this case, the respective windows can be tiled (arranged) as shown in fig. 12, and the window showing the actual design contents can be closed while only the window showing the design support information is displayed. according to the present invention, the design support system is configured such that the design work history for creating a shape model is divided into parts of the shape model and kept as plural pieces of unit work history data, at least two selected pieces of unit work history data are taken from the plural pieces of unit work history data held and combined, and design work data for creating a combined shape model having the part shape models corresponding to the respective pieces of unit work history data connected is output. thus, reusability of the past work history data can be improved by making it possible to divide the design work history into pieces for parts, to keep them and to combine them later. according to the present invention, the design support system, which outputs work data for creating a shape model of a design target in order to create the shape model of the design target conforming to a standard shape, comprises holding a plurality of unit work history data which are obtained by dividing a history of a design work performed with reference to a first standard shape for each design work history corresponding to a shape model of a predetermined portion; accepting designation of data about a second standard shape; fetching multiple unit work history data selected from the multiple unit work history data held to combine them; and reproducing design work with reference to the designated second standard shape for the design work performed with reference to the first standard shape among the design work contained in the unit work history data, and outputting work data corresponding to a combined shape model conforming to the second standard shape. thus, reusability of the past work history data can be improved by making it possible to divide the design work history into pieces for parts, to keep them and to combine them later. according to the present invention, the design support system, which holds a series of design work histories to reuse as work history data and creates a shape based on the work history data, comprises the steps of analyzing the work history data to extract input work performed by a person in charge of work; showing the extracted input work to the person in charge of work to receive input of design support information; and recording the design support information in the work history data when the design support information is input so to show when the design support information is reused. thus, reusability of the work history data is promoted, and design work efficiency is improved. reusability can be improved furthermore because the work history data is divided into predetermined work units for each design target and separately stored as unit work history data. besides, according to the present invention, the design support system comprises the step of accumulating unit work history data which is formed by dividing a history of past design work into work units determined for each design target and contains design support information related to input work in the design work; selectively showing the unit work history upon receiving designation of the design target; creating a shape by sequentially reproducing the selected unit work history; and providing design support information related to input work when the input work is demanded while the unit work history is being reproduced. thus, understanding of the meaning and content of each input work is additionally facilitated by virtue of the design support information, reuse of the work history data is promoted, and efficiency of the design work is improved. here, it is judged whether the work history to be reproduced agrees with predetermined guidance display conditions while the unit work history is being reproduced and, if the work history agrees with the guidance display conditions, a guidance display determined in connection with the conditions is carried out. accordingly, more detailed information is provided to facilitate understanding of the work history data and to provide additional improvement of the design work efficiency. while there have been described what are at present considered to be preferred embodiments of the invention, it is to be understood that various modifications may be made thereto, and it is intended that the appended claims cover all such modifications as fall within the true spirit and scope of the invention. to provide a design support system which can enhance reusability of historical data about past design work and improve work efficiency, design work history data is divided according to an instruction to generate unit work history data, input work made by a person in charge of work in a history is retrieved, input of design support information for the work is accepted, and the input design support information is inserted into the unit work history data to be stored in a database 1. the person in charge of work who reuses the unit work history data performs design work with reference to the design work history data which is previously reproduced in a design support window shown on a display section 24 of a design support device 2 and the design support information contained in it.
|
075-772-772-348-914
|
JP
|
[
"US",
"JP"
] |
G06F15/16,G06F3/048,H04L29/08,G06F13/00,G06F3/0481,G06F3/0484,H04L29/06
| 2007-09-28T00:00:00 |
2007
|
[
"G06",
"H04"
] |
automating user's operations
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to select a communication sequence for automating user's operations, a system performing a user's operation is provided, which acquires and stores a communication history of a client with a server in receipt of a user's operation; accesses the storage to detect from the history a plurality of communication sequences that cause the same screen transition on the client; accesses the storage to select an input parameter that is included in all of the plurality of communication sequences and that has a parameter value changed for each communication sequence; accepts an input of a new parameter value to be set as a value of the selected input parameter; and sets the new parameter value to the selected input parameter in response to the input of the new parameter value, to execute a communication sequence that causes the same screen transition as that caused by the detected communication sequences.
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1. a system performing a user's operation on behalf of a user, comprising: a storage device; a processor operably connected with the storage device; a history acquisition unit encoded on the storage device and executable by the processor to acquire a history of communication of a client computer with a server computer in receipt of a user's operation and store the history in the storage device, wherein the history of communication is to include at least two sequences of screen transitions; a detection unit encoded on the storage device and executable by the processor to access the storage device to detect from the history a plurality of communication sequences that each cause a screen transition of common occurrence on the client computer, wherein at least one screen transition of common occurrence is to include a serial transition of a first screen to at least a second screen, and wherein at least one communication sequence of the plurality of communication sequences is to cause the same serial transition of the first screen to the at least second screen in two of the at least two sequences of screen transitions; a first selection unit encoded on the storage device and executable by the processor to access the storage device and select an input parameter that is included in all of the plurality of communication sequences and that has a parameter value changed for each communication sequence; an input accepting unit encoded on the storage device and executable by the processor to cause the client computer to accept an input of a new parameter value to be set as a parameter value of the selected input parameter; and an execution unit encoded on the storage device and executable by the processor to set the new parameter value to the selected input parameter in response to the input of the new parameter value, and cause the client computer to execute a communication sequence that causes the screen transition of common occurrence. 2. the system according to claim 1 , further comprising a second selection unit encoded on the storage device and executable by the processor to access the storage device and select, for at least one of the plurality of communication sequences detected by the detection unit, a plurality of input parameters having the same parameter value set therefor, wherein the input accepting unit causes the client computer to accept an input of a new parameter value to be set commonly for the plurality of input parameters selected by the second selection unit, and the execution unit sets the accepted parameter value to each of the plurality of input parameters selected by the second selection unit, for execution of the communication sequence. 3. the system according to claim 1 , wherein: the history acquisition unit acquires, as the history, a request that the client computer transmits to the server computer and a response that the server computer returns to the client computer in response to the request, the system further comprises a match determination unit encoded on the storage device and executable by the processor to access the storage device and determine, for at least one of the plurality of communication sequences detected by the detection unit, whether the parameter value of a first parameter included in a first response matches the parameter value of a second parameter included in a second request transmitted later than the first response, and on the condition that the parameter values of the first and second parameters match, the execution unit causes the parameter value of the first parameter received as a part of the first response to be set to the second parameter included in the second request transmitted later than the first response, during execution of the communication sequence. 4. the system according to claim 1 , further comprising a setting unit encoded on the storage device and executable by the processor to perform setting as to whether to allow the input accepting unit to accept an input of a new parameter value to be set for the input parameter selected by the first selection unit based on an instruction from the user, wherein: the input accepting unit causes the client computer to accept the input of the new parameter value on the condition that the setting unit allows the input accepting unit to accept the input of the new parameter value. 5. the system according to claim 4 , wherein: in the case of not accepting the input of the new parameter value to be set for the input parameter selected by the first selection unit, the setting unit sets a fixed parameter to be set for the input parameter based on an instruction from the user, and in the case of not accepting the input of the new parameter value to be set for the input parameter selected by the first selection unit, the execution unit sets the fixed parameter set by the setting unit to the input parameter selected by the first selection unit, for execution of the communication sequence. 6. the system according to claim 1 , wherein: the input accepting unit displays a form for accepting an input of the new parameter value on a web browser operating in the client computer, and the execution unit sets the parameter value input to the form to the selected input parameter in accordance with an instruction of the user, for execution of a communication sequence that causes the screen transition of common occurrence. 7. the system according to claim 1 , further comprising a generating unit encoded on the storage device and executable by the processor to generate a program for causing the client computer to function as the input accepting unit and the execution unit, the generating unit accepting an input of a program name from the user and storing the program in the storage device in association with the input program name, wherein: the client computer reads the program name from the storage device for display, and reads the program corresponding to the program name designated by the user from the storage device for execution. 8. the system according to claim 1 , further comprising a setting unit encoded on the storage device and executable by the processor to set, based on an instruction from the user, a screen at which a screen transition by the communication sequence executed by the execution unit is to be interrupted, wherein: the execution unit interrupts execution of the communication sequence on the condition that communication corresponding to transition to the screen set by the setting unit is performed during the execution of the communication sequence, when the execution of the communication sequence is interrupted, the input accepting unit causes the client computer to accept an input of a new parameter value to be set for a parameter in the communication after restart, and on the condition that the input of the new parameter value is accepted, the execution unit sets the new parameter value and restarts the communication sequence. 9. the system according to claim 1 , wherein the detection unit detects as one or more of the communication sequences of the plurality a communication sequence which is to appear with a frequency equal to or greater than a predetermined reference frequency of occurrence, wherein the predetermined reference frequency of occurrence is to include a frequency of at least two. 10. the system according to claim 9 , wherein the detection unit classifies the history into communication sessions, and for each of the classified sessions, detects as one or more of the communication sequences of the plurality a communication sequence which is to appear with a frequency equal to or greater than the predetermined reference frequency of occurrence. 11. the system according to claim 10 , wherein the communication sequence includes a request and a response in http (hypertext transfer protocol), the screen transition includes a plurality of web pages displayed sequentially, the history acquisition unit acquires, as the history, a request that the client computer transmits to the server computer and a response that the server computer returns to the client computer in response to the request, and the detection unit selects any request corresponding to a response of html data from among the history, and detects as one or more of the communication sequences of the plurality a communication sequence which is to appear with a frequency equal to or greater than the predetermined reference frequency of occurrence from among sequences of the requests selected. 12. the system according to claim 11 , wherein the detection unit eliminates from the history any request corresponding to a response having a status code indicating error or invalidity, and detects as one or more of the communication sequences a communication sequence which is to appear with a frequency equal to or greater than the predetermined reference frequency of occurrence from among the remaining sequences of the requests. 13. the system according to claim 1 , wherein the execution unit stops the execution of the communication sequence on the condition that a response having a status code indicating error or invalidity is received during the execution of the communication sequence. 14. the system according to claim 13 , wherein the execution unit causes the execution of the communication sequence to be continued on the condition that the response received during the execution of the communication sequence matches the response included in the history except for the parameter value. 15. the system according to claim 1 , wherein the detection unit detects as one or more of communication sequences of the plurality a communication sequence which is to appear a predetermined number of times to cause the screen transition of common occurrence, wherein the predetermined number of times is to include at least two. 16. the system according to claim 1 , wherein the detection unit detects as one or more of communication sequences of the plurality a communication sequence which is to appear a predetermined number of times within a predetermined period of time to cause the screen transition of common occurrence, wherein the predetermined number of times is to include at least two. 17. the system according to claim 1 , wherein the detection unit detects as one or more of communication sequences of the plurality a communication sequence which is to appear a predetermined number of times to cause the screen transition of common occurrence and which is to include a predetermined number of screens that transition in the screen transition of common occurrence, wherein the predetermined number of times is to include at least two, and wherein the predetermined number of screens is to include a longest portion out of a common portion among the at least two sequences of screen transitions. 18. the system according to claim 1 , wherein the detection unit is to eliminate from the target of detection a communication sequence that causes a number of screens to transition which is smaller than a reference number. 19. a computer program product for causing a computer having a storage device to function as a system performing a user's operation on behalf of a user, the program product comprising a non-transitory computer-readable storage media having encoded thereon a computer executable program of instructions, comprising: a history acquisition unit which acquires a history of communication of a client computer with a server computer in receipt of a user's operation and stores the history in the storage device, wherein the history of communication is to include at least two sequences of screen transitions; a detection unit which accesses the storage device to detect from the history a plurality of communication sequences that each cause a screen transition of common occurrence on the client computer, wherein at least one screen transition of common occurrence is to include a serial transition of a first screen to at least a second screen, and wherein at least one communication sequence of the plurality of communication sequences is to cause the same serial transition of the first screen to the at least second screen in two of the at least two sequences of screen transitions; a first selection unit which accesses the storage device to select an input parameter that is included in all of the plurality of communication sequences and that has a parameter value changed for each communication sequence; an input accepting unit which causes the client computer to accept an input of a new parameter value to be set as a parameter value of the selected input parameter; and an execution unit which sets the new parameter value to the selected input parameter in response to the input of the new parameter value, and causes the client computer to execute a communication sequence that causes the screen transition of common occurrence. 20. a method for performing a user's operation on behalf of a user by a computer having a storage device, comprising the steps of: the computer acquiring a history of communication of a client computer with a server computer in receipt of a user's operation and storing the history in the storage device, wherein the history of communication includes at least two sequences of screen transitions; the computer accessing the storage device and detecting from the history a plurality of communication sequences that each cause a screen transition of common occurrence on the client computer, wherein at least one screen transition of common occurrence includes a serial transition of a first screen to at least a second screen, and wherein at least one communication sequence of the plurality of communication sequences causes the same serial transition of the first screen to the at least second screen in two of the at least two sequences of screen transitions; the computer accessing the storage device and selecting an input parameter that is included in all of the plurality of communication sequences and that has a parameter value changed for each communication sequence; the computer causing the client computer to accept an input of a new parameter value to be set as a parameter value of the selected input parameter; and the computer setting the new parameter value to the selected input parameter in response to the input of the new parameter value, and causing the client computer to execute a communication sequence that causes the screen transition of common occurrence.
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field of the invention the present invention relates to a technique of automating user's operations. more particularly, the present invention relates to a technique of automating user's operations based on a communication history. background recently, web pages are provided with various objects, such as check boxes, radio buttons and input forms, for accepting users' inputs. a user performs operations on the objects on the sequentially displayed web pages so as to accomplish a specific purpose, which may be, e.g., purchase of a product, display of information, or change of a preset value. a series of operations the user performs may be similar to those the user performed in the past. even in such a case, the user is required to perform the series of operations from the beginning to accomplish the intended purpose. the following three patent documents each disclose a technique of automating user's operations: japanese unexamined patent publication (kokai) no. 10-340277; japanese unexamined patent publication (kokai) no. 2002-007020; and japanese unexamined patent publication (kokai) no. 2001-290809. summary a conceivable method of automating the user's operations is to reproduce the operations received via the mouse and keyboard. this method, however, requires that the computer for storing the operations and the computer for reproducing the operations are substantially identical to each other, which renders the method unpractical. for example, if the computer for storing the operations and the computer for reproducing them differ from each other in terms of resolution of the screen or arrangement of the windows, the operations may not be reproduced properly. further, it may not be useful to simply reproduce the operations exactly the same as those performed in the past. for example, in purchase of products, although the purchasing processes may be similar, the products to be purchased will differ in many cases. furthermore, in change of preset values, even if the changing procedure may be similar, the preset values themselves often differ from each other. therefore, determination as to which portion of the operations to automate and which portion not to automate will be left to the user, which is troublesome for the user. in view of the foregoing, an object of the present invention is to provide a system, method and program that can solve the above-described problems. the object is achieved by a combination of the features recited in the independent claims of the present application. the dependent claims define further advantageous embodiments of the present invention. summary to solve the above-described problems, in a first aspect of the present invention, there is provided a system performing a user's operation on behalf of a user, which includes: a storage device; a history acquisition unit which acquires a history of communication of a client computer with a server computer in receipt of a user's operation and stores the history in the storage device; a detection unit which accesses the storage device to detect from the history a plurality of communication sequences that cause the same screen transition on the client computer; a first selection unit which accesses the storage device to select an input parameter that is included in all of the plurality of communication sequences and that has a parameter value changed for each communication sequence; an input accepting unit which causes the client computer to accept an input of a new parameter value to be set as a parameter value of the selected input parameter; and an execution unit which sets the new parameter value to the selected input parameter in response to the input of the new parameter value, and causes the client computer to execute a communication sequence that causes the same screen transition as the screen transition caused by the detected communication sequences. also provided are a program for causing a computer to function as the system, and a method for performing a user's operation on behalf of a user by the system. it is noted that the above summary does not list all the necessary features of the present invention, and that a sub-combination of these features may also implement the invention. brief description of the drawings fig. 1 schematically shows the overall configuration of an information system 10 according to an embodiment of the present invention; fig. 2 shows a specific example where a client computer 100 according to the embodiment communicates with a server computer 200 ; fig. 3 shows an example of a request 50 a according to the embodiment; fig. 4 shows an example of a response 52 a according to the embodiment; fig. 5 shows an example of a screen 106 a displayed by a web browser 106 of the embodiment in response to the response 52 a; fig. 6 shows an example of a request 50 b according to the embodiment; fig. 7 shows an example of a response 52 b according to the embodiment; fig. 8 shows an example of a screen 106 b displayed by the web browser 106 of the embodiment in response to the response 52 b; fig. 9 shows an example of a request 50 c according to the embodiment; fig. 10 shows an example of a response 52 c according to the embodiment; fig. 11 shows an example of a screen 106 c displayed by the web browser 106 of the embodiment in response to the response 52 c; fig. 12 shows an example of a request 50 d according to the embodiment; fig. 13 shows an example of the functional configuration of an agent system 108 according to the embodiment; fig. 14 shows a flow of the processing in which the agent system 108 of the embodiment generates a program based on a communication history; fig. 15 shows details of the flow of the process in s 1410 ; fig. 16 shows an example of a screen 106 x displayed on the web browser 106 in s 1450 ; fig. 17 shows an example of the screen 106 x displayed on the web browser 106 in s 1460 ; fig. 18 shows a flow of the processing in which the agent system 108 of the embodiment carries out operations on behalf of the user based on the user's instruction; fig. 19 shows an example of a screen 106 y displayed on the web browser 106 in s 1805 ; and fig. 20 shows an example of the hardware configuration of the client computer 100 according to the embodiment. detailed description while the present invention will now be described with reference to an embodiment, it should be noted that the following embodiment is not intended to restrict the claimed invention. it should also be noted that all the combinations of the features explained in the following embodiment are not necessarily indispensable for the solving means of the present invention. fig. 1 schematically shows an overall configuration of an information system 10 according to an embodiment of the present invention. the information system 10 includes a client computer 100 and a server computer 200 . the client computer 100 has, as its fundamental hardware, a communication interface 102 such as a network interface card, and a storage device 104 such as a hard disk drive. when a program stored in the storage device 104 is executed by a central processing unit, the client computer 100 serves as a web browser 106 and an agent system 108 . the server computer 200 has, as its fundamental hardware, a communication interface 202 such as a network interface card, and a storage device 204 such as a hard disk drive. when a program stored in the storage device 204 is executed by a central processing unit, the server computer 200 serves as a web server 206 . the web browser 106 , in response to a user's operation, transmits a request 50 in compliance with a communication protocol such as http (hypertext transfer protocol) to the web server 206 . in response, the web server 206 returns a response 52 in compliance with http or the like to the web browser 106 . this causes transition of the screen displayed on the web browser 106 to another screen. the user performs operations on the screens thus changed sequentially, to thereby accomplish an intended purpose, which may be change of a preset value saved in the server computer 200 , purchase of a product on a web site implemented by the server computer 200 , or the like. the agent system 108 records a history of communication of the client computer 100 with the server computer 200 which has been performed in response to the user's operations. then, the agent system 108 detects from the history any communication sequences repeated with a high frequency, for example. further, the agent system 108 selects, from these communication sequences, any input parameter having a parameter value changed for each communication sequence. the agent system 108 accepts an input of a new parameter value to be set for the selected input parameter, and reproduces the communication sequence according to the input of the parameter value. this causes the client computer 100 to operate as if it received a series of operations from the user again. in this manner, the processing carried out in the past can be reproduced with only an initial input of a parameter value by the user. as described above, the agent system 108 according to the present embodiment aims at, not only reproducing a communication sequence, but also automatically detecting a sequence suitable for reproduction and automatically selecting a necessary variable parameter, so as to improve usability for the user. hereinafter, the present invention will be explained in more detail. fig. 2 shows a specific example where the client computer 100 of the present embodiment communicates with the server computer 200 . a user may carry out prescribed operations on a plurality of web pages sequentially changed, so as to accomplish a certain purpose. in fig. 2 , screens 106 a, 106 b and 106 c represent such a set of web pages. further, a request 50 a indicates the request transmitted by the client computer 100 to cause the screen 106 a to be displayed by the web browser 106 , and a response 52 a is the response to the request 50 a. a request 50 b indicates the request transmitted by the client computer 100 in response to the user operating the screen 106 a, and a response 52 b is the response to the request 50 b. in receipt of the response 52 b, the web browser 106 displays the screen 106 b. further, a request 50 c indicates the request transmitted by the client computer 100 in response to the user operating the screen 106 b, and a response 52 c is the response to the request 50 c. the web browser 106 displays the screen 106 c in receipt of the response 52 c. a request 50 d indicates the request transmitted by the client computer 100 in response to the user operating the screen 106 c. fig. 3 shows an example of the request 50 a according to the present embodiment. the first line is a request line, which includes a command name “post”, a path name “/admin/secure/logon.do”, and a protocol name “http/1.1”. the second through fourth lines indicate attributes of the files accepted by the web browser 106 . the fifth line indicates the type of the web browser 106 . the sixth line indicates a host name of the server computer 200 which is the destination of the request. in this example, “terminal□□□” is the host name of the server computer 200 . in conjunction with the first line, this request 50 a is a request for the web page designated by the url “terminal□□□/admin/secure/logon.do”. the seventh line shows that continuation of connection is requested. fig. 4 shows an example of the response 52 a according to the present embodiment. the response 52 a shown in fig. 4 is returned in response to the request 50 a shown in fig. 3 . the first line includes the protocol name “http/1.1” and an identifier “200 ok” indicating that communication was successful. the second line shows date and time of communication. the third line shows the type of the web server 206 . the fourth line shows the type of the content included in the response 52 a. specifically, “text/html” indicates that it is the html data. further, “utf-8” shows a character set. the fifth line indicates language setting for the content included in the response 52 a. the seventh and following lines show the web page to be displayed on the web browser 106 . in the example shown in fig. 4 , the web page starts with an html tag and a head tag. in receipt of this response 52 a, the web browser 106 displays the screen 106 a shown in fig. 5 . fig. 5 shows an example of the screen 106 a which is displayed by the web browser 106 of the present embodiment in receipt of the response 52 a. for example, the screen 106 a corresponds to a screen for administration of a prescribed server (the server computer 200 may also serve as this server) or for change of setting of the server. specifically, on the address field, the url “terminal□□□/admin/secure/logon.do” designated by the request 50 a is displayed. further, on the left side of the screen, various menus for changing the settings are displayed. when the user clicks on “virtual host” in the menus, the window as in the lower right of the screen is displayed. the “virtual host” indicates a function to cause a single physical computer to be recognized by another computer as if a plurality of computers were operating. in this window, an operation for creating a new virtual host is received from the user. for example, when the user operates the button “new” near the lower center of the screen 106 a, the server computer 200 starts processing of creating a new virtual host. a request that the web browser 106 transmits as this button is operated is shown in fig. 6 . fig. 6 shows an example of the request 50 b according to the present embodiment. the first line is similar to the request line shown in fig. 3 , except that the path name is different. specifically, the first line indicates that the web page designated by the path name “/admin/virtualhostcollection.do” is requested. the second through seventh lines are approximately the same as those of the request 50 a shown in fig. 3 , and thus, description thereof will not be repeated. following the first through seventh lines (called the “header part”) is a body part of the request 50 b. for example, the x-th line shows an input parameter based on a user's operation. the portion “button.new=xxxx” in the line indicates that the “new” button was operated by the user. as such, the user's operation is expressed as a set of the input parameter “button.new” and its parameter value “xxxx”, and is transmitted to the web server 206 as a part of the request 50 b. fig. 7 shows an example of the response 52 b according to the present embodiment. the header part on the first through fifth lines is approximately the same as that of the response 52 a shown in fig. 4 , and thus, description thereof will not be repeated. the body part following the header part shows the web page to be displayed on the web browser 106 . for example, the y-th through (y+8)-th lines include various tags for displaying texts and input field in an aligned manner using the html table function. specifically, the <tr> tag designates an element in the row direction in the table, and the <td> tag designates a cell included in a certain row in the table. as a result, the text “name” included in the (y+2)-th line is displayed in a prescribed position on the web page. further, the image data designated by the (y+6)-th line and the input field designated by the (y+7)-th line are displayed side by side. fig. 8 shows an example of the screen 106 b which is displayed by the web browser 106 of the present embodiment in receipt of the response 52 b. when the user operates the “new” button on the screen 106 a, the screen on the web browser 106 is changed to this screen 106 b. a window for accepting an input of the name of the virtual host is displayed on the lower right of the screen 106 b. in this window, as explained above with reference to fig. 7 , the text data “name”, the image data having, for example, a star shape, and the input field are displayed in alignment. the user can determine the name of the virtual host by inputting a character string in the input field and operating the “ok” button. here, it is assumed that the “ok” button is operated following the input of the character string “vh 005 ”. fig. 9 shows an example of the request 50 c according to the present embodiment. the first line is similar to the request line shown in fig. 3 , except that the path name is different. that is, the first line indicates that the web page designated by the path name “/admin/virtualhostdetail.do” is requested. the second through seventh lines are approximately the same as those of the request 50 a shown in fig. 3 , and thus, description thereof will not be repeated. following the header part on the first through seventh lines is the body part of the request 50 c. for example, the z-th line indicates an input parameter based on a user's operation. the portion “action=new” in the line indicates that creation of a new virtual host has been designated, and the portion “name=vh 005 ” indicates that the name of the virtual host is “vh 005 ”, and the portion “save=ok” indicates that the setting of the virtual host should be saved. fig. 10 shows an example of the response 52 c according to the present embodiment. the header part on the first through fifth lines is approximately the same as that of the response 52 a shown in fig. 4 , and thus, description thereof will not be repeated. the body part following the header part indicates the web page to be displayed on the web browser 106 . for example, the w-th through (w+9)-th lines indicate a pull-down menu for setting a parameter value for the input parameter “column 2 ”. specifically, the w-th line indicates that the input parameter to be set is “column 2 ”. the (w+1)-th through (w+8)-th lines respectively show terms to be displayed on the pull-down menu, which are: “default”, “admin_host”, “test1 host”, “vh 001 ”, “vh 002 ”, “vh 003 ”, “vh 004 ”, and “vh 005 ”. fig. 11 shows an example of the screen 106 c which is displayed by the web browser 106 of the present embodiment in receipt of the response 52 c. in response to the user's operation of the “ok” button on the screen 106 b, the screen of the web browser 106 changes from the screen 106 b to the screen 106 c. a window for performing detailed setting of the virtual host is displayed on the lower right of the screen 106 c. in this window, as explained above with reference to fig. 10 , the pull-down menu for setting a parameter value for the input parameter is displayed. the user can use this pull-down menu to select a parameter value to thereby determine, for example, the host for installing a web module. here, it is assumed that “vh 005 ” is selected. fig. 12 shows an example of the request 50 d according to the present embodiment. the first through seventh lines are approximately the same as those in the request 50 c shown in fig. 9 , and thus, description thereof will not be repeated. the l-th line in the body part indicates that the parameter value “vh 005 ” is set for the input parameter “column 2 ”. in response, installation processing for the virtual host vh 005 is started in the server computer 200 . as described above with reference to figs. 2-12 , the user performs various operations on the sequentially displayed screens of the web browser 106 to achieve the purpose of, e.g., creating a new virtual host. the operations not only include clicking on a button or an object such as a tag, but also include inputting of characters to the input field. in response to these operations, as the internal processing, the web browser 106 sequentially transmits requests to the web server 206 , and the web server 206 sequentially returns responses to the web browser 106 . the agent system 108 according to the present embodiment takes out a communication sequence to be automated from among the series of communication sequences in the past as described above and provides it to the user to carry out the operations on behalf of the user. this will now be explained with reference to fig. 13 . fig. 13 shows an example of the functional configuration of the agent system 108 according to the present embodiment. the agent system 108 has a history acquisition unit 300 , a detection unit 310 , a first selection unit 320 , a second selection unit 330 , a match determination unit 340 , a setting unit 350 , and a generating unit 360 . the history acquisition unit 300 acquires a history of the client computer 100 communicating with the server computer 200 in receipt of user's operations, and stores the history in the storage device 104 . the history includes a request, a response, or a combination thereof, as those shown in figs. 1-12 . this means that the history includes a variety of pieces of information including not only the http command and the requested url but also the input parameter and its parameter value. in the present embodiment, the history acquisition unit 300 is provided in the client computer 100 , and acquires the request the web browser 106 is about to transmit to the web server 206 as well as the response the web browser 106 is about to receive from the web server 206 as the history. alternatively, the history acquisition unit 300 may be provided in the server computer 200 , in which case it may acquire the request the web server 206 is about to receive from the web browser 106 and the response the web server 206 is about to transmit to the web browser 106 as the history. still alternatively, the history acquisition unit 300 may be provided in a proxy server relaying communication between the client computer 100 and the server computer 200 , in which case it may acquire, as the history, the request and response transferred over the communication line. the detection unit 310 accesses the storage device 104 to detect from the history a plurality of communication sequences that cause the same screen transition on the client computer 100 . as used herein, the “screen transition” refers to transition of screens determined for example by the urls sequentially transmitted as parts of the requests. specifically, in the example shown in figs. 1-12 , the screen transition includes transition of the screen designated by the url “/admin/secure/logon.do” to the screen designated by the url “/admin/virtualhostcollection.do”, and then to the screen designated by the url “/admin/virtualhostdetail.do”. for detection of the communication sequence, the request line of each request transmitted from the client computer 100 to the server computer 200 , i.e., the first line in the examples shown in figs. 1-12 , is referred to. more specifically, for example, the detection unit 310 firstly sorts the requests included in the history in time series, and eliminates any unnecessary request indicating occurrence of an error or the like. the detection unit 310 then extracts the command name and the url from each request. provided that the command name indicates a request for a page (for example, on the condition of post or get in http), the detection unit 310 selects the url corresponding to the command name. the sequence of the urls thus selected indicates the screen transition. the detection unit 310 specifies all the screen transitions included in the history in this manner, and then detects from the history a plurality of communication sequences that cause the same screen transition. for example, the detection unit 310 may detect as each of the communication sequences the one that appears with a frequency equal to or greater than a predetermined reference frequency. this may be done for example by detecting any communication sequence that appears a predetermined number of times or more within a predetermined period in the past. as a result, the screen transition of frequent occurrence is specified. next, the first selection unit 320 accesses the storage device 104 , and selects an input parameter that is included in all of the detected communication sequences and that has a parameter value changed for each communication sequence. for example, in the example shown in figs. 5 and 6 above, the parameter value “xxxx” set for the input parameter “button.new” when the button “new” is operated is not changed for each communication sequence. in contrast, in the example shown in figs. 8 and 9 above, the parameter value “vh 005 ” set for the input parameter “name” may be changed according to the user's operation. the first selection unit 320 selects such an input parameter based on the history that the user actually changed the parameter value. by way of example, if the input parameter “name” has been changed to “vh 001 ”, “vh 002 ” or “vh 003 ” for each communication sequence, the first selection unit 320 selects this input parameter “name”. the second selection unit 330 accesses the storage device 104 and selects, for at least one of the plurality of communication sequences detected by the detection unit 310 , a plurality of input parameters having the same parameter value set therefor. for example, in the above-described example in fig. 9 , the parameter value “vh 005 ” is set for the input parameter “name”. in the above-described example in fig. 12 , the parameter value “vh 005 ” is set for the input parameter “column 2 ” as well. accordingly, the second selection unit 330 selects these input parameters “name” and “column 2 ”. the match determination unit 340 accesses the storage device 104 and determines, for at least one of the communication sequences detected by the detection unit 310 , whether the parameter value of a first parameter included in a first response matches the parameter value of a second parameter included in a second request transmitted later than the first response. for example, assume that the parameter value “vh 005 ” for the first parameter “value” on the (w+8)-th line in fig. 10 above is set as the parameter value for the second parameter “column 2 ” on the l-th line in fig. 12 above. in this case, the match determination unit 340 determines that the parameter values of these parameters match. next, the setting unit 350 displays the selected results of the first selection unit 320 and the second selection unit 330 as well as the determined result of the match determination unit 340 to the user for confirmation as to whether the communication sequence may be automated based on the results. the screen for such confirmation will be illustrated as a screen 106 x later. the generating unit 360 generates a program for causing the client computer 100 to reproduce the communication sequence based on the result of confirmation by the setting unit 350 , and stores the program in the storage device 104 . this program is a so-called wizard program, which accepts an input of the parameter value from the user in an interactive manner for reproduction of the communication sequence. the program may be carried out by the agent system 108 itself. in such a case, the agent system 108 serves as an input accepting unit 370 and an execution unit 380 . the input accepting unit 370 causes the web browser 106 of the client computer 100 , for example, to accept an input of a new parameter value to be set as the parameter value of the input parameter selected by the first selection unit 320 . further, the input accepting unit 370 causes the web browser 106 of the client computer 100 , for example, to accept an input of a new parameter value to be set commonly for the plurality of input parameters selected by the second selection unit 330 . it should be noted that whether to accept the inputs of the new parameter values for the input parameters depends on the result of confirmation with the user by the generating unit 360 . the execution unit 380 , in response to the inputs of the new parameter values, sets the new parameter values to the respective input parameters selected by the first selection unit 320 and the second selection unit 330 , to thereby reproduce the communication sequence. this communication sequence causes the same screen transition as the one caused by the communication sequences detected by the detection unit 310 . for example, the execution unit 380 may read the communication sequence from the storage device 104 and transmit it to the web server 206 after changing only the parameter values of the input parameters. further, the execution unit 380 may automatically set the parameter value based on the result of determination by the match determination unit 340 . specifically, the execution unit 380 may set the parameter value of the first parameter, received as a part of the first response during the execution of the communication sequence, to the second parameter included in the second request transmitted later than the first response. in this manner, a subsequent request can be determined based on the response, which ensures a wider range of variations for automation. it is noted that the input accepting unit 370 and the execution unit 380 may work on another client computer other than the client computer 100 , to cause the other client computer to reproduce communication. specifically, the program generated in the storage device 104 may be transferred to the other client computer by a recording medium or via a telecommunication line and executed by the other client computer. as such, the computer that acquires the history and the computer that reproduces the communication sequence based on the history may be different from each other. fig. 14 shows a flow of the processing in which the agent system 108 according to the present embodiment generates a program based on a communication history. the history acquisition unit 300 acquires and stores in the storage device 104 the history of the client computer 100 communicating with the server computer 200 in receipt of user's operations (s 1400 ). next, the detection unit 310 detects a plurality of communication sequences that cause the same screen transition on the client computer 100 and that appear with a frequency equal to or greater than a predetermined reference frequency (s 1410 ). next, the first selection unit 320 selects an input parameter that is included in all of the detected communication sequences and that has its parameter value changed for each communication sequence (s 1420 ). further, the second selection unit 330 selects, for at least one of the plurality of communication sequences detected by the detection unit 310 , a plurality of input parameters having the same parameter value set therefor (s 1430 ). these input parameters are grouped together for a batch entry, on the condition of agreement by the user. that is, during reproduction of the communication sequence, the same parameter value is set for each of these input parameters. further, the match determination unit 340 checks, for at least one of the plurality of communication sequences detected by the detection unit 310 , for a match between the parameter value of a first parameter included in a first response and the parameter value of a second parameter included in a second request transmitted later than the first response (s 1440 ). next, the setting unit 350 displays the selected results of the first selection unit 320 and the second selection unit 330 as well as the checked result of the match determination unit 340 (s 1450 ), and confirms to the user whether the communication sequence may be automated based on the results (s 1460 ). the generating unit 360 generates and stores in the storage device 104 a program for causing the client computer 100 to reproduce the communication sequence based on the result of confirmation by the setting unit 350 (s 1470 ). this program may be output externally to another client computer. fig. 15 shows details of the flow of the process performed in s 1410 . firstly, the detection unit 310 accesses the storage device 104 to read a communication history (s 1500 ). it is assumed that this communication conforms to http. next, the detection unit 310 classifies the read history into communication sessions (s 1510 ). the method of implementing such classification depends on the method of implementing the sessions. for example, the detection unit 310 may classify an http request according to a session id set in a prescribed field of that http request. alternatively, the detection unit 310 may classify an http request according to a session id added to the end of a destination url of that http request. next, the detection unit 310 eliminates any request including a command other than the get command or the post command from the respective parts of the classified history (s 1520 ). further, the detection unit 310 eliminates the response corresponding to the eliminated request. next, the detection unit 310 selects any response of html data from the respective parts of the classified history (s 1530 ). this is implemented by selecting any http response having the content-type field set as “text/html”. then, the detection unit 310 eliminates the request corresponding to the response other than the selected responses. this can eliminate the request for an image constituting a part of a screen or the like. next, the detection unit 310 selects any response having a status code indicating error or invalidity from the respective parts of the classified history (s 1540 ). then, the detection unit 310 eliminates the request corresponding to the selected response from the history. the detection unit 310 then detects, from the history classified into sessions and having the unnecessary portions eliminated based on the above-described conditions, any communication sequence that appears with a frequency equal to or greater than a predetermined reference frequency (s 1550 ). for example, the detection unit 310 sequentially scans the communication history in time series from the beginning, and detects a plurality of communication sequences having the longest match. specifically, for example in the case where the transition of screens 1 , 2 , 3 and 4 and the transition of screens 5 , 1 , 2 and 3 are included in the history, the communication sequences causing the transition of the screens 1 , 2 and 3 corresponding to the longest portion out of the common portion are detected. it is noted that the communication sequence that appears with a frequency equal to or greater than the reference frequency but that has the number of transiting screens smaller than a reference number may be eliminated from the target of detection, because such a communication sequence would not be very convenient even if automated. rather, detecting such a communication sequence as well would increase the number of detected communication sequences too much, thereby rendering a more important communication sequence inconspicuous. fig. 16 shows an example of the screen 106 x displayed on the web browser 106 in s 1450 . the setting unit 350 displays the communication sequences detected by the detection unit 310 on the screen 106 x as a list. specifically, the setting unit 350 may display, for each communication sequence, an identification number (id), thumbnail images of the transiting screens, the number of requests included in the communication sequence, and the frequency of detection. in addition, the setting unit 350 accepts an input as to whether to generate a program for reproducing each of the communication sequences. for example, the right-most column on the screen 106 x has a hyperlink for generation of the program. when the user clicks on the hyperlink, generation of the program for reproducing the corresponding communication sequence is started. the screen 106 x in that case is shown in fig. 17 . fig. 17 shows an example of the screen 106 x displayed on the web browser 106 in s 1460 . as shown in the upper part of the screen 106 x, the generating unit 360 accepts an input of the program name from the user. the program name input here is stored in the storage device 104 in association with the program generated. additionally, the generating unit 360 may accept an input of explanation of the program from the user and store the explanation in the storage device 104 in association with the program. further, the setting unit 350 accepts inputs of settings for various input parameters at the center to the lower part of the screen 106 x. the input parameters displayed here include those selected by the first selection unit 320 or the second selection unit 330 , or those checked by the match determination unit 340 . for example, the input parameter of no. 1 indicates the input parameter selected by the first selection unit 320 . for this, the setting unit 350 displays the id of the input parameter, and the parameter values set for this input parameter in the history. here, “name” is displayed as the id and “vh 001 , vh 002 , vh 003 ” are displayed as the parameter values. this input parameter corresponds to the input parameter “name” set in the above-described request 50 c shown in fig. 9 , for example. when different parameter values such as “vh 001 , vh 002 , vh 003 ” are set for this “name” in the respective communication sequences, the setting unit 350 provides such a display as shown in the screen 106 x to indicate the same. in addition, the setting unit 350 performs setting as to whether to cause the input accepting unit 370 to accept an input of a new parameter value to be set for the input parameter, based on a user's instruction. this is implemented via a radio button in the right-most column on the screen 106 x, for example. when the radio button for “variable parameter” is selected, the input accepting unit 370 accepts an input of the new parameter value to be set for the input parameter in accordance with the operation of the program based on the setting. in this case, the setting unit 350 further accepts inputs of the label name and explanation to be set for the input parameter. the label name and the explanation input here may be displayed for guidance of inputs by the user during execution of the communication sequence by the input accepting unit 370 . on the other hand, in the case where the radio button for “fixed parameter” is selected, the setting unit 350 does not accept an input of the new parameter value to be set for the input parameter. in this case, the setting unit 350 may accept an input of the fixed parameter to be set for the input parameter. for example, a character string input in the input box displayed corresponding to the radio button for “fixed parameter” may be set as the fixed parameter. in this case, the input accepting unit 370 sets this fixed parameter to the input parameter selected by the first selection unit 320 , for execution of the communication sequence. the input parameter of no. 2 collectively indicates a plurality of input parameters selected by the second selection unit 330 . for this, the setting unit 350 displays the ids of the respective input parameters and the parameter value set commonly for these input parameters in the history. here, “name, id, param” and “term 002 ” are displayed as the ids and the parameter value, respectively, indicating that the parameter value “term 002 ” was set commonly for the parameters “name”, “id” and “param”. the setting unit 350 performs setting as to whether to group the input parameters together, according to a user's instruction. this is implemented via the right-most column in the screen 106 x, for example. that is, in the case where the radio button for “yes” is selected, the setting unit 350 groups the input parameters together. when this setting is effected, the input accepting unit 370 accepts an input of the parameter value to be set commonly for the input parameters during execution of the communication sequence. in this case, the input accepting unit 370 may display the label name and explanation input to the screen 106 x, similarly as in the above-described example of the parameter of no. 1. the input parameter of no. 3 indicates the parameter that is checked by the match determination unit 340 and determined to match the parameter included in the response. for this, the setting unit 350 displays the id of the parameter set in the response, the id of the parameter set in the request transmitted after that response, and the parameter value set commonly for these parameters. in the example of the screen 106 x, “secure id”, “auth id” and “323564” are displayed as the response-side id, the request-side id, and the common parameter value, respectively. the setting unit 350 then accepts an input as to whether the parameter value set for the parameter corresponding to the response-side id should be set as the parameter value for the parameter corresponding to the id of the subsequent request as it is, during reproduction of the communication sequence. this is implemented via the right-most column in the screen 106 x. that is, in the case where the radio button for “yes” is selected, the setting unit 350 allows the parameter value set for the response to be set for the request during reproduction of the communication sequence. in contrast, when the radio button for “no” is selected, the setting unit 350 does not allow the parameter value set for the response to be set for the request during reproduction of the communication sequence. in this case, the setting unit 350 causes the input accepting unit 370 to accept an input of the parameter value to be set for the request during reproduction of the communication sequence. at this time, the label name and explanation input to the screen 106 x may be displayed on the screen 106 y, like the above example. in addition to the above-described settings of the input parameters, the setting unit 350 may perform setting to interrupt automatic execution of the communication sequence. specifically, the setting unit 350 may designate interruption of the automatic execution of the communication sequence on the screen related to the input parameter, through an option for no. 1 on the screen 106 x. the screen at which automatic execution will be interrupted may be designated by the screen number counted from the first one, or by the url of the relevant screen. based on such an input, the setting unit 350 sets one of the screens included in the screen transition by the communication sequence executed by the execution unit 380 at which the transition will be interrupted temporarily. in response to an operation of the “enter” button, the generating unit 360 generates a program reflecting the above-described settings and stores it in the storage device 104 . this program includes at least a plurality of requests to be sequentially transmitted for reproduction of the communication sequence and an instruction to accept an input of a new parameter value. an example of the flow of the processing carried out by the input accepting unit 370 and the execution unit 380 based on this program is shown in fig. 18 . fig. 18 shows a flow of the processing in which the agent system 108 according to the present embodiment performs the operations on behalf of the user based on an instruction of the user. the client computer 100 or another client computer reads program names from a storage device such as the storage device 104 and displays them in the form of a list (s 1800 ). when the user designates one of the program names, it reads the program corresponding to the designated program name from the storage device and executes the same to perform the following processing. firstly, the input accepting unit 370 displays a form for accepting an input of a new parameter value on the web browser 106 (s 1805 ). the form may be displayed together with the label name and the explanation set by the setting unit 350 . when an interrupt of the communication sequence has been set, the input accepting unit 370 accepts an input of the parameter value to be set for the request being transmitted before the interrupt, while it does not accept an input of the parameter value to be set for the request being transmitted after restart. on the condition that an instruction to start execution of the communication sequence is received (yes in s 1810 ), the execution unit 380 transmits a first request (s 1820 ). in the request, a newly accepted parameter value may be set as appropriate. on the condition that a response to the request is received (yes in s 1830 ), the execution unit 380 determines whether a predetermined termination condition is satisfied (s 1840 ). the termination condition may include one for normal termination and one for abnormal termination due to occurrence of an error. the termination condition for the normal termination is that transmission of all the requests included in the communication sequence is finished. the termination condition for the abnormal termination due to occurrence of an error may be as follows. the execution unit 380 determines whether a response having the status code indicating error or invalidity has been received during execution of the communication sequence. when such a response is received, the execution unit 380 terminates the processing in fig. 18 , determining that the termination condition for the abnormal termination due to occurrence of an error has been satisfied. further, the execution unit 380 may compare the response received during execution of the communication sequence with the response included in the history for determination of occurrence of an error. as a result, if they match except for the parameter values, it continues execution of the communication sequence, whereas if they do not match, it may determine that an error occurred in the communication sequence. to this end, it is desirable that the program includes the responses stored as the history. when the termination condition is not satisfied (no in s 1840 ), the execution unit 380 determines whether communication corresponding to the transition to the screen set for the interruption by the setting unit 350 has been performed (s 1850 ). for the determination as to whether such communication has been performed, for example, the number of times of screen transition set by the setting unit 350 may be compared with the number of requests transmitted by the execution unit 380 . on the condition that such communication has been performed (yes in s 1850 ), execution of the communication sequence is interrupted, and the input accepting unit 370 displays an input form for accepting an input of a new parameter value to be set for each request included in the communication sequence after restart (s 1860 ). in this case, the necessary part of the response received immediately before may be displayed as well. then, on the condition that an instruction to restart the communication is received (yes in s 1870 ), the execution unit 380 restarts the communication sequence by setting the new parameter value input to the input form. specifically, the execution unit 380 transmits a next request yet to be processed (s 1880 ). thereafter, the process returns to s 1830 , and the communication sequence is continuously carried out until the termination condition is satisfied. fig. 19 shows an example of the screen 106 y displayed on the web browser 106 in s 1805 . the input accepting unit 370 displays the label name such as “virtual host name” or “web module name” in association with the input field of the parameter value. the execution unit 380 then executes the communication sequence in response to an operation of the “execute” button. at this time, the parameter value input to the input field is set for the request. fig. 20 shows an example of the hardware configuration of the client computer 100 according to the present embodiment. the client computer 100 includes: a cpu peripheral portion having a cpu 1000 , a ram 1020 and a graphic controller 1075 connected to each other via a host controller 1082 ; an input/output portion having a communication interface 102 , a hard disk drive 104 and a cd-rom drive 1060 connected to the host controller 1082 via an input/output controller 1084 ; and a legacy input/output portion having a rom 1010 , a flexible disk drive 1050 and an input/output chip 1070 connected to the input/output controller 1084 . the host controller 1082 connects the ram 1020 with the cpu 1000 and the graphic controller 1075 which access the ram 1020 at a high transfer rate. the cpu 1000 operates based on the programs stored in the rom 1010 and the ram 1020 for control of the respective portions. the graphic controller 1075 acquires image data generated by the cpu 1000 or the like on a frame buffer provided in the ram 1020 , for display on the display device 1080 . alternatively, the graphic controller 1075 may include therein a frame buffer for storing the image data generated by the cpu 1000 or the like. the input/output controller 1084 connects the host controller 1082 with the communication interface 102 , the hard disk drive 104 and the cd-rom drive 1060 which are relatively fast input/output devices. the communication interface 102 communicates with an external device via a network. the hard disk drive 104 stores the program and data used by the client computer 100 . the cd-rom drive 1060 reads the program or the data from the cd-rom 1095 and provides the same to the ram 1020 or the hard disk drive 104 . further, the input/output controller 1084 is connected with the rom 1010 and the relatively slow input/output devices such as the flexible disk drive 1050 and the input/output chip 1070 . the rom 1010 stores a boot program executed by the cpu 1000 at the time of activation of the client computer 100 and a program dependent on the hardware of the client computer 100 . the flexible disk drive 1050 reads a program or data from the flexible disk 1090 and provides the same to the ram 1020 or the hard disk drive 104 via the input/output chip 1070 . the input/output chip 1070 establishes connection with the flexible disk 1090 , and with various input/output devices via interface ports such as a parallel port, serial port, keyboard port, and mouse port. the program provided to the client computer 100 is stored in a recording medium such as the flexible disk 1090 , the cd-rom 1095 or an ic card, and provided by the user. the program is read from the recording medium and installed to the client computer 100 for execution, via the input/output chip 1070 and/or the input/output controller 1084 . the operations the program works on and causes the client computer 100 or the like to do are identical to those of the client computer 100 explained in conjunction with figs. 1-19 above, and thus, description thereof will not be repeated. the program described above may be stored in an external storage medium, which may be, besides the flexible disk 1090 and the cd-rom 1095 , an optical recording medium such as a dvd or a pd, a magneto-optical recording medium such as an md, a tape medium, or a semiconductor memory such as an ic card. further, a hard disk provided in a server system connected to a dedicated communication network or the internet, or a storage device such as a ram may be used as the recording medium, and the program may be provided to the client computer 100 via the network. as described above, according to the client computer 100 of the present embodiment, a communication sequence that appears frequently in the communication history in the past may be selected and reproduced to automate a series of operations performed on a plurality of screens, to alleviate the load of the user. further, the client computer 100 detects a parameter that is changed for each communication sequence and parameters for which the same parameter value is set, to set them as the input parameters upon automatic execution of the communication sequence. in this manner, it is possible to reproduce not only the operations exactly the same as those in the communication sequence included in the history, but also the operations changed as necessary upon automatic execution, to improve usability for the user. furthermore, the communication sequence to be executed may be adjusted more meticulously through interruption of the automatic execution or various settings therefor. while the present invention has been described with reference to the embodiment, the description of the embodiment does not restrict the technical scope of the present invention. it is apparent to those skilled in the art that various modifications and improvements are possible for the above-described embodiment. it is evident from description of the claims that the embodiments modified or improved are also within the technical scope of the present invention.
|
076-034-033-975-342
|
EP
|
[
"WO",
"US",
"CN",
"PL",
"EP",
"TR",
"ES",
"DK"
] |
D05C15/08,D05B71/00,D05C15/20
| 2015-04-16T00:00:00 |
2015
|
[
"D05"
] |
tufting machine
|
a tufting machine comprises a needle bar and a needle bar drive mechanism for moving the needle bar towards and away from a backing material passed through a tufting zone by means of a backing material feed mechanism. the machine further comprises at least one controller (18, 20, 22) and a cooling liquid system (10) for cooling at least one controller (18, 20, 22), the cooling liquid system (10) comprising at least one cooling member (56) having a cooling liquid channel (60) for the passage of a cooling liquid and being in heat transfer contact with at least a part of the electrical components of a controller (18, 20, 22).
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tufting machine, comprising a needle bar and a needle bar drive mechanism for moving the needle bar towards and away from a backing material passed through a tufting zone by means of a backing material feed mechanism, further comprising at least one controller (18, 20, 22) and a cooling liquid system (10) for cooling at least one controller (18, 20, 22), the cooling liquid system (10) comprising at least one cooling member (56) having a cooling liquid channel (60) for the passage of a cooling liquid and being in heat transfer contact with at least a part of the electrical components (1 12, 1 14) of a controller (18, 20, 22). the machine according to claim 1 , wherein at least one cooling member (56) comprises at least one cooling plate (58), at least a part of the electrical components (1 12, 1 14) being supported by at least one cooling plate (58), and/or wherein at least one cooling member (56) comprises a body of an electrical component. the machine according to claim 1 or 2, wherein the cooling liquid system (10) comprises a primary cooling liquid circuit (36) and a primary cooling liquid flowing through the primary cooling liquid circuit (36), further comprising a primary heat exchanger (40) for cooling the primary cooling liquid. the machine according to claim 3, wherein the cooling liquid system (10) comprises at least one secondary cooling liquid circuit (42, 44, 46) and a secondary cooling liquid flowing through the secondary cooling liquid circuit (42, 44, 46) and passing through the cooling liquid channel (60) of at least one cooling member (56). the machine according to claim 4, wherein the cooling liquid system (10) comprises at least one secondary heat exchanger (52) for transferring heat from the secondary cooling liquid of at least one secondary cooling circuit (42, 44, 46) to the primary cooling liquid of the primary cooling circuit (36), and/or wherein the cooling liquid system (10) comprises at least one valve means (54) for bringing at least one secondary cooling liquid circuit (42, 44, 46) into and out of cooling liquid exchange communication with the primary cooling liquid circuit (36). the machine according to claim 5, wherein the cooling liquid system (10) comprises at least one multifunctional regulator (50) comprising a valve means (54) and a secondary heat exchanger (52) for cooling a secondary cooling liquid by means of the primary cooling liquid in a condition in which the primary cooling liquid circuit (36) is brought out of cooling liquid exchange communication with at least one secondary cooling liquid circuit (42, 44, 46) by the valve means (54). the machine according to claim 5 or 6, wherein at least one secondary heat exchanger (52) is arranged for transferring heat from the secondary cooling liquids of at least two secondary cooling liquid circuits (42, 44) to the primary cooling liquid of the primary cooling liquid circuit (36), and/or wherein at least one valve means (54) is arranged for bringing at least one secondary cooling liquid circuit (42, 44) of a plurality of secondary cooling liquid circuits (42, 44) into and out of cooling liquid exchange communication with the primary cooling liquid circuit (36). the machine according to one of claims 1 to 7, wherein at least one cooling member (56) comprises a first cooling member portion (62) in heat transfer contact with electrical components (1 12, 1 14) of a controller (18, 20, 22) and a second cooling member portion (64) not in heat transfer contact with electrical components (1 12, 1 14) of a controller (18, 20, 22) for providing a heat exchanger area for cooling ambient air. the machine according to one of claims 1 to 8, wherein a fan (66) is associated with at least one controller (18, 20, 22) for generating an ambient air flow through the controller (18, 20, 22). the machine according to one of claims 1 to 9, wherein means (38, 48, 54, 94, 96) for adjusting the amount of cooling liquid passing through the cooling liquid channel (60) of at least one cooling member (56) are provided, and/or wherein means (38) for adjusting the temperature of the cooling liquid passing through the cooling liquid channel (60) of at least one cooling member (56) are provided. the machine according to claim 10, wherein the means (38, 48, 54, 94, 96) for adjusting the amount of cooling liquid passing through the cooling channel (60) of at least one cooling member (56) comprise a cooling liquid pump (38, 48) and/or a valve (54, 94, 96). the machine according to claim 5 and claim 10 or 1 1 , wherein the means (38) for adjusting the temperature of the cooling liquid passing through the cooling liquid channel (60) of at least one cooling member comprise means (38) for adjusting the amount of primary cooling liquid flowing through at least one first secondary heat exchanger (52). the machine according to one of claims 1 to 12, wherein at least one controller (18, 20, 22) comprises a controller cabinet (30), at least part of the electrical components (1 12, 1 14) of the controller (18, 20, 22) and at least one cooling member (56) being arranged inside the controller cabinet (30). 14. the machine according to one of claims 1 to 13, wherein one controller (18, 20) is provided for controlling the operation of all motors of the tufting machine. 15. the machine according to one of claims 1 to 13, wherein a plurality of controllers (18, 20) are provided for controlling the operation of all motors of the tufting machine. 16. the machine according to one of claims 1 to 15, wherein, in at least one cooling liquid circuit (42) of the cooling liquid system (10), at least two cooling members (56) are arranged serially and/or at least two cooling members (56) are arranged in parallel with each other for the passage of cooling liquid flowing in the cooling liquid circuit (10). the machine according to claim 16, wherein at least two of the cool members (56) are associated with different controllers (18, 20). 18. the machine according to one of claims 1 to 1 7, wherein at least one motor (24, 26, 28) controlled by a controller (18, 20, 22) is cooled by a cooling liquid flowing in a cooling liquid circuit (44, 36) of the cooling liquid system (10). 19. the machine according to claim 18, wherein, in at least one cooling liquid circuit (44), at least one cooling member (56) and at least one motor (26) are arranged serially or in parallel to each other for the passage of cooling liquid flowing in the cooling liquid circuit (44). 20. the machine according to one of claims 1 to 19, wherein at least one cooling member (56) is in heat transfer contact with electrical components (1 12, 1 14) at two opposing sides (1 16, 1 18) thereof, and/or wherein at at least one side (1 16, 1 18) of at least one cooling member (56) at least one electrical component (1 12, 1 14) is removably supported. 21 . method of operating a cooling system, preferably of a tufting machine according to one of the preceding claims, wherein a cooling liquid temperature is controlled such as to have a predetermined preferably substantially constant deviation from an ambient air temperature.
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tufting machine description the present invention relates to a tufting machine for producing tufted fabrics, for example carpets. such a tufting machine is known from wo 2010/003050 a2. this tufting machine comprises a needle bar and a needle bar drive mechanism for moving the needle bar towards and away from a backing material that is passed through a tufting zone by means of a backing feed mechanism. for shifting the needle bar in a direction perpendicular with respect to the backing material feeding direction a needle bar shifting mechanism is provided. for feeding yarns to the needles of the needle bar yarn feed assemblies are provided. further a hook assembly is provided below the tufting zone. as the needles penetrate the backing material the yarns moved by the needles are engaged by the hook assembly so as to form loops of yarn. the various movable components of the tufting machine or moved by motors associated to these components. for example the needle bar is moved by a motor of the needle bar drive mechanism. the backing material is passed through the tufting zone by means of one or a plurality of motors driving respective backing feed rolls. further the yarn feed assemblies as well as the hook assembly have motors associated thereto. all the motors are under the control of a common controller. the controller monitors and controls the operation of the operative elements, e.g. the various motors, of the tufting machine. it is an object of the present invention to provide a tufting machine in which the thermal load of components thereof can be reduced. according to the present invention, this object is achieved by a tufting machine, comprising a needle bar and a needle bar drive mechanism for moving the needle bar towards and away from a backing material passed through a tufting zone by means of a backing material feed mechanism, further comprising at least one controller and a cooling liquid system for cooling at least one controller, the cooling liquid system comprising at least one cooling member having a cooling liquid channel for the passage of a cooling liquid and being in heat transfer contact with at least a part of the electrical components of a controller. in the machine according to the present invention, electrical components of at least one controller are cooled by providing a direct heat transfer contact between these components and the cooling liquid system. therefore, the use of an air flow for taking up heat from the electrical components to be cooled and transferring this heat to the cooling liquid, for example, in a secondary heat exchanger, can be avoided. due to this, the cooling liquid system used in the machine of the present invention provides a substantially increased cooling efficiency. for providing an efficient heat transfer between electrical components to be cooled and the cooling liquid system, at least one cooling member may comprise at least one cooling plate, at least a part of the electrical components being supported by at least one cooling plate, and/or at least one cooling member may comprise a body of an electrical component, such that a cooling liquid can be passed directly through such an electrical component. the cooling liquid system may comprise a primary cooling liquid circuit and a primary cooling liquid flowing through the primary cooling liquid circuit, and may further comprise a primary heat exchanger for cooling the primary cooling liquid. by the use of such a primary heat exchanger, the primary cooling liquid can be cooled for providing this primary cooling liquid in a condition in which heat can be withdrawn from electrical components to be cooled. for further enhancing the efficiency of the machine according to the present invention, the cooling liquid system may comprise at least one secondary cooling liquid circuit and a secondary cooling liquid flowing through the secondary cooling liquid circuit and passing through the cooling liquid channel of at least one cooling member. by using one or a plurality of such secondary cooling liquid circuits, the heat transfer capacity can be easily adapted to the cooling requirements of the various controllers to be cooled. for transferring heat between the primary cooling liquid circuit and one or a plurality of secondary cooling liquid circuits, the cooling liquid system may comprise at least one secondary heat exchanger for transferring heat from the secondary cooling liquid of at least one secondary cooling circuit to the primary cooling liquid of the primary cooling circuit, and/or the cooling liquid system may comprise at least one valve means for bringing at least one secondary cooling liquid circuit into and out of cooling liquid exchange communication with the first cooling liquid circuit. for providing the thermal interaction between the primary cooling liquid circuit and at least one secondary cooling liquid circuit on the one hand and for additionally providing the option of generating a cooling liquid exchange communication between the primary cooling liquid circuit and at least one secondary cooling liquid circuit, the cooling liquid system may comprise at least one multifunctional regulator comprising a valve means and a secondary heat exchanger for cooling a secondary cooling liquid by means of the primary cooling liquid in a condition in which the primary cooling liquid circuit is brought out of cooling liquid exchange communication with at least one secondary cooling liquid circuit by the valve means. according to an advantageous aspect of the present invention, at least one secondary heat exchanger may be arranged for transferring heat from the secondary cooling liquids of at least two secondary cooling liquid circuits to the primary cooling liquid of the primary cooling liquid circuit, and/or at least one valve means may be arranged for bringing at least one secondary cooling liquid circuit of a plurality of secondary cooling liquid circuits into and out of cooling liquid exchange communication with the primary cooling liquid circuit. in such a system, a plurality of controllers can be cooled independently of each other by using different secondary cooling liquid circuits in association with each one of these controllers. for further enhancing the cooling capacity of the machine according to the present invention, at least one cooling member may comprise a first cooling member portion in heat transfer contact with electrical components of a controller and a second cooling member portion not in heat transfer contact with electrical components of a controller for providing a heat exchanger area for cooling ambient air. in such an embodiment, it is further advantageous to provide a fan associated with at least one controller for generating an ambient air flow through the controller. this air flow can be passed around the second cooling member portion for cooling this air flow and for using this cooled air flow as an additional means for cooling components of a controller. for avoiding overheating of electrical components as well as for avoiding a situation in which the temperature of electrical components drops below a desired level, means for adjusting the amount of cooling liquid passing through the cooling liquid channel of at least one cooling member may be provided, and/or means for adjusting the temperature of the cooling liquid passing through the cooling liquid channel of at least one cooling member may be provided. for example, the machine may be arranged such that the means for adjusting the amount of cooling liquid passing through the cooling channel of at least one cooling member comprise a cooling liquid pump and/or a valve, and/or the means for adjusting the temperature of the cooling liquid passing through the cooling liquid channel of at least one cooling member comprise means for adjusting the amount of primary cooling liquid flowing through at least one first secondary heat exchanger. for protecting the electrical components of the controller and for further increasing the cooling efficiency of the cooling liquid system according to the present invention, at least one controller may comprise a controller cabinet, at least part of the electrical components of the controller and at least one cooling member being arranged inside the controller cabinet. the tufting machine of the present invention may be arranged such that one controller is provided for controlling the operation of all motors of the tufting machine. in an alternative embodiment a plurality of controllers may be provided for controlling the operation of all motors of the tufting machine. in either case the cooling liquid system may be arranged such as to cool components of one or a plurality of tufting machines. for enhancing the cooling capacity of the cooling system in at least one cooling liquid circuit of the cooling liquid system at least two cooling members may be arranged serially and/or at least two cooling members are arranged in parallel with each other for the passage of cooling liquid flowing in the cooling liquid circuit, wherein at least two of the cooling members may be associated with different controllers. further, at least one motor controlled by a controller may be cooled by a cooling liquid flowing in a cooling liquid circuit of the cooling liquid system. preferably, in at least one cooling liquid circuit, at least one cooling member and at least one motor may be arranged serially or in parallel to each other for the passage of cooling liquid flowing in the cooling liquid circuit. for providing an increased heat transfer capacity according to an advantageous aspect of the present invention at least one cooling member may be in heat transfer contact with electrical components at two opposing sides thereof. for allowing a simple and quick installation and/or exchange of electrical components at at least one side of at least one cooling member at least one electrical component may be removably supported. it is to be noted that in the context of the present invention the expression "removably supported" means that such an electrical component can be attached to and detached from the supporting cooling plate without destroying the cooling plate and the electrical component. for providing such a removable connection of an electrical component with a cooling member connecting means like screws, rivets, snap fit connectors or press fit connectors may be used. according to a further aspect, the present invention provides a method of operating a cooling system, for example, of a machine according to the present invention, wherein a cooling liquid temperature is controlled such as to have a predetermined preferably substantially constant deviation from an ambient air temperature. by controlling the cooling liquid temperature in such a manner, water condensation can be avoided, which is of great importance if such a cooling system is used for cooling electrical components, for example, of a controller. the present invention will now be explained with respect to the drawings in which: fig. 1 shows the principal construction of a cooling system in a tufting machine for producing tufted fabrics; fig. 2 shows an alternative embodiment of a portion of the cooling system of fig. 1 ; fig. 3 shows a further alternative embodiment of a portion of the cooling system of fig. 1 ; fig. 4 shows a further alternative embodiment of a portion of the cooling system of fig. 1 ; fig. 5 shows a further alternative embodiment of a portion of the cooling system of fig. 1 ; fig. 6 shows a top view of a cooling plate having a plurality of electrical components supported thereon; fig. 7 shows a cross sectional view of the cooling plate of fig.6 along line vii-vii in fig. 6. in fig. 1 , a cooling liquid system 10 for a tufting machine is shown. the principal construction of such a tufting machine has been described above with reference to the prior art. it is to be noted that, insofar as the overall construction of the tufting machine of the present invention is concerned, the machine may be arranged in a manner known in the prior art, for example as known from wo 2010/003050 a2. this means that the tufting machine according to the present invention comprises various operative assemblies, e.g. the needle bar drive mechanism, the needle bar shifting mechanism, the backing feed mechanism, the hook assembly, the yarn feed assembly as well as all the further assemblies which have to be controlled for carrying out the tufting procedure. as at least a part of these assemblies, preferably all these assemblies, comprise motors which for moving associated components have to be controlled by an associated controller. according to the principles of the present invention one single controller may be provided for controlling all the operative assemblies of one tufting machine. however, in association to one tufting machine there may be plurality of controllers for controlling different operative assemblies of this tufting machine. for example, there may be one controller for controlling the operation of the needle bar drive mechanism, while there is another controller for controlling the operation of the needle bar shifting mechanism. in the following description referring to the various embodiments shown in the figures, a plurality of controllers and their thermal interaction with the cooling liquid system 10 will be described. in fig. 1 , for example three such controllers 18, 20, 22 are shown. these controllers may be controllers of one single tufting machine provided for controlling the operation of different assemblies of this tufting machine. however, the controllers shown in the figures and described with respect to the figures may be controllers of different tufting machines for example located within the same building, each one of these tufting machines for example comprising only one controller for controlling the operation of all the assemblies, i.e. all the motors, thereof. it is to be noted that, while the following description will be given with respect to the controllers 18, 20, 22 shown in fig. 1 , there may be other controllers which, insofar as their principal construction and their interaction with the cooling liquid system 10 is concerned, may have the same structure as the controllers 18, 20, 22 shown in fig. 1 . however, of course, there may be other or additional controllers having another construction and another way of interaction with the cooling liquid system 10. there may even be controllers which do not have a thermal interaction with the cooling liquid 10, but which, for example, may be cooled by other means. each one of the controllers 18, 20, 22 comprises a controller cabinet 30 containing electrical components of the controllers 18, 20, 22. for example, each controller 18, 20, 22 may comprise a controller unit 32 having one or a plurality of microcontrollers and/or other electrical components. these controller units 32 are used for generating control signals, for example, for controlling the operation of the respective motors 24, 26, 28 based on programs stored in the respective controller units 32 and/or based on information input into such a controller unit 32. further, the controllers 18, 20, 22 comprise electrical components which are provided for outputting the power for energizing the respective motors 24, 26, 28. these electrical components, for example, may comprise inverters for applying a high voltage to the respective motors 24, 26, 28. these electrical components which generally may be considered as providing drives 34 for the motors 24, 26, 28 and which may comprise printed circuit boards are the components which, due to their high load in operation, produce quite high amounts of heat. these drives 34, together with other electrical components of the respective controllers 18, 20, 22, e.g. the control units 32, are contained within the respective controller cabinets 30. it is the primary focus of the cooling liquid system 10 of the present invention to take up heat generated by these drives 34 such as to avoid overheating of the electrical components contained within the respective controller cabinets 30. however, it is to be noted that, by means of the cooling liquid system 10 of the present invention, other or additional electrical components of one or of a plurality of the controllers 18, 20, 22 can be cooled. the cooling liquid system 10 of the present invention comprises a primary cooling liquid circuit 36 in which, by means of a pump 38, a primary cooling liquid, for example, water, is circulated. for cooling this primary cooling liquid, the primary cooling liquid circuit 30 comprises a primary heat exchanger 40. for example, this primary heat exchanger 40 may be part of an air-cooled refrigeration condensing unit in which a cooling liquid is circulated between a condenser and an evaporator. in the primary heat exchanger 40, the heat transported in the primary cooling liquid, for example, may be transferred to the ambient air outside a building in which one or a plurality of tufting machines are positioned. in association with each one of the controllers 18, 20, 22, there is provided a respective secondary cooling liquid circuit 42, 44, 46. each of these secondary cooling liquid circuits 42, 44, 46 comprises a respective pump 48 by means of which a secondary cooling liquid is circulated within the secondary cooling liquid circuits 42, 44, 46. for example, the secondary cooling liquid used in the secondary cooling liquid circuits 42, 44, 46 may be water. in association with each one of the secondary cooling liquid circuits 42, 44, 46, there is provided a multifunctional regulator 50 which, in a condition shown in fig. 1 , is operated as a secondary heat exchanger 52 for transferring heat from the secondary cooling liquid flowing in the secondary cooling liquid circuits 42, 44, 46 to the primary cooling liquid flowing in the primary cooling liquid circuit 36. in this operational condition, the multifunctional regulator 50 separates the primary cooling liquid circuit 36 from the various secondary cooling liquid circuits 42, 44, 46, but provides a heat transfer contact between the secondary cooling liquids flowing in the secondary cooling liquid circuits 42, 44, 46 and the primary cooling liquid flowing in the primary cooling liquid circuit 36. the multifunctional regulators 50 may further comprise valve means 54 by means of which the primary cooling liquid circuit 36 can be separated from the secondary cooling liquid circuits 42, 44, 46 for providing the condition shown in fig. 1 . in another switching mode of the valve means 54, the primary cooling liquid circuit 36 is brought into cooling liquid exchange communication with the respective secondary cooling liquid circuits 42, 44, 46, as shown by dashed lines within the respective multifunctional regulators 50 of fig. 1 . in this condition, the primary cooling liquid flowing in the primary cooling liquid circuit 36 may enter the respective secondary cooling liquid circuits 42, 44, 46 for passing through the respective controllers 18, 20, 22 and then flowing back to the primary cooling liquid circuit 36 via the associated multifunctional regulators 50. in this condition, the primary cooling liquid circuit 36 and the secondary cooling liquid circuits 42, 44, 46, which are in cooling liquid exchange communication with the primary cooling liquid circuit 36, act as one cooling liquid circuit having one and the same cooling liquid passing there through. due to this, it is advantageous to use the same kind of cooling liquid for the primary cooling liquid circuit 36 and the secondary cooling liquid circuits 42, 44, 46 as, in the condition in which there is a cooling liquid exchange communication, these cooling liquids will become intermixed. as indicated in fig. 1 , each one of the multifunctional regulators 50 is under control of the control unit 32 of the one controller 18, 20, 22 which is to be cooled by the respective secondary cooling liquid circuit 42, 44, 46, such that the multifunctional regulators 50 can be switched between the two above- referenced conditions independently of each other. for example, during cooling operation, the secondary cooling liquid circuit 42 may be separated from the primary cooling liquid circuit 36, while the other secondary cooling liquid circuits 44, 46 are in cooling liquid exchange communication with the primary cooling liquid circuit 36. the respective switching condition of the multifunctional regulators 50 can be selected on the basis of various parameters, for example, on the basis of the amount of heat which has to be withdrawn from the respective controllers 18, 20, 22. for withdrawing heat in particular from the heat generating drives 34 of the various controllers 18, 20, 22, the cooling liquid system 10 comprises at least one cooling member 56 in association with each one of the controllers 18, 20, 22. in the embodiment shown in fig. 1 , one such cooling member 56 is provided within the controller cabinet 30 of each one of the controllers 18, 20, 22. in an advantageous embodiment, each cooling member 56 may comprise at least one cooling plate 58, for example, made of metal material and providing a cooling liquid channel 60 for the passage of the cooling liquid, for example, the secondary cooling liquid, flowing in the associated secondary cooling liquid circuit 42, 44, 46. the drives 34 which are to be cooled by means of the cooling liquid circuit 10 are directly mounted on at least one side of the cooling plates 58 such that there is a direct thermal contact between these drives 34 and their electrical components, respectively, and the cooling plates 58. due to this direct heat transfer contact, the heat generated by the electrical components of the drives 34 can be withdrawn from the drives 34 and taken up in the secondary cooling liquid flowing through a respective cooling liquid channel 60 in a very efficient manner. in a further embodiment, the electrical components to be cooled, i.e. electrical components of the drives 34, may be arranged such as to have bodies providing cooling liquid channels such that the cooling liquid can be passed directly through these electrical components to be cooled. in figs. 6 and 7 one example of attaching electrical components to a cooling plate 58 providing a cooling member 56 is shown. cooling plate 58, which for example may be made of metal material, provides an undulating cooling liquid channel 100 having two connecting openings 102, 104 for connecting this cooling liquid channel 100 to a respective cooling liquid circuit. at two opposing side faces 106, 108 the channel 1 00 is closed by plate shaped closure members 1 10. electrical components 1 12, 1 14 are attached to two opposing sides 1 16, 1 18 of the cooling plate 58. in the example shown in figs. 6 and 7 electrical components 1 12, 1 14 are fixed to the cooling plate 58 by using screws 120 passing through openings 122 provided in the electrical components 1 12, 1 14 and screwed into screw holes 124 of the cooling plate 58. by using screws 120 for fixing the electrical components 1 12, 1 14 to the cooling plate 58 the electrical components 1 12, 1 14 are removably supported on the cooling plate 58 in direct heat transfer contact therewith. therefore the electrical components 1 12, 1 14 can be attached to the cooling plate 58 in a simple and quick manner and can be detached from the cooling plate 58 in a simple and quick manner without destroying the electrical components 1 12, 1 14 and the cooling plate 58. it is to be noted that other means can be used for removably attaching the electrical components 1 12, 1 14 to the cooling plate 58. for example rivets, snap fit connectors or press fit connectors may be used for fixing the electrical components 1 12, 1 14 to the cooling plate 58. different means for fixing electrical components to the cooling plate 58 may be used in association to different electrical components. for example the electrical components 1 14, which might be or comprise converters producing a high amount of heat during operation, may be fixed to the cooling plate by means of the shown screws, while the electrical components 1 12, which might be or comprise printed circuit boards supporting a plurality of transistors, resistors, capacitors and the like, may be fixed to the cooling plate 58 by means of rivets or other fixation means. while it is advantageous to have all electrical components removably fixed to the supporting cooling plates, at least some of the electrical components may be fixed to at least one supporting cooling plate in a non-removable manner, for example by gluing them to a surface of a cooling plate. further electrical components may be provided on both opposing sides of only some of the cooling plates or of all the cooling plates. as shown in association with the controllers 18, 22, the cooling members 56 may be arranged such as to provide a first cooling member portion 62. in this first cooling member portion 62, the electrical components to be cooled are arranged in direct thermal contact with the respective cooling members 56. further, these cooling members 56 provide second cooling member portions 64. in these second cooling member portions 64, no electrical components to be cooled are arranged, such that these second cooling member portions 64 are in thermal contact with the ambient air contained within a respective controller cabinet 30. due to this thermal contact, the air contained within the controller cabinets 30 can be cooled. by means of a respective fan 66, an air circulation may be generated within the controller cabinets 30 such that, by the use of the circulation of cooled air, other electrical components, for example, the controller units 32, which are not in direct thermal contact with the cooling members 56 contained within the controller cabinets 30, can be cooled. the operation of these fans 66 as well as the operation of the pumps 48 associated with the secondary cooling liquid circuits 42, 44, 46 may be controlled by the controller units 32 of the controllers 18, 20, 22. for controlling the fans 66 and/or the pumps 48, the controller units 32 may be arranged to receive information from a temperature sensor 68 measuring the temperature of the secondary cooling liquid flowing to the controllers 18, 20, 22, a temperature sensor 70 measuring the temperature of the secondary cooling liquid exiting the controllers 18, 20, 22, and a temperature sensor 72 measuring the ambient temperature, for example, outside the controller cabinets 30. there may be one single temperature sensor 72 for providing the temperature signal for all the controllers 18, 20, 22. in the embodiment shown in fig. 1 , there are a plurality of such temperature sensors 72 such that each controller unit 32 can carry out the control on the basis of a temperature signal indicating a temperature of the ambient air, for example, near the controller cabinet 30 of the associated controller 18, 20, 22. according to the principles of the present invention, the flow of cooling liquid through the various cooling members 56 may be adjusted such that the temperature of the cooling liquid flowing to a respective cooling member 56 has a predetermined constant deviation from the ambient air temperature, i.e. the temperature detected by the temperature sensors 72. for example, the temperature of the cooling liquid flowing to a respective cooling member, which temperature is measured by the temperature sensors 68, may be adjusted such as to be in a temperature range of plus or minus 5°c around the ambient air temperature. for adjusting the temperature of the cooling liquid flowing through the cooling members 56, the amount of secondary cooling liquid pumped by the pumps 48 may be adjusted and/or the multifunctional regulators 50 may be switched between the above-referenced two operational conditions for thereby adjusting the amount of heat transferred between the secondary cooling liquid circuits 42, 44, 46 and the primary cooling liquid circuit 36. by controlling the temperature of the cooling liquid flowing to the controllers 18, 20, 22 to be cooled to be within the above-referenced range, water condensation within the controller cabinets, in particular in the area of the drives 34, which are in direct thermal contact with the cooling members 56, can be avoided. as shown in fig. 1 , a secondary cooling liquid circuit, for example, secondary cooling liquid circuit 44, may be arranged such as to additionally provide a cooling function for at least one motor 26. for example, this can be a motor which is controlled by the one controller 20 that is cooled by the same secondary cooling liquid circuit 44. in the embodiment shown in fig. 1 , the cooling member 56 and the motor 26 which are cooled by the secondary cooling liquid of the same secondary cooling liquid circuit 44 may be arranged such that they are in parallel to each other. optionally, these components may be arranged serially within the respective cooling liquid circuit. as further shown in fig. 1 , the primary cooling liquid circuit 36 may comprise further connections 74 by means of which the primary cooling liquid circulated within the primary cooling liquid circuit 36 can be directed to additional components to be cooled. for example, the controllers of further tufting machines may be connected to the primary cooling liquid circuit 36 by using such additional connectors 74. in the embodiment shown in fig. 1 , the motor 28 is directly connected to the primary cooling liquid circuit 36 via the additional connectors 74. therefore, motor 28 can be cooled by the primary cooling liquid flowing in the primary cooling liquid circuit 36. fig. 2 shows a variation of the cooling liquid system 10. in this variation, the secondary cooling liquid circuit 42 is used for cooling electrical components of two controllers 18, 20. as can be seen, the cooling members 56 associated to these two controllers 18, 20 are arranged serially within the secondary cooling liquid circuit 42 such that the secondary cooling liquid pumped by pump 48 is delivered to the cooling member 56 of the controller 20 and, after having passed through this cooling member 56, is passed through the cooling member 56 of the controller 18. it is to be noted that more than two controllers can be cooled by one and the same secondary cooling liquid circuit. further, the cooling members associated to different controllers can be arranged in parallel to each other instead of the serial arrangement shown in fig. 2. further, a combination of cooling members arranged serially with respect to each other and cooling members arranged in parallel with respect to each other can be used. in fig. 3, a further variation of the cooling liquid system 10 is shown. here, one multifunctional regulator 50 is used in association with two secondary cooling liquid circuits 42, 44. each one of these secondary cooling liquid circuits 42, 44 is used for cooling one controller 18, 20. for example, at least one of these cooling liquid circuit 42, 44 might be used for cooling a plurality of controllers, as is shown in fig. 2. the multifunctional regulator 50 of the embodiment shown in fig. 3, on the one hand, is arranged such as to provide the secondary heat exchanger 52 for transferring heat between the two secondary cooling liquid circuits 42, 44 and the primary cooling liquid circuit 36. the multifunctional regulator 50 is further arranged such as to provide the valve means 54 for generating a cooling liquid exchange communication between the secondary cooling liquid circuits 42, 44 and the primary cooling liquid circuit 36. the arrangement can be such that the two secondary cooling liquid circuits 42, 44 can be brought into cooling liquid exchange communication with the primary cooling liquid circuit 36 independently of each other, such that, for example, the secondary cooling liquid circuit 42 is in cooling liquid exchange communication with the primary cooling liquid circuit 36, while the secondary cooling liquid circuit 44 is in heat transfer communication, but not in cooling liquid exchange communication with the primary cooling liquid circuit 36. further, the valve means 54 can be switched such that both the secondary cooling liquid circuits 42, 44 are in cooling liquid exchange communication with the primary cooling liquid circuit 36. again, it is to be noted that, by means of one and the same multifunctional regulator, more than two secondary cooling liquid circuits can be brought into and out of cooling liquid exchange communication with the primary cooling liquid circuit. fig. 4 shows a further alternative aspect of a cooling liquid system 10. it is to be mentioned that the aspect shown in fig. 4, of course, can be combined with one or a plurality of the constructional variations shown in and described with respect to the other figures. in the variation shown in fig. 4, there are two controllers 18, 20 contained in associated controller cabinets 30. the secondary cooling liquid circuit 42 used for cooling electrical components of these two controllers 18, 20 comprises two parallel branches 90, 92. the secondary cooling liquid circulated by the pump 48 of this secondary cooling liquid 42 flows through the cooling members 56 of the two controllers 18, 20 in a parallel manner such that the same cooling effect can be obtained in both the controllers 18, 20. for selectively connecting and disconnecting the secondary cooling liquid circuit 42 to and from the primary cooling liquid circuit 36, a valve 94, e.g. a 3-port valve, may be arranged between the primary cooling liquid circuit 36 and the secondary cooling liquid circuit 42. for example, by means of the controller unit 32 of the controller 18 this valve 94 is controlled such as to adjust the amount of cooling liquid exchanged between the primary cooling liquid circuit 36 and the secondary cooling liquid circuit 42. if a high amount of heat has to be withdrawn from the controllers 18, 20, then the valve 94 may be controlled such as to provide a maximum cooling liquid exchange communication between the primary cooling liquid circuit 36 and the secondary cooling liquid circuit 42. if less heat has to be withdrawn, then the valve 94 can be controlled such as to reduce the amount of cooling liquid exchanged between the two cooling liquid circuits 36, 42 or to even completely disconnect the secondary cooling liquid circuit 42 from the primary cooling liquid circuit 36 such that the secondary cooling liquid circulated within the secondary cooling liquid circuit 42 by means of the pump 48 will only be circulated within this secondary cooling liquid circuit 42. the control can be such that, for example, depending on the temperature detected by the temperature sensors 68 and/or 70 and/or 72, the temperature of the secondary cooling liquid circuit flowing through the cooling members 56 is adjusted such as to be equal to or below a desired temperature within the controller cabinets 30 or in the area surrounding the controller cabinets 30. for further adjusting the amount of cooling liquid passed through the respective cooling members 56 of the controllers 18, 20 in association with each one of the branches 90, 92 a further valve 96 may be provided, which, for example, may also be a 3-port valve and which may be controlled by the controller units 32 of the associated controllers 18, 20. by means of these valves 96, in each one of the branches 90, 92, the amount of cooling liquid passed through the cooling members 56 thereof can be adjusted individually. therefore, even if a high amount of cooling is necessary in controller 18, while, due to a reduced load, substantially no cooling is necessary in the controller 20, the valve 96 associated with the branch 92 of the controller 20 can be controlled such as to reduce the flow of cooling liquid through the cooling member 56 of the controller 20 or to completely lock off this branch 92 such that a more efficient cooling can be obtained in the other branch 90. again, the control of the valves 96 can be based on the temperature of the cooling liquid flowing in the respective branches 90, 92 and the desired temperature of the controllers 18, 20. it is to be noted that more than two such branches can be associated with one and the same secondary cooling liquid circuit or that a plurality of secondary cooling liquid circuits, each one comprising at least two such parallel branches, may be provided. there even may be a combination of parallel and serial arrangement of controllers to be cooled within one and the same secondary cooling liquid circuit or within different secondary cooling liquid circuits. it is further to be noted that in the embodiment shown in fig. 4 as well as in the embodiments shown in the other figures one or a plurality of the valves may be arranged such as to be controllable by one or a plurality of controller units, as shown in the figures. alternatively one or a plurality of the valves may be arranged such as to be manually controllable. for example, one or a plurality of the valves 96 for opening or closing the respective branches 90, 92 of the secondary cooling liquid circuit 42 may be manually controllable valves. further the valve 94 for connecting or disconnecting the secondary cooling liquid circuit 42 to and from the primary cooling liquid circuit 36 may be a manually controllable valve. in the arrangement shown in fig. 4 as well as in all the other arrangements shown in the other figures in association to the secondary cooling liquid circuit 42 and/or in association to any other cooling liquid circuit a flow meter may be provided for providing information about the flow of cooling liquid within a respective cooling liquid circuit. this information may be used by any controller unit controlling one or a plurality of valves and/or pumps for indicating to one or a plurality of the controller units 32 of the controllers 30 that there is a sufficient flow of cooling liquid and that therefore the controllers can be operated for activating the motors or any other devices controlled by them. a further variation of the cooling liquid system 10 of the present invention is shown in fig. 5. in the variation of fig. 5, there again are two secondary cooling liquid circuits 18, 20 which, by means of respective multifunctional regulators 50, can be connected, disconnected or brought into thermal contact with the primary cooling liquid circuit 36. in association with the controller 18 cooled by the secondary cooling liquid circuit 42, there is shown one motor 24 which, for example, may be used for moving a needle bar. the drive 34 and the electrical components thereof, respectively, associated with this motor 24 are arranged in direct thermal contact with the cooling plate 58 arranged within the controller cabinet 30 of the controller 18. due to this arrangement, the drive 34 is cooled by the secondary cooling liquid circulated in the secondary cooling liquid circuit 42. in association with the controller 20 shown on the right-hand side of fig. 5, there is provided a motor 26 having an integrated drive 34 for applying the energizing voltage to this motor 26. this means that the drive 34, as well as the motor 26, is not arranged within the controller cabinet 30 of this controller 20. however, there is a control connection between this drive 34 and the controller unit 32 of the controller 20 such that the controller unit 32 can control the operation of the motor 26 by outputting control signals to the drive 34 associated with this motor 26. for cooling this motor 26 and/or the drive 34 associated with this motor 26, the primary cooling liquid circuit 36 comprises a branch 98 for passing the primary cooling liquid circulated in the primary cooling liquid circuit through a cooling liquid channel provided within the motor 26 and/or the drive 34. such a branch 98 of the primary cooling liquid circuit 36 can also be seen in the embodiment of fig. 1 . from the above explanation, it becomes clear that, according to an advantageous aspect of the present invention, a cooling liquid can be used to withdraw heat from electrical components and/or motors by using a direct thermal contact. according to a further advantageous aspect, the cooling liquid system of the present invention may be subdivided into one or a plurality of primary cooling liquid circuits and one or a plurality of secondary cooling liquid circuits. due to the fact that each one of these cooling liquid circuits has its own pump associated therewith, the cooling liquids provided in these various cooling liquid circuits may be circulated independently of each other for adapting the cooling behavior to the amount of cooling that, based on the thermal condition within a respective controller or in the area surrounding the controllers, is necessary. of course, this cooling effect can be used for cooling any kind of electrical or electronic components, for example, of a drive or a controller unit. while, with reference to the drawings, specific embodiments of the cooling liquid system according to the present invention have been described, it is to be noted that the principles shown with respect to the different embodiments can be combined. further, it is to be noted that, instead of individually controlling each one of the secondary cooling liquid circuits by means of a controller unit associated with a respective controller cooled by specific secondary cooling liquid circuit, a controller unit may control more than one secondary cooling liquid circuit or there may be a central cooling liquid circuit control unit receiving the temperature signals from the various temperature sensors and controlling the operation of the various multifunctional regulators and/or pumps for adjusting the heat transfer capacity of each one of the secondary cooling liquid circuits and the primary cooling liquid circuit, respectively.
|
076-344-451-697-57X
|
GB
|
[
"GB",
"EP",
"JP",
"DK",
"CA",
"WO",
"AU",
"ES",
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B64C3/56,B64C39/00,B64C39/02,B64C1/26,B64C3/38,B64C3/54,B64C3/16
| 2015-08-13T00:00:00 |
2015
|
[
"B64"
] |
an unmanned aerial vehicle
|
an unmanned aerial vehicle 2 comprises a fuselage 4 and a wing 6 comprising a central wing section 12 pivotably mounted to the fuselage 4 and a pair of outer wing sections 14a, 14b pivotably mounted to the central wing section 12, the wing 6 having a folded configuration in which the central wing section 12 and the outer wing sections 14a, 14b are stacked on top of one another and are aligned with a longitudinal axis of the fuselage 4 and a deployed configuration in which the central wing section 12 is substantially perpendicular to the fuselage 4 and the outer wing sections 14a, 14b extend from the central wing section 12 away from the fuselage 4. a second pair of outer wing section may be pivotably mounted to the first pair of outer wing sections 14a, 14b. at least one of the outer wing sections 14a, 14b may move vertically during deployment such that the pair 14a, 14b are aligned with one another and with the central section 12. the wing 6 may be spring biased to the deployed configuration. a latch may be provided to hold the wing 6 in the folded configuration. the vehicle 2 may be housed within a tube which retains the wing 6 in the folded configuration.
|
an unmanned aerial vehicle comprising: a fuselage; and a wing comprising a central wing section pivotably mounted to the fuselage and a pair of outer wing sections pivotably mounted to the central wing section; wherein the wing has: a folded configuration in which the central wing section and the outer wing sections are stacked on top of one another and are aligned with a longitudinal axis of the fuselage; and a deployed configuration in which the central wing section is substantially perpendicular to the fuselage and the outer wing sections extend from the central wing section away from the fuselage. an unmanned aerial vehicle as claimed in claim 1, further comprising a second pair of outer wing sections pivotably mounted to the first pair of outer wing sections. an unmanned aerial vehicle as claimed in claim 1 or 2, wherein at least one of the outer wing sections moves vertically during a transition from the folded configuration to the deployed configuration such that the outer wing sections are aligned with one another when in the deployed configuration. an unmanned aerial vehicle as claimed in claim 1 or 2, wherein the outer wing sections move vertically during a transition from the folded configuration to the deployed configuration such that the outer wing sections are aligned with one another and the central wing section when in the deployed configuration. an unmanned aerial vehicle as claimed in any of the preceding claims, wherein the outer wing elements are angled relative to the central wing section when in the deployed configuration such that the wing has a dihedral or anhedral angle. an unmanned aerial vehicle as claimed in any preceding claim, wherein the wing is biased towards the deployed configuration. an unmanned aerial vehicle as claimed in claim 6, wherein the central wing section is biased by means of a torsion spring. an unmanned aerial vehicle as claimed in claim 7, wherein the fuselage comprises a stop which limits rotation of the central wing section relative to the fuselage. an unmanned aerial vehicle as claimed in any of claims 6 to 8, wherein each of the outer wing sections is biased by means of a tension spring. an unmanned aerial vehicle as claimed in claim 9, wherein the tension spring is connected at one end to the central wing section and at the other end to the outer wing section via a pulley such that rotation of the outer wing section relative to the central wing section extends the tension spring. an unmanned aerial vehicle as claimed in any of claims 6 to 10, further comprising a latch which holds the wing in the folded configuration against the bias and which is released so as to allow the wing to be deployed. an unmanned aerial vehicle as claimed in claim 11, wherein the latch is released remotely or automatically. an unmanned aerial vehicle as claimed in any preceding claim, wherein the vehicle is housed within a tube which retains the wing in the folded configuration. an unmanned aerial vehicle as claimed in claim 13, wherein the wing is unfolded into the deployed configuration when released from within the tube.
|
the invention relates to an unmanned aerial vehicle (uav) and a folding mechanism of aerofoil components for an unmanned aerial vehicle. the design of uavs has seen great advancement in recent years. the field grew mainly out of military development, where uavs are commonly used for surveillance, but has expanded further into commercial uses, such as in delivery and filmmaking, which enforces a position at the forefront of technological research. uavs have been developed in various forms, such as single- or multi-rotor helicopters or fixed wing aircraft. with the evolution of ever decreasing electronic and mechanical components, micro- and even nano- versions of uavs continue to be developed. one issue with the development of uavs is that there are advantages to having large wingspans or sizeable rotors in comparison to their fuselage length. these advantages include the ability to create low drag fixed wing aircraft, which allow for long flight times. any aircraft with a large span will cause problems when it comes to transportation, which has led to disassemblable and foldable designs. it may be useful to transport the uav in existing available storage, which in military uses, may be on larger aircraft, ships or submarines. another problem arises when it comes to launch procedure. while launch devices are available for missiles and other munitions, they may not be available for specific uav designs and it may not necessarily be possible to perform a horizontal takeoff. the present invention seeks to provide a uav which overcomes some or all of the disadvantages associated with existing designs. in accordance with a first aspect of the invention there is provided an unmanned aerial vehicle comprising: a fuselage; and a wing comprising a central wing section pivotably mounted to the fuselage and a pair of outer wing sections pivotably mounted to the central wing section; wherein the wing has: a folded configuration in which the central wing section and the outer wing sections are stacked on top of one another and are aligned with a longitudinal axis of the fuselage; and a deployed configuration in which the central wing section is substantially perpendicular to the fuselage and the outer wing sections extend from the central wing section away from the fuselage. the unmanned aerial vehicle may further comprise a second pair of outer wing sections pivotably mounted to the first pair of outer wing sections. at least one of the outer wing sections may move vertically during a transition from the folded configuration to the deployed configuration such that the outer wing sections are aligned with one another when in the deployed configuration. the outer wing sections may move vertically during a transition from the folded configuration to the deployed configuration such that the outer wing sections are aligned with one another and the central wing section when in the deployed configuration. the outer wing elements may be angled relative to the central wing section when in the deployed configuration such that the wing has a dihedral or anhedral angle. the wing may be biased towards the deployed configuration. the central wing section may be biased by means of a torsion spring. the fuselage may comprise a stop which limits rotation of the central wing section relative to the fuselage. each of the outer wing sections may be biased by means of a tension spring. the tension spring may be connected at one end to the central wing section and at the other end to the outer wing section via a pulley such that rotation of the outer wing section relative to the central wing section extends the tension spring. the unmanned aerial vehicle may further comprise a latch which holds the wing in the folded configuration against the bias and which is released so as to allow the wing to be deployed. the latch may be released remotely or automatically (e.g. immediately after launch or after a fixed time from launch). the vehicle may housed within a tube which retains the wing in the folded configuration. the wing may be unfolded into the deployed configuration when released from within the tube. for a better understanding of the invention, and to show more clearly how it may be carried into effect, reference will now be made, by way of example, to the accompanying drawings showing a uav with foldable wings, in which:- figure 1 is a perspective view of a uav according to an embodiment of the invention; figure 2 is a perspective view showing the outer wing pivoting mechanism; figure 3 is a perspective view showing a central wing pivoting mechanism within the fuselage; and figure 4 is a front view of the uav with the wings in a retracted position. figure 1 shows a uav 2 according to an embodiment of the invention. the uav 2 generally comprises a fuselage 4 on which is mounted a wing 6. as shown, the fuselage 4 comprises a semicylindrical front section 8 and a cylindrical rear section 10. at least part of the fuselage 4 may be hollow so as to house the electronics and the engine of the uav 2. the wing 6 is mounted to the front section 8 of the fuselage midway along the length of the front section 8. the wing 6 comprises a central wing section 12 and first and second outer wing sections 14a, 14b. the central wing section 12 and the outer wing sections 14a, 14b each have an aerofoil profile to provide lift to the uav 2. the outer wing sections 14a, 14b are also provided with ailerons 16 to allow for control of the uav 2. the central wing section 12 is pivotably connected at its centre to the front section 8 of the fuselage 4. in turn, the outer wing sections 14a, 14b are pivotably connected to the central wing section 12. specifically, the first outer wing section 14a is connected via one of its ends to the central wing section 12 at or near a distal, free end of the central wing section 12. similarly, the second outer wing section 14b is connected via one of its ends to the central wing section 12 at or near an opposing distal, free end of the central wing section 12. in particular, as shown in figure 2 , the outer wing sections 14a, 14b are each provided with a shaft 18 which projects from an underside of the outer wing section 14a, 14b. the shaft 18 is received by a bearing 20 located within the central wing section 12 which allows for rotation of the outer wing section 14a, 14b relative to the central wing section 12. the shaft 18 is connected to a bias mechanism located within the central wing section 12. the bias mechanism comprises a tension spring 22 which is fixed at one end to a bracket 24 located within the central wing section 12. the other end of the tension spring 22 is coupled to a pulley disposed on the shaft 18 via a string 26 (see figure 4 ). accordingly, rotation of the shaft 18 causes the tension spring 22 to be extended and thus placed under tension. as shown in figure 3 , the central wing section 12 comprises a shaft which extends into the interior of the front section 8 of the fuselage 4 where it passes through a boss 28. the free end of the shaft located within the front section 8 of the fuselage 4 is connected to a mount 30 which in turn is connected to a torsion spring (not shown). the mount 30 has the form of a circular sector having a pair of radial surfaces connected by an arcuate surface. the torsion spring is attached to the mount 30 via the arcuate surface. the boss 28 has a flange 32 from which a stop 34 projects into the plane of the mount 30. the stop 34 limits rotation of the mount 30 (through contact with one of the radial surfaces of the mount 30) and thus of the central wing section 12. as described previously, the central wing section 12 is pivotably connected to the fuselage 4 and the outer wing sections 14a, 14b are in turn pivotably connected to the central wing section 12. as a result, the wing 6 can be folded such that the outer wing sections 14a, 14b are rotated so that they overlap with the central wing section 12 and the central wing section 12 can then be rotated so as to align its longitudinal axis with that of the fuselage 4. as shown in figure 4 , the central wing section 12 and the outer wing sections 14a, 14b are thus stacked on top of one another. to allow this, the outer wing sections 14a, 14b are offset vertically from the central wing section 12 by different distances, at least when in the folded configuration. the pivotable connection between the outer wing sections 14a, 14b and the central wing section 12 may be arranged such that the outer wing sections 14a, 14b are vertically level with one another when deployed. the outer wing sections 14a, 14b may also be level with the central wing section 12 when in the deployed configuration. for example, the opposing ends of the outer wing sections 14a, 14b and the central wing section 12 may be angled so as to cause the outer wing sections 14a, 14b to ride up over the central wing section 12 when folded. as shown in figure 4 , the central wing section 12 and the outer wing sections 14a, 14b combined with the semicylindrical front section 8 of the fuselage 4 occupy a substantially cylindrical domain when in the folded configuration. the torsion spring and tension spring 22 bias the central wing section 12 and the outer wing sections 14a, 14b towards the deployed configuration where they are aligned with one another and perpendicular to the longitudinal axis of the fuselage 4 (as depicted in figure 1 ). therefore, the central wing section 12 and the outer wing sections 14a, 14b must be restrained in order to retain the wing in the folded configuration. for example, the uav 2 may be housed within a tube which prevents the wing 6 from being deployed. however, once released, the wing automatically unfolds into the deployed configuration. specifically, the central wing section 12 is rotated 90° about the fuselage 4 and the outer wing sections 14a, 14b are rotated 180° relative to the central wing section 12. the unfolding of the wing 6 can thus be performed post-launch, extending in mid-air and transitioning to the flight phase. although the outer wing sections 14a, 14b have been described as being aligned with the central wing section 12 when in the deployed configuration, they may instead be swept backward. the wing 6 may be arranged so as to provide a dihedral or anhedral angle with respect to the fuselage 4. this may increase stability in sideslip conditions. this may be created by the central wing section 12 or from the outer wing sections 14a, 14b. in particular, the outer wing sections 14a, 14b may be deflected upwards (dihedral) or downwards (anhedral) as they pivot relative to the central wing section 12, such that they are parallel with the central wing section 12 when folded and angled when deployed. in other embodiments, the wing 6 may comprise additional wing sections in order to increase the length of the wing 6 relative to the folded dimensions of the uav 2. although the fuselage 4 has been described as comprising a semicylindrical front section 8 and a cylindrical rear section 10, it will be appreciated that the shape of the fuselage 4 may vary. in particular, the cross-section of the fuselage 4 may be constant (i.e. the same shape and/or dimensions) along its entire length. it also need not be curved. the uav 2 may therefore be stored and/or deployed within a non-circular housing. the unfolding of the wing 6 need not be automatic and may instead be triggered electronically, either by timing after launch or by a remote user. for example, the uav 2 may comprise a latch which fixes the wing 6 in the folded configuration against the bias of the torsion spring and tension spring 22, and is released to allow the wing 6 to unfold. further, the wing 6 may be deployed using any power source and is not limited to the use of springs. in particular, the wing 6 may be actuated using solenoids, gas springs, pyrotechnics, electric motors, etc. the deployment of the wing 6 may also be initiated through aerodynamic or inertial forces. the wing 6 may have an aerofoil cross-section only over part of its length. in particular, only a portion of the central wing section 12 may have an aerofoil cross-section and outer wing sections 14a, 14b the invention is not limited to the embodiments described herein, and may be modified or adapted without departing from the scope of the present invention.
|
076-368-217-953-172
|
US
|
[
"US"
] |
G05B19/042,F24F11/08,H04N5/44,G05B15/02,H04L12/28,H04L29/06,H04N21/41,H04N21/4227,H04N21/475
| 2015-12-31T00:00:00 |
2015
|
[
"G05",
"F24",
"H04"
] |
methods and systems for control of home automation activity based on user characteristics
|
the present technology relates to systems and methods for control of home automation activity based on user preferences. more specifically, the present technology relates to using a home automation system to control home automation activity based on user preferences. example embodiments include receiving an input from a user including a set of preferences, generating a user profile using the set of preferences, receiving data indicating that a mobile device has moved from a first location to a second location, transmitting the user profile to the mobile device for application to the home automation system, receiving data indicating that the mobile device has been at the second location for a period of time, comparing the period of time to a predetermined threshold period of time, and applying the home automation settings associated with the second location to the home automation system.
|
1 . a computer-implemented method, the method comprising: receiving, at a television receiver, an input from a user including a set of preferences associated with a home automation system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. 2 . the method of claim 1 , further comprising: receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the user profile based on the data recorded by sensors in the home automation system. 3 . the method of claim 1 , further comprising: receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the threshold period of time based on the data. 4 . the method of claim 1 , wherein the data indicating that the mobile device has moved from the first location to the second location includes data corresponding to communications between the mobile device and a sensor at the first location and a sensor at the second location. 5 . the method of claim 1 , further comprising: transmitting, by the television receiver, the user profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. 6 . the method of claim 1 , further comprising: receiving updated data indicating one or more characteristics of the user; updating the user profile using the received updated data; and applying the settings of the updated user profile to the home automation system. 7 . the method of claim 1 , further comprising: identifying the user as one of a stored list of users associated with the home automation system; retrieving a stored user profile associated with the user; updating the stored user profile with the received stored user profile; and store the updated user profile. 8 . the method of claim 1 , further comprising: determining that the mobile device has moved from the first location to the second location using the data indicating that the mobile device has moved from the first location to the second location; wherein determining a location of the mobile device includes using one or more devices of the home automation system, wherein the one or more devices includes a video camera, a microphone, or a motion detector. 9 . the method of claim 1 , further comprising: receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device. 10 . a television receiver, comprising: one or more processors; a wireless transceiver communicatively coupled to the one or more processors; a non-transitory computer readable storage medium communicatively coupled to the one or more processors, wherein the non-transitory computer readable storage medium includes instructions that, when executed by the one or more processors, cause the one or more processors to perform operations including: receiving, at a television receiver, an input from a user including a set of preferences associated with a home automation system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. 11 . the television receiver of claim 10 , wherein the operations further include: receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the user profile based on the data recorded by sensors in the home automation system. 12 . the television receiver of claim 10 , wherein the operations further include: receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the threshold period of time based on the data. 13 . the television receiver of claim 10 , wherein the data indicating that the mobile device has moved from the first location to the second location includes data corresponding to communications between the mobile device and a sensor at the first location and a sensor at the second location. 14 . the television receiver of claim 10 , wherein the operations further include: transmitting, by the television receiver, the user profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. 15 . the television receiver of claim 10 , wherein the operations further include: receiving updated data indicating one or more characteristics of the user; updating the user profile using the received updated data; and applying the settings of the updated user profile to the home automation system. 16 . the television receiver of claim 10 , wherein the operations further include: identifying the user as one of a stored list of users associated with the home automation system; retrieving a stored user profile associated with the user; updating the stored user profile with the received stored user profile; and store the updated user profile. 17 . the television receiver of claim 10 , wherein the operations further include: determining that the mobile device has moved from the first location to the second location using the data indicating that the mobile device has moved from the first location to the second location; wherein determining a location of the mobile device includes using one or more devices of the home automation system, wherein the one or more devices includes a video camera, a microphone, or a motion detector. 18 . the television receiver of claim 10 , wherein the operations further include: receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device. 19 . a non-transitory computer readable medium comprising instructions that, when executed by one or more processors, cause the one or more processors to perform operations including: receiving, at a television receiver, an input from a user including a set of preferences associated with a home automation system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. 20 . the non-transitory computer readable medium of claim 19 , wherein detecting the wireless signal further includes: receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device.
|
technical field the present technology relates to systems and methods for control of home automation activity based on user preferences. more specifically, the present technology relates to using a home automation system to control home automation activity based on user preferences. background home automation systems provide a plethora of valuable benefits. from monitoring ongoing activities to securing the home, these systems can be configured to monitor many activities. however, valuable resources can be wasted based on home automation devices being used when they are not necessary. furthermore, limited resources can be used inefficiently based on a lack of data being shared between network devices within the home automation system. thus, there is a need for improved methods and systems for control of home automation activity based on user preferences and other data. these and other needs are addressed by the present technology. summary embodiments of the present technology are directed to a computer-implemented method. the method may include receiving, by a television receiver connected to a home automation system, an input from a user including a set of preferences associated with an hvac system connected to the home automation system in a structure; assigning, by the television receiver, a weight to each of two or more hvac sensors of the hvac system using the received set of preferences, wherein the hvac sensors are each distributed in different rooms of the structure; generating, by the television receiver, an hvac profile using the set of preferences and the weights assigned to the hvac sensors, wherein the hvac profile includes settings associated with proportions of conditioned air to be distributed to a plurality of rooms of the structure; transmitting, by the television receiver, the hvac profile to the hvac system, wherein when the hvac profile is received, the hvac profile is used to run the hvac system; receiving, at the television receiver, hvac data recorded by the hvac sensors, wherein the hvac data includes temperature data recorded in the different rooms over a period of time; updating, by the television receiver, the hvac profile using the received hvac data and the set of preferences; and transmitting, by the television receiver, the updated hvac profile, wherein when the updated hvac profile is received, at least a portion of the updated hvac profile is displayable on a television display device. in alternative aspects, the method further comprises transmitting, by the television receiver, the updated hvac profile to the hvac system, wherein when the updated hvac profile is received, the updated hvac profile is used to run the hvac system instead of the hvac profile. in alternative aspects, transmitting the updated hvac profile for display and transmitting the updated hvac profile to the hvac system are included in one transmission. in alternative aspects, the method further comprises transmitting, by the television receiver, the updated hvac profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, upon transmitting the hvac profile to the hvac sensors, the hvac profile causes the hvac sensors to adjust based on the settings. in alternative aspects, the user inputs the preferences into a television receiver of a satellite television distribution system. in alternative aspects, the weight of the two or more hvac sensors include at least one of a percentage and a ranking. in alternative aspects, the method further comprises determining a room of the structure where the user is located; and setting a temperature at a room hvac sensor in the room using the hvac profile. in alternative aspects, the method further comprises detecting, by the room hvac sensor, a change in temperature in the room; detecting that the change in temperature is greater than a predetermined threshold change; and transmitting a communication to an hvac device to adjust the temperature in the room. alternative embodiments of the present technology are directed to a television receiver, comprising one or more processors, a wireless transceiver communicatively coupled to the one or more processors, and a non-transitory computer readable storage medium communicatively coupled to the one or more processors, wherein the non-transitory computer readable storage medium includes instructions that, when executed by the one or more processors, cause the one or more processors to perform operations. the operations may include receiving, by a television receiver connected to a home automation system, an input from a user including a set of preferences associated with an hvac system connected to the home automation system in a structure; assigning, by the television receiver, a weight to each of two or more hvac sensors of the hvac system using the received set of preferences, wherein the hvac sensors are each distributed in different rooms of the structure; generating, by the television receiver, an hvac profile using the set of preferences and the weights assigned to the hvac sensors, wherein the hvac profile includes settings associated with proportions of conditioned air to be distributed to a plurality of rooms of the structure; transmitting, by the television receiver, the hvac profile to the hvac system, wherein when the hvac profile is received, the hvac profile is used to run the hvac system; receiving, at the television receiver, hvac data recorded by the hvac sensors, wherein the hvac data includes temperature data recorded in the different rooms over a period of time; updating, by the television receiver, the hvac profile using the received hvac data and the set of preferences; and transmitting, by the television receiver, the updated hvac profile, wherein when the updated hvac profile is received, at least a portion of the updated hvac profile is displayable on a television display device. in alternative aspects, the operations further include transmitting, by the television receiver, the updated hvac profile to the hvac system, wherein when the updated hvac profile is received, the updated hvac profile is used to run the hvac system instead of the hvac profile. in alternative aspects, transmitting the updated hvac profile for display and transmitting the updated hvac profile to the hvac system are included in one transmission. in alternative aspects, the operations further include transmitting, by the television receiver, the updated hvac profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, upon transmitting the hvac profile to the hvac sensors, the hvac profile causes the hvac sensors to adjust based on the settings. in alternative aspects, the user inputs the preferences into a television receiver of a satellite television distribution system. in alternative aspects, the weight of the two or more hvac sensors include at least one of a percentage and a ranking. in alternative aspects, the operations further include determining a room of the structure where the user is located; and setting a temperature at a room hvac sensor in the room using the hvac profile. in alternative aspects, the operations further include detecting, by the room hvac sensor, a change in temperature in the room; detecting that the change in temperature is greater than a predetermined threshold change; and transmitting a communication to an hvac device to adjust the temperature in the room. alternative embodiments of the present technology are directed to a non-transitory computer readable medium comprising instructions that, when executed by one or more processors, cause the one or more processors to perform operations. the operations may include receiving, by a television receiver connected to a home automation system, an input from a user including a set of preferences associated with an hvac system connected to the home automation system in a structure; assigning, by the television receiver, a weight to each of two or more hvac sensors of the hvac system using the received set of preferences, wherein the hvac sensors are each distributed in different rooms of the structure; generating, by the television receiver, an hvac profile using the set of preferences and the weights assigned to the hvac sensors, wherein the hvac profile includes settings associated with proportions of conditioned air to be distributed to a plurality of rooms of the structure; transmitting, by the television receiver, the hvac profile to the hvac system, wherein when the hvac profile is received, the hvac profile is used to run the hvac system; receiving, at the television receiver, hvac data recorded by the hvac sensors, wherein the hvac data includes temperature data recorded in the different rooms over a period of time; updating, by the television receiver, the hvac profile using the received hvac data and the set of preferences; and transmitting, by the television receiver, the updated hvac profile, wherein when the updated hvac profile is received, at least a portion of the updated hvac profile is displayable on a television display device. in alternative aspects, the operations further include transmitting, by the television receiver, the updated hvac profile to the hvac system, wherein when the updated hvac profile is received, the updated hvac profile is used to run the hvac system instead of the hvac profile. in alternative aspects, transmitting the updated hvac profile for display and transmitting the updated hvac profile to the hvac system are included in one transmission. in alternative aspects, the operations further include transmitting, by the television receiver, the updated hvac profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, upon transmitting the hvac profile to the hvac sensors, the hvac profile causes the hvac sensors to adjust based on the settings. in alternative aspects, the user inputs the preferences into a television receiver of a satellite television distribution system. in alternative aspects, the weight of the two or more hvac sensors include at least one of a percentage and a ranking. in alternative aspects, the operations further include determining a room of the structure where the user is located; and setting a temperature at a room hvac sensor in the room using the hvac profile. in alternative aspects, the operations further include detecting, by the room hvac sensor, a change in temperature in the room; detecting that the change in temperature is greater than a predetermined threshold change; and transmitting a communication to an hvac device to adjust the temperature in the room. embodiments of the present technology are directed to a computer-implemented method. the method may include receiving, at a television receiver of a satellite distribution system, an input from a user including a set of preferences associated with a home automation system connected to the satellite distribution system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. in alternative aspects, the method further comprises receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the user profile based on the data recorded by sensors in the home automation system. in alternative aspects, the method further comprises receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the threshold period of time based on the data. in alternative aspects, the data indicating that the mobile device has moved from the first location to the second location includes data corresponding to communications between the mobile device and a sensor at the first location and a sensor at the second location. in alternative aspects, the method further comprise transmitting, by the television receiver, the user profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, the method further comprises receiving updated data indicating one or more characteristics of the user; updating the user profile using the received updated data; and applying the settings of the updated user profile to the home automation system. in alternative aspects, the method further comprises identifying the user as one of a stored list of users associated with the home automation system; retrieving a stored user profile associated with the user; updating the stored user profile with the received stored user profile; and store the updated user profile. in alternative aspects, the method further comprises determining that the mobile device has moved from the first location to the second location using the data indicating that the mobile device has moved from the first location to the second location, wherein determining a location of the mobile device includes using one or more devices of the home automation system, wherein the one or more devices includes a video camera, a microphone, or a motion detector. in alternative aspects, the method further comprises receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device. alternative embodiments of the present technology are directed to a television receiver, comprising one or more processors, a wireless transceiver communicatively coupled to the one or more processors, and a non-transitory computer readable storage medium communicatively coupled to the one or more processors, wherein the non-transitory computer readable storage medium includes instructions that, when executed by the one or more processors, cause the one or more processors to perform operations. the operations may include receiving, at a television receiver of a satellite distribution system, an input from a user including a set of preferences associated with a home automation system connected to the satellite distribution system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. in alternative aspects, operations further include receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the user profile based on the data recorded by sensors in the home automation system. in alternative aspects, operations further include receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the threshold period of time based on the data. in alternative aspects, the data indicating that the mobile device has moved from the first location to the second location includes data corresponding to communications between the mobile device and a sensor at the first location and a sensor at the second location. in alternative aspects, operations further include transmitting, by the television receiver, the user profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, operations further include receiving updated data indicating one or more characteristics of the user; updating the user profile using the received updated data; and applying the settings of the updated user profile to the home automation system. in alternative aspects, operations further include identifying the user as one of a stored list of users associated with the home automation system; retrieving a stored user profile associated with the user; updating the stored user profile with the received stored user profile; and store the updated user profile. in alternative aspects, operations further include determining that the mobile device has moved from the first location to the second location using the data indicating that the mobile device has moved from the first location to the second location, wherein determining a location of the mobile device includes using one or more devices of the home automation system, wherein the one or more devices includes a video camera, a microphone, or a motion detector. in alternative aspects, operations further include receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device. alternative embodiments of the present technology are directed to a non-transitory computer readable medium comprising instructions that, when executed by one or more processors, cause the one or more processors to perform operations. the operations may include receiving, at a television receiver of a satellite distribution system, an input from a user including a set of preferences associated with a home automation system connected to the satellite distribution system; generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location; receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location; transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system; receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time; comparing, by the television receiver, the period of time to a predetermined threshold period of time; and in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. in alternative aspects, operations further include receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the user profile based on the data recorded by sensors in the home automation system. in alternative aspects, operations further include receiving, at the television receiver, data recorded by sensors in the home automation system; and updating the threshold period of time based on the data. in alternative aspects, the data indicating that the mobile device has moved from the first location to the second location includes data corresponding to communications between the mobile device and a sensor at the first location and a sensor at the second location. in alternative aspects, operations further include transmitting, by the television receiver, the user profile to a second television receiver, wherein the television receiver and second television receiver are connected to two different networks and are located in two different structures. in alternative aspects, operations further include receiving updated data indicating one or more characteristics of the user; updating the user profile using the received updated data; and applying the settings of the updated user profile to the home automation system. in alternative aspects, operations further include identifying the user as one of a stored list of users associated with the home automation system; retrieving a stored user profile associated with the user; updating the stored user profile with the received stored user profile; and store the updated user profile. in alternative aspects, operations further include determining that the mobile device has moved from the first location to the second location using the data indicating that the mobile device has moved from the first location to the second location, wherein determining a location of the mobile device includes using one or more devices of the home automation system, wherein the one or more devices includes a video camera, a microphone, or a motion detector. in alternative aspects, operations further include receiving data associated with a home automation device in a room of a structure, wherein the home automation device is part of the home automation system and the home automation system is in the structure; determining that the data associated with a home automation device in the room is associated with the user; and determining a location of the user in the room using the data associated with a home automation device. alternative embodiments of the present technology are directed to a computer-implemented method, a television receiver, comprising one or more processors, a wireless transceiver communicatively coupled to the one or more processors, and a non-transitory computer readable storage medium communicatively coupled to the one or more processors, wherein the non-transitory computer readable storage medium includes instructions that, when executed by the one or more processors, cause the one or more processors to perform operations, and/or a non-transitory computer readable medium comprising instructions that, when executed by one or more processors, cause the one or more processors to perform operations. the method and/or operations may include receiving data from a sensor in a home automation system, the data associated with a user; determining, using the data, a location of the user, the location including an indication of a distance between the user and a structure; comparing the distance with a predetermined threshold distance; determining an amount of time for which the user has crossed the threshold distance; comparing the amount of time to a threshold amount of time; and activating a change in a home security system associated with the home automation system based on the user crossing the threshold amount of time. brief description of the drawings a further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings. fig. 1 shows a simplified media service system that may be used in accordance with embodiments of the present technology. fig. 2 illustrates an exemplary electronic device that may be used in accordance with embodiments of the present technology. fig. 3 illustrates an exemplary home automation system setup in accordance with embodiments of the present technology. fig. 4 illustrates an embodiment of a home automation system in accordance with embodiments of the present technology. fig. 5 illustrates an embodiment of a home automation engine using various communication paths to communicate with one or more mobile devices in accordance with embodiments of the present technology. fig. 6 illustrates an embodiment of a mobile device executing an application that monitors various communication paths in accordance with embodiments of the present technology. fig. 7 illustrates a structure that includes a dwelling and an hvac system connected to the dwelling, according to embodiments of the present technology. fig. 8 illustrates a block diagram of a system that includes an hvac system integrated into a home automation network, according to embodiments of the present technology. figs. 9a and 9b show tables that include weight and ranking data associated with each of four sensors, each located in a different room of a dwelling, according to embodiments of the present technology. figs. 9c and 9d show tables that include weight and energy data associated with each of four sensors, each located in a different room of a dwelling, according to embodiments of the present technology. fig. 10 illustrates a structure that includes a dwelling, according to embodiments of the present technology. fig. 11 illustrates a block diagram of a system that includes a home automation network of home automation devices and sensors, according to embodiments of the present technology. figs. 12a-12b illustrate tables including data collected by sensors and used within a home automation system, according to embodiments of the present technology. fig. 13 illustrates a structure that includes a dwelling with a home automation system, according to embodiments of the present technology. fig. 14 illustrates a table including example stored data used within a home automation system, according to embodiments of the present technology. fig. 15 is a flow chart of an example process used to control a home automation system based on a user's location, according to embodiments of the present technology. fig. 16 is a flow chart of another example process used to control a home automation system based on a user's location, according to embodiments of the present technology. fig. 17 is a flow chart of another example process used to control a home automation system based on a user's location, according to embodiments of the present technology. fig. 18 shows a simplified computer system that may be utilized to perform one or more of the operations discussed. in the appended figures, similar components and/or features may have the same numerical reference label. further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components and/or features. if only the first numerical reference label is used in the specification, the description is applicable to any one of the similar components and/or features having the same first numerical reference label irrespective of the letter suffix. detailed description a television receiver may serve as a host for a home automation system. by using a television receiver to host a home automation system, various advantages may be realized. many of these advantages are discussed below with respect to figs. 1-18 . fig. 1 illustrates an embodiment of a satellite television distribution system 100 . while a home automation system may be incorporated with various types of television receivers, various embodiments may be part of a satellite-based television distribution system. cable, ip-based, wireless, and broadcast focused systems are also possible. satellite television distribution system 100 may include: television service provider system 110 , satellite transmitter equipment 120 , satellites 130 , satellite dish 140 , television receiver 150 , home automation service server 112 , and display device 160 . the display device 160 can be controlled by a user 153 using a remote control device 155 that can send wired or wireless signals 157 to communicate with the stb 150 and/or display device 160 . alternate embodiments of satellite television distribution system 100 may include fewer or greater numbers of components. while only one satellite dish 140 , television receiver 150 , and display device 160 (collectively referred to as “user equipment”) are illustrated, it should be understood that multiple (e.g., tens, thousands, millions of) instances and types of user equipment may receive data and television signals from television service provider system 110 via satellites 130 . television service provider system 110 and satellite transmitter equipment 120 may be operated by a television service provider. a television service provider may distribute television channels, on-demand programming, programming information, and/or other content/services to users. television service provider system 110 may receive feeds of one or more television channels and content from various sources. such television channels may include multiple television channels that contain at least some of the same content (e.g., network affiliates). to distribute television channels for presentation to users, feeds of the television channels may be relayed to user equipment via multiple television distribution satellites. each satellite may relay multiple transponder streams. satellite transmitter equipment 120 may be used to transmit a feed of one or more television channels from television service provider system 110 to one or more satellites 130 . while a single television service provider system 110 and satellite transmitter equipment 120 are illustrated as part of satellite television distribution system 100 , it should be understood that multiple instances of transmitter equipment may be used, possibly scattered geographically, to communicate with satellites 130 . such multiple instances of satellite transmitting equipment may communicate with the same or with different satellites. different television channels may be transmitted to satellites 130 from different instances of transmitting equipment. for instance, a different satellite dish of satellite transmitter equipment 120 may be used for communication with satellites in different orbital slots. satellites 130 may be configured to receive signals, such as streams of television channels, from one or more satellite uplinks such as satellite transmitter equipment 120 . satellites 130 may relay received signals from satellite transmitter equipment 120 (and/or other satellite transmitter equipment) to multiple instances of user equipment via transponder streams. different frequencies may be used for uplink signals 170 from downlink signals 180 . satellites 130 may be in geosynchronous orbit. each of the transponder streams transmitted by satellites 130 may contain multiple television channels transmitted as packetized data. for example, a single transponder stream may be a serial digital packet stream containing multiple television channels. therefore, packets for multiple television channels may be interspersed. further, information used by television receiver 150 for home automation functions may also be relayed to a television receiver via one or more transponder streams. multiple satellites 130 may be used to relay television channels from television service provider system 110 to satellite dish 140 . different television channels may be carried using different satellites. different television channels may also be carried using different transponders of the same satellite; thus, such television channels may be transmitted at different frequencies and/or different frequency ranges. as an example, a first and second television channel may be relayed via a first transponder of satellite 130 a . a third, fourth, and fifth television channel may be relayed via a different satellite or a different transponder of the same satellite relaying the transponder stream at a different frequency. a transponder stream transmitted by a particular transponder of a particular satellite may include a finite number of television channels, such as seven. accordingly, if many television channels are to be made available for viewing and recording, multiple transponder streams may be necessary to transmit all of the television channels to the instances of user equipment. satellite dish 140 may be a piece of user equipment that is used to receive transponder streams from one or more satellites, such as satellites 130 . satellite dish 140 may be provided to a subscriber for use on a subscription basis to receive television channels provided by the television service provider system 110 , satellite transmitter equipment 120 , and/or satellites 130 . satellite dish 140 , which may include one or more low noise blocks (lnbs), may be configured to receive transponder streams from multiple satellites and/or multiple transponders of the same satellite. satellite dish 140 may be configured to receive television channels via transponder streams on multiple frequencies. based on the characteristics of television receiver 150 and/or satellite dish 140 , it may only be possible to capture transponder streams from a limited number of transponders concurrently. for example, a tuner of television receiver 150 may only be able to tune to a single transponder stream from a transponder of a single satellite at a given time. the tuner can then be re-tuned to another transponder of the same or a different satellite. a television receiver 150 having multiple tuners may allow for multiple transponder streams to be received at the same time. in communication with satellite dish 140 may be one or more television receivers. television receivers may be configured to decode signals received from satellites 130 via satellite dish 140 for output and presentation via a display device, such as display device 160 . a television receiver may be incorporated as part of a television or may be part of a separate device, commonly referred to as a set-top box (stb). television receiver 150 may decode signals received via satellite dish 140 and provide an output to display device 160 . on-demand content, such as ppv content, may be stored to a computer-readable storage medium. a television receiver is defined to include set-top boxes (stbs), and also circuitry having similar functionality that may be incorporated with another device. for instance, circuitry similar to that of a television receiver may be incorporated as part of a television. as such, while fig. 1 illustrates an embodiment of television receiver 150 as separate from display device 160 , it should be understood that, in other embodiments, similar functions may be performed by a television receiver integrated with display device 160 . television receiver 150 may include home automation engine 211 , as detailed in relation to fig. 2 . display device 160 may be used to present video and/or audio decoded and output by television receiver 150 . television receiver 150 may also output a display of one or more interfaces to display device 160 , such as an electronic programming guide (epg). in many embodiments, display device 160 is a television. display device 160 may also be a monitor, computer, or some other device configured to display video and, possibly, play audio. uplink signal 170 a represents a signal between satellite transmitter equipment 120 and satellite 130 a . uplink signal 170 b represents a signal between satellite transmitter equipment 120 and satellite 130 b . each of uplink signals 170 may contain streams of one or more different television channels. for example, uplink signal 170 a may contain a first group of television channels, while uplink signal 170 b contains a second group of television channels. each of these television channels may be scrambled such that unauthorized persons are prevented from accessing the television channels. downlink signal 180 a represents a signal between satellite 130 a and satellite dish 140 . downlink signal 180 b represents a signal between satellite 130 b and satellite dish 140 . each of downlink signals 180 may contain one or more different television channels, which may be at least partially scrambled. a downlink signal may be in the form of a transponder stream. a single transponder stream may be tuned to at a given time by a tuner of a television receiver. for example, downlink signal 180 a may be a first transponder stream containing a first group of television channels, while downlink signal 180 b may be a second transponder stream containing a different group of television channels. in addition to or instead of containing television channels, a transponder stream can be used to transmit on-demand content to television receivers, including ppv content, which may be stored locally by the television receiver until output for presentation. fig. 1 illustrates downlink signal 180 a and downlink signal 180 b , being received by satellite dish 140 and distributed to television receiver 150 . for a first group of television channels, satellite dish 140 may receive downlink signal 180 a and for a second group of channels, downlink signal 180 b may be received. television receiver 150 may decode the received transponder streams. as such, depending on which television channels are desired to be presented or stored, various transponder streams from various satellites may be received, descrambled, and decoded by television receiver 150 . network 190 , which may include the internet, may allow for bidirectional communication between television receiver 150 and television service provider system 110 , such as for home automation related services provided by home automation service server 112 . although illustrated as part of the television service provider system, the home automation service server 112 may be provided by a third party in embodiments. in addition or in alternate to network 190 , a telephone, e.g., landline, or cellular connection may be used to enable communication between television receiver 150 and television service provider system 110 . fig. 2 illustrates an embodiment of a television receiver 200 , which may represent television receiver 150 of fig. 1 . television receiver 200 may be configured to function as a host for a home automation system either alone or in conjunction with a communication device. television receiver 200 may be in the form of a separate device configured to be connected with a display device, such as a television. embodiments of television receiver 200 can include set top boxes (stbs). in addition to being in the form of an stb, a television receiver may be incorporated as part of another device, such as a television, other form of display device, video game console, computer, mobile phone or tablet, or the like. for example, a television may have an integrated television receiver, which does not involve an external stb being coupled with the television. television receiver 200 may be incorporated as part of a television, such as display device 160 of fig. 1 . television receiver 200 may include: processors 210 , which may include control processor 210 a , tuning management processor 210 b , and possibly additional processors, tuners 215 , network interface 220 , non-transitory computer-readable storage medium 225 , electronic programming guide (epg) database 230 , television interface 235 , digital video recorder (dvr) database 245 , which may include provider-managed television programming storage and/or user-defined television programming, on-demand programming database 227 , home automation settings database 247 , home automation script database 248 , remote control interface 250 , security device 260 , and/or descrambling engine 265 . in other embodiments of television receiver 200 , fewer or greater numbers of components may be present. it should be understood that the various components of television receiver 200 may be implemented using hardware, firmware, software, and/or some combination thereof. functionality of components may be combined; for example, functions of descrambling engine 265 may be performed by tuning management processor 210 b . further, functionality of components may be spread among additional components. processors 210 may include one or more specialized and/or general-purpose processors configured to perform processes such as tuning to a particular channel, accessing and displaying epg information from epg database 230 , and/or receiving and processing input from a user. it should be understood that the functions performed by various modules of fig. 2 may be performed using one or more processors. as such, for example, functions of descrambling engine 265 may be performed by control processor 210 a. control processor 210 a may communicate with tuning management processor 210 b . control processor 210 a may control the recording of television channels based on timers stored in dvr database 245 . control processor 210 a may also provide commands to tuning management processor 210 b when recording of a television channel is to cease. in addition to providing commands relating to the recording of television channels, control processor 210 a may provide commands to tuning management processor 210 b that indicate television channels to be output to decoder module 233 for output to a display device. control processor 210 a may also communicate with network interface 220 and remote control interface 250 . control processor 210 a may handle incoming data from network interface 220 and remote control interface 250 . additionally, control processor 210 a may be configured to output data via network interface 220 . control processor 210 a may include home automation engine 211 . home automation engine 211 may permit television receiver and control processor 210 a to provide home automation functionality. home automation engine 211 may have a json (javascript object notation) command interpreter or some other form of command interpreter that is configured to communicate with wireless devices via network interface 220 and a message server, possibly via a message server client. such a command interpreter of home automation engine 211 may also communicate via a local area network with devices without using the internet. home automation engine 211 may contain multiple controllers specific to different protocols; for instance, a zigbee® controller, a z-wave® controller, and/or an ip camera controller, wireless lan, 802.11, may be present. home automation engine 211 may contain a media server configured to serve streaming audio and/or video to remote devices on a local area network or the internet. television receiver may be able to serve such devices with recorded content, live content, and/or content recorded using one or more home automation devices, such as cameras. tuners 215 may include one or more tuners used to tune to transponders that include broadcasts of one or more television channels. such tuners may be used also to receive for storage on-demand content and/or addressable television commercials. in some embodiments, two, three, or more than three tuners may be present, such as four, six, or eight tuners. each tuner contained in tuners 215 may be capable of receiving and processing a single transponder stream from a satellite transponder or from a cable network at a given time. as such, a single tuner may tune to a single transponder stream at a given time. if tuners 215 include multiple tuners, one tuner may be used to tune to a television channel on a first transponder stream for display using a television, while another tuner may be used to tune to a television channel on a second transponder for recording and viewing at some other time. if multiple television channels transmitted on the same transponder stream are desired, a single tuner of tuners 215 may be used to receive the signal containing the multiple television channels for presentation and/or recording. tuners 215 may receive commands from tuning management processor 210 b . such commands may instruct tuners 215 to which frequencies are to be tuned. network interface 220 may be used to communicate via an alternate communication channel with a television service provider, if such communication channel is available. a communication channel may be via satellite, which may be unidirectional to television receiver 200 , and the alternate communication channel, which may be bidirectional, may be via a network, such as the internet. data may be transmitted from television receiver 200 to a television service provider system and from the television service provider system to television receiver 200 . information may be transmitted and/or received via network interface 220 . for instance, instructions from a television service provider may also be received via network interface 220 , if connected with the internet. besides the primary communication channel being satellite, cable network, an ip-based network, or broadcast network may be used. network interface 220 may permit wireless communication with one or more types of networks, including using home automation network protocols and wireless network protocols. also, wired networks may be connected to and communicated with via network interface 220 . device interface 221 may represent a usb port or some other form of communication port that permits communication with a communication device as will be explained further below. storage medium 225 may represent one or more non-transitory computer-readable storage mediums. storage medium 225 may include memory and/or a hard drive. storage medium 225 may be used to store information received from one or more satellites and/or information received via network interface 220 . storage medium 225 may store information related to on-demand programming database 227 , epg database 230 , dvr database 245 , home automation settings database 247 , and/or home automation script database 248 . recorded television programs may be stored using storage medium 225 as part of dvr database 245 . storage medium 225 may be partitioned or otherwise divided, such as into folders, such that predefined amounts of storage medium 225 are devoted to storage of television programs recorded due to user-defined timers and stored television programs recorded due to provider-defined timers. home automation settings database 247 may allow configuration settings of home automation devices and user preferences to be stored. home automation settings database 247 may store data related to various devices that have been set up to communicate with television receiver 200 . for instance, home automation settings database 247 may be configured to store information on which types of events should be indicated to users, to which users, in what order, and what communication methods should be used. for instance, an event such as an open garage may only be notified to certain wireless devices, e.g., a cellular phone associated with a parent, not a child, notification may be by a third-party notification server, email, text message, and/or phone call. in some embodiments, a second notification method may only be used if a first fails. for instance, if a notification cannot be sent to the user via a third-party notification server, an email may be sent. home automation settings database 247 may store information that allows for the configuration and control of individual home automation devices which may operate using z-wave and zigbee-specific protocols. to do so, home automation engine 211 may create a proxy for each device that allows for settings for the device to be passed through a ui, e.g., presented on a television, to allow for settings to be solicited for and collected via a user interface presented by television receiver or overlay device. the received settings may then be handled by the proxy specific to the protocol, allowing for the settings to be passed on to the appropriate device. such an arrangement may allow for settings to be collected and received via a ui of the television receiver or overlay device and passed to the appropriate home automation device and/or used for managing the appropriate home automation device. for example, a piece of exercise equipment that is enabled to interface with the home automation engine 211 , such as via device interface 221 , may be configured at the electronic device 211 in addition to on the piece of exercise equipment itself. additionally, a mobile device or application residing on a mobile device and utilized with exercise equipment may be configured in such a fashion as well for displaying received fitness information on a coupled display device. home automation script database 248 may store scripts that detail how home automation devices are to function based on various events occurring. for instance, if stored content starts being played back by television receiver 200 , lights in the vicinity of display device 160 may be dimmed and shades may be lowered by communicatively coupled and controlled shade controller. as another example, when a user shuts programming off late in the evening, there may be an assumption the user is going to bed. therefore, the user may configure television receiver 200 to lock all doors via a lock controller, shut the garage door via garage controller, lower a heat setting of thermostat, shut off all lights via a light controller, and determine if any windows or doors are open via window sensors and door sensors, and, if so, alert the user. such scripts or programs may be predefined by the home automation/television service provider and/or may be defined by a user. in some embodiments, home automation script database 248 may allow for various music profiles to be implemented. for instance, based on home automation settings within a structure, appropriate music may be played. for instance, when a piece of exercise equipment is connected or is used, energizing music may be played. conversely, based on the music being played, settings of home automation devices may be determined. if television programming, such as a movie, is output for playback by television receiver 150 , a particular home automation script may be used to adjust home automation settings, e.g., lower lights, raise temperature, and lock doors. epg database 230 may store information related to television channels and the timing of programs appearing on such television channels. epg database 230 may be stored using storage medium 225 , which may be a hard drive or solid-state drive. information from epg database 230 may be used to inform users of what television channels or programs are popular and/or provide recommendations to the user. information from epg database 230 may provide the user with a visual interface displayed by a television that allows a user to browse and select television channels and/or television programs for viewing and/or recording. information used to populate epg database 230 may be received via network interface 220 , via satellite, or some other communication link with a television service provider, e.g., a cable network. updates to epg database 230 may be received periodically. epg database 230 may serve as an interface for a user to control dvr functions of television receiver 200 , and/or to enable viewing and/or recording of multiple television channels simultaneously. epg database 240 may also contain information about on-demand content or any other form of accessible content. decoder module 233 may serve to convert encoded video and audio into a format suitable for output to a display device. for instance, decoder module 233 may receive mpeg video and audio from storage medium 225 or descrambling engine 265 to be output to a television. mpeg video and audio from storage medium 225 may have been recorded to dvr database 245 as part of a previously-recorded television program. decoder module 233 may convert the mpeg video and audio into a format appropriate to be displayed by a television or other form of display device and audio into a format appropriate to be output from speakers, respectively. decoder module 233 may have the ability to convert a finite number of television channel streams received from storage medium 225 or descrambling engine 265 , simultaneously. for instance, decoders within decoder module 233 may be able to only decode a single television channel at a time. decoder module 233 may have various numbers of decoders. television interface 235 may serve to output a signal to a television or another form of display device in a proper format for display of video and playback of audio. as such, television interface 235 may output one or more television channels, stored television programming from storage medium 225 , e.g., television programs from dvr database 245 , television programs from on-demand programming 230 and/or information from epg database 230 , to a television for presentation. television interface 235 may also serve to output a customized video mosaic (cvm). digital video recorder (dvr) functionality may permit a television channel to be recorded for a period of time. dvr functionality of television receiver 200 may be managed by control processor 210 a . control processor 210 a may coordinate the television channel, start time, and stop time of when recording of a television channel is to occur. dvr database 245 may store information related to the recording of television channels. dvr database 245 may store timers that are used by control processor 210 a to determine when a television channel should be tuned to and its programs recorded to dvr database 245 of storage medium 225 . in some embodiments, a limited amount of storage medium 225 may be devoted to dvr database 245 . timers may be set by the television service provider and/or one or more users of television receiver 200 . dvr database 245 may also be used to record recordings of service provider-defined television channels. for each day, an array of files may be created. for example, based on provider-defined timers, a file may be created for each recorded television channel for a day. for example, if four television channels are recorded from 6-10 pm on a given day, four files may be created; one for each television channel. within each file, one or more television programs may be present. the service provider may define the television channels, the dates, and the time periods for which the television channels are recorded for the provider-defined timers. the provider-defined timers may be transmitted to television receiver 200 via the television provider's network. for example, in a satellite-based television service provider system, data necessary to create the provider-defined timers at television receiver 150 may be received via satellite. on-demand programming database 227 may store additional television programming. on-demand programming database 227 may include television programming that was not recorded to storage medium 225 via a timer, either user- or provider-defined. rather, on-demand programming may be programming provided to the television receiver directly for storage by the television receiver and for later presentation to one or more users. on-demand programming may not be user-selected. as such, the television programming stored to on-demand programming database 227 may be the same for each television receiver of a television service provider. on-demand programming database 227 may include pay-per-view (ppv) programming that a user must pay and/or use an amount of credits to view. for instance, on-demand programming database 227 may include movies that are not available for purchase or rental yet. referring back to tuners 215 , television channels received via satellite or cable may contain at least some scrambled data. packets of audio and video may be scrambled to prevent unauthorized users, e.g., nonsubscribers, from receiving television programming without paying the television service provider. when a tuner of tuners 215 is receiving data from a particular transponder of a satellite, the transponder stream may be a series of data packets corresponding to multiple television channels. each data packet may contain a packet identifier (pid), which can be determined to be associated with a particular television channel. particular data packets, referred to as entitlement control messages (ecms), may be periodically transmitted. ecms may be associated with another pid and may be encrypted; television receiver 200 may use decryption engine 261 of security device 260 to decrypt ecms. decryption of an ecm may only be possible if the user has authorization to access the particular television channel associated with the ecm. when an ecm is determined to correspond to a television channel being stored and/or displayed, the ecm may be provided to security device 260 for decryption. when security device 260 receives an encrypted ecm, security device 260 may decrypt the ecm to obtain some number of control words. in some embodiments, from each ecm received by security device 260 , two control words are obtained. in some embodiments, when security device 260 receives an ecm, it compares the ecm to the previously received ecm. if the two ecms match, the second ecm is not decrypted because the same control words would be obtained. in other embodiments, each ecm received by security device 260 is decrypted; however, if a second ecm matches a first ecm, the outputted control words will match; thus, effectively, the second ecm does not affect the control words output by security device 260 . security device 260 may be permanently part of television receiver 200 or may be configured to be inserted and removed from television receiver 200 , such as a smart card, cable card, or the like. tuning management processor 210 b may be in communication with tuners 215 and control processor 210 a . tuning management processor 210 b may be configured to receive commands from control processor 210 a . such commands may indicate when to start/stop receiving and/or recording of a television channel and/or when to start/stop causing a television channel to be output to a television. tuning management processor 210 b may control tuners 215 . tuning management processor 210 b may provide commands to tuners 215 that instruct the tuners which satellite, transponder, and/or frequency to tune to. from tuners 215 , tuning management processor 210 b may receive transponder streams of packetized data. descrambling engine 265 may use the control words output by security device 260 in order to descramble video and/or audio corresponding to television channels for storage and/or presentation. video and/or audio data contained in the transponder data stream received by tuners 215 may be scrambled. video and/or audio data may be descrambled by descrambling engine 265 using a particular control word. which control word output by security device 260 to be used for successful descrambling may be indicated by a scramble control identifier present within the data packet containing the scrambled video or audio. descrambled video and/or audio may be output by descrambling engine 265 to storage medium 225 for storage, in dvr database 245 , and/or to decoder module 233 for output to a television or other presentation equipment via television interface 235 . in some embodiments, the television receiver 200 may be configured to periodically reboot in order to install software updates downloaded over the network 190 or satellites 130 . such reboots may occur for example during the night when the users are likely asleep and not watching television. if the system utilizes a single processing module to provide television receiving and home automation functionality, then the security functions may be temporarily deactivated. in order to increase the security of the system, the television receiver 200 may be configured to reboot at random times during the night in order to allow for installation of updates. thus, an intruder is less likely to guess the time when the system is rebooting. in some embodiments, the television receiver 200 may include multiple processing modules for providing different functionality, such as television receiving functionality and home automation, such that an update to one module does not necessitate reboot of the whole system. in other embodiments, multiple processing modules may be made available as a primary and a backup during any installation or update procedures. for simplicity, television receiver 200 of fig. 2 has been reduced to a block diagram; commonly known parts, such as a power supply, have been omitted. further, some routing between the various modules of television receiver 200 has been illustrated. such illustrations are for exemplary purposes only. the state of two modules not being directly or indirectly connected does not indicate the modules cannot communicate. rather, connections between modules of the television receiver 200 are intended only to indicate possible common data routing. it should be understood that the modules of television receiver 200 may be combined into a fewer number of modules or divided into a greater number of modules. further, the components of television receiver 200 may be part of another device, such as built into a television. television receiver 200 may include one or more instances of various computerized components. while the television receiver 200 has been illustrated as a satellite-based television receiver, it is to be appreciated that techniques below may be implemented in other types of television receiving devices, such a cable receivers, terrestrial receivers, iptv receivers or the like. in some embodiments, the television receiver 200 may be configured as a hybrid receiving device, capable of receiving content from disparate communication networks, such as satellite and terrestrial television broadcasts. in some embodiments, the tuners may be in the form of network interfaces capable of receiving content from designated network locations. the home automation functions of television receiver 200 may be performed by an overlay device. if such an overlay device is used, television programming functions may still be provided by a television receiver that is not used to provide home automation functions. fig. 3 illustrates an embodiment of a home automation system 300 hosted by a television receiver. television receiver 350 may be configured to receive television programming from a satellite-based television service provider; in other embodiments other forms of television service provider networks may be used, such as an ip-based network (e.g., fiber network), a cable based network, a wireless broadcast-based network, etc. television receiver 350 may be configured to communicate with multiple in-home home automation devices. the devices with which television receiver 350 communicates may use different communication standards. for instance, one or more devices may use a zigbee® communication protocol while one or more other devices communicate with the television receiver using a z-wave® communication protocol. other forms of wireless communication may be used by devices and the television receiver. for instance, television receiver 350 and one or more devices may be configured to communicate using a wireless local area network, which may use a communication protocol such as ieee 802.11. in some embodiments, a separate device may be connected with television receiver 350 to enable communication with home automation devices. for instance, communication device 352 may be attached to television receiver 350 . communication device 352 may be in the form of a dongle. communication device 352 may be configured to allow for zigbee®, z-wave®, and/or other forms of wireless communication. the communication device may connect with television receiver 350 via a usb port or via some other type of (wired) communication port. communication device 352 may be powered by the television receiver or may be separately coupled with a power source. in some embodiments, television receiver 350 may be enabled to communicate with a local wireless network and may use communication device 352 in order to communicate with devices that use a zigbee® communication protocol, z-wave® communication protocol, and/or some other home wireless communication protocols. communication device 352 may also serve to allow additional components to be connected with television receiver 350 . for instance, communication device 352 may include additional audio/video inputs (e.g., hdmi), a component, and/or a composite input to allow for additional devices (e.g., blu-ray players) to be connected with television receiver 350 . such connection may allow video from such additional devices to be overlaid with home automation information. whether home automation information is overlaid onto video may be triggered based on a user's press of a remote control button. regardless of whether television receiver 350 uses communication device 352 to communicate with home automation devices, television receiver 350 may be configured to output home automation information for presentation to a user via display device 360 , which may be a television, monitor, or other form of device capable of presenting visual information. such information may be presented simultaneously with television programming received by television receiver 350 . television receiver 350 may also, at a given time, output only television programming or only home automation information based on a user's preference. the user may be able to provide input to television receiver 350 to control the home automation system hosted by television receiver 350 or by overlay device 351 , as detailed below. in some embodiments, television receiver 350 may not be used as a host for a home automation system. rather, a separate device may be coupled with television receiver 350 that allows for home automation information to be presented to a user via display device 360 . this separate device may be coupled with television receiver 350 . in some embodiments, the separate device is referred to as overlay device 351 . overlay device 351 may be configured to overlay information, such as home automation information, onto a signal to be visually presented via display device 360 , such as a television. in some embodiments, overlay device 351 may be coupled between television receiver 350 , which may be in the form of a set top box, and display device 360 , which may be a television. in such embodiments, television receiver 350 may receive, decode, descramble, decrypt, store, and/or output television programming. television receiver 350 may output a signal, such as in the form of an hdmi signal. rather than be directly input to display device 360 , the output of television receiver 350 may be input to overlay device 351 . overlay device 351 may receive the video and/or audio output from television receiver 350 . overlay device 351 may add additional information to the video and/or audio signal received from television receiver 350 . the modified video and/or audio signal may be output to display device 360 for presentation. in some embodiments, overlay device 351 has an hdmi input and an hdmi output, with the hdmi output being connected to display device 360 . to be clear, while fig. 3 illustrates lines illustrating communication between television receiver 350 and various devices, it should be understood that such communication may exist, in addition or alternatively via communication device 352 and/or with overlay device 351 . in some embodiments, television receiver 350 may be used to provide home automation functionality but overlay device 351 may be used to present information via display device 360 . it should be understood that the home automation functionality detailed herein in relation to a television receiver may alternatively be provided via overlay device 351 . in some embodiments, overlay device 351 may provide home automation functionality and be used to present information via display device 360 . using overlay device 351 to present automation information via display device 360 may have additional benefits. for instance, multiple devices may provide input video to overlay device 351 . for instance, television receiver 350 may provide television programming to overlay device 351 , a dvd/blu-ray player may provide video overlay device 351 , and a separate internet-tv device may stream other programming to overlay device 351 . regardless of the source of the video/audio, overlay device 351 may output video and/or audio that has been modified to include home automation information and output to display device 360 . as such, in such embodiments, regardless of the source of video/audio, overlay device 351 may modify the audio/video to include home automation information and, possibly, solicit for user input. for instance, in some embodiments, overlay device 351 may have four video inputs (e.g., four hdmi inputs) and a single video output (e.g., an hdmi output). in other embodiments, such overlay functionality may be part of television receiver 350 . as such, a separate device, such as a blu-ray player, may be connected with a video input of television receiver 350 , thus allowing television receiver 350 to overlay home automation information when content from the blu-ray player is being output to display device 360 . regardless of whether television receiver 350 is itself configured to provide home automation functionality and output home automation input for display via display device 360 or such home automation functionality is provided via overlay device 351 , home automation information may be presented by display device 360 while television programming is also being presented by display device 360 . for instance, home automation information may be overlaid or may replace a portion of television programming (e.g., broadcast content, stored content, on-demand content, etc.) presented via display device 360 . television receiver 350 or overlay device 351 may be configured to communicate with one or more wireless devices, such as wireless device 316 . wireless device 316 may represent a tablet computer, cellular phone, laptop computer, remote computer, or some other device through which a user may desire to control home automation settings and view home automation information. such a device also need not be wireless, such as a desktop computer. television receiver 350 , communication device 352 , or overlay device 351 may communicate directly with wireless device 316 , or may use a local wireless network, such as network 370 . wireless device 316 may be remotely located and not connected with a same local wireless network. via the internet, television receiver 350 or overlay device 351 may be configured to transmit a notification to wireless device 316 regarding home automation information. for instance, in some embodiments, a third-party notification server system, such as the notification server system operated by apple®, may be used to send such notifications to wireless device 316 . in some embodiments, a location of wireless device 316 may be monitored. for instance, if wireless device 316 is a cellular phone, when its position indicates it has neared a door, the door may be unlocked. a user may be able to define which home automation functions are controlled based on a position of wireless device 316 . other functions could include opening and/or closing a garage door, adjusting temperature settings, turning on and/or off lights, opening and/or closing shades, etc. such location-based control may also take into account the detection of motion via one or more motion sensors that are integrated into other home automation devices and/or stand-alone motion sensors in communication with television receiver 350 . in some embodiments, little to no setup of network 370 may be necessary to permit television receiver 350 to stream data out to the internet. for instance, television receiver 350 and network 370 may be configured, via a service such as sling® or other video streaming service, to allow for video to be streamed from television receiver 350 to devices accessible via the internet. such streaming capabilities may be “piggybacked” to allow for home automation data to be streamed to devices accessible via the internet. for example, u.s. patent application ser. no. 12/645,870, filed on dec. 23, 2009, entitled “systems and methods for remotely controlling a media server via a network”, which is hereby incorporated by reference, describes one such system for allowing remote access and control of a local device. u.s. pat. no. 8,171,148, filed apr. 17, 2009, entitled “systems and methods for establishing connections between devices communicating over a network”, which is hereby incorporated by reference, describes a system for establishing connection between devices over a network. u.s. patent application ser. no. 12/619,192, filed may 19, 2011, entitled “systems and methods for delivering messages over a network”, which is hereby incorporated by reference, describes a message server that provides messages to clients located behind a firewall. wireless device 316 may serve as an input device for television receiver 350 . for instance, wireless device 316 may be a tablet computer that allows text to be typed by a user and provided to television receiver 350 . such an arrangement may be useful for text messaging, group chat sessions, or any other form of text-based communication. other types of input may be received for the television receiver from a tablet computer or other device, such as lighting commands, security alarm settings and door lock commands. while wireless device 316 may be used as the input device for typing text, television receiver 350 may output for display text to display device 360 . in some embodiments, a cellular modem 353 may be connected with either overlay device 351 or television receiver 350 . cellular modem 353 may be useful if a local wireless network is not available. for instance, cellular modem 353 may permit access to the internet and/or communication with a television service provider. communication with a television service provider may also occur via a local wireless or wired network connected with the internet. in some embodiments, information for home automation purposes may be transmitted by a television service provider system to television receiver 350 or overlay device 351 via the television service provider's distribution network. various home automation devices may be in communication with television receiver 350 or overlay device 351 . such home automation devices may use disparate communication protocols. such home automation devices may communicate with television receiver 350 directly or via communication device 352 . such home automation devices may be controlled by a user and/or have a status viewed by a user via display device 360 and/or wireless device 316 . home automation devices may include: smoke/carbon monoxide detector, home security system 307 , pet door/feeder 311 , camera 312 , window sensor 309 , irrigation controller 332 , weather sensor 306 , shade controller 304 , utility monitor 302 , heath sensor 314 , intercom 318 , light controller 320 , thermostat 322 , leak detection sensor 324 , appliance controller 326 , garage door controller 328 , doorbell sensor 323 , and voip controller 325 . door sensor 308 and lock controller 330 may be incorporated into a single device, such as a door lock or sensor unit, and may allow for a door's position (e.g., open or closed) to be determined and for a lock's state to be determined and changed. door sensor 308 may transmit data to television receiver 350 (possibly via communication device 352 ) or overlay device 351 that indicates the status of a window or door, respectively. such status may indicate open or closed. when a status change occurs, the user may be notified as such via wireless device 316 or display device 360 . further, a user may be able to view a status screen to view the status of one or more door sensors throughout the location. window sensor 309 and/or door sensor 308 may have integrated glass break sensors to determine if glass has been broken. lock controller 330 may permit a door to be locked and unlocked and/or monitored by a user via television receiver 350 or overlay device 351 . a mechanical or electrical component may need to be integrated separately into a door or door frame to provide such functionality. such a single device may have a single power source that allows for sensing of the lock position, sensing of the door position, and for engagement and disengagement of the lock. additional forms of sensors not illustrated in fig. 3 may also be incorporated as part of a home automation system. for instance, a mailbox sensor may be attached to a mailbox to determine when mail is present and/or has been picked up. the ability to control one or more showers, baths, and/or faucets from television receiver 350 and/or wireless device 316 may also be possible. pool and/or hot tub monitors may be incorporated into a home automation system. such sensors may detect whether or not a pump is running, water temperature, ph level, a splash/whether something has fallen in, etc. further, various characteristics of the pool and/or hot tub may be controlled via the home automation system. in some embodiments, a vehicle dashcam may upload or otherwise make video/audio available to television receiver 350 when within range. for instance, when a vehicle has been parked within range of a local wireless network with which television receiver 350 is connected, video and/or audio may be transmitted from the dashcam to the television receiver for storage and/or uploading to a remote server. to be clear, the home automation functions detailed herein that are attributed to television receiver 350 may alternatively or additionally be incorporated into overlay device 351 or some separate computerized home automation host system. fig. 4 shows an embodiment of a system for home monitoring and control that includes a television receiver 450 . the system 400 may include a television receiver that is directly or indirectly coupled to one or more display devices 460 such as a television or a monitor. the television receiver may be communicatively coupled to other display and notification devices 461 such as stereo systems, speakers, lights, mobile phones, tablets, and the like. the television receiver may be configured to receive readings from one or more sensors 442 , 448 , or sensor systems 446 and may be configured to provide signals for controlling one or more control units 443 , 447 or control systems 446 . in embodiments the television receiver may include a monitoring and control module 440 , 441 and may be directly or indirectly connected or coupled to one or more sensors and/or control units. sensors and control units may be wired or wirelessly coupled with the television receiver. the sensors and control units may be coupled and connected in a serial, parallel, star, hierarchical, and/or the like topologies and may communicate to the television receiver via one or more serial, bus, or wireless protocols and technologies which may include, for example, wifi, can bus, bluetooth, i2c bus, zigbee, z-wave and/or the like. the system may include one or more monitoring and control modules 440 , 441 that are external to the television receiver 450 . the television receiver may interface to sensors and control units via one or more of the monitoring and control modules. the external monitoring and control modules 440 , 441 may be wired or wirelessly coupled with the television receiver. in some embodiments, the monitoring and control modules may connect to the television receiver via a communication port such as a usb port, serial port, and/or the like, or may connect to the television receiver via a wireless communication protocol such as wi-fi, bluetooth, z-wave, zigbee, and the like. the external monitoring and control modules may be a separate device that may be positioned near the television receiver or may be in a different location, remote from the television receiver. in embodiments, the monitoring and control modules 440 , 441 may provide protocol, communication, and interface support for each sensor and/or control unit of the system. the monitoring and control module may receive and transmit readings and provide a low level interface for controlling and/or monitoring the sensors and/or control units. the readings processed by the monitoring and control modules 440 , 441 may be used by the other elements of the television receiver. for example, in some embodiments the readings from the monitoring and control modules may be logged and analyzed by the data processing and storage 422 module. the data processing and storage 422 module may analyze the received data and generate control signals, schedules, and/or sequences for controlling the control units. additionally, the data processing and storage module 422 may utilize input data to generate additional outputs. for example, the module 422 may receive from a sensor 442 information from a communicatively coupled piece of equipment. the sensor may be a part of or attached to the equipment in various embodiments. the equipment may provide information regarding movements, alarms, or notifications associated with the home, and the data processing module 422 may use this data to generate relative distance information to be output to and displayed by display device 460 . in some embodiments, the monitoring and control modules 440 , 441 may be configured to receive and/or send digital signals and commands to the sensors and control units. the monitoring and control modules may be configured to receive and/or send analog signals and commands to the sensors and control units. sensors and control units may be wired or wirelessly coupled to the monitoring and control modules 440 , 441 or directly or indirectly coupled with the receiver 450 itself. the sensors and control units may be coupled and connected in a serial, parallel, star, hierarchical, and/or the like topologies and may communicate to the monitoring and control modules via one or more serial, bus, or wireless protocols and technologies. the sensors may include any number of temperature, humidity, sound, proximity, field, electromagnetic, magnetic sensors, cameras, infrared detectors, motion sensors, pressure sensors, smoke sensors, fire sensors, water sensors, and/or the like. the sensors may also be part of or attached to other pieces of equipment, such as exercise equipment, doors or windows, or home appliances, or may be applications or other sensors as part of mobile devices. the monitoring and control modules 440 , 441 may be coupled with one or more control units. the control units may include any number of switches, solenoids, solid state devices and/or the like for making noise, turning on/off electronics, heating and cooling elements, controlling appliances, hvac systems, lights, and/or the like. for example, a control unit may be a device that plugs into an electrical outlet of a home. other devices, such as an appliance, may be plugged into the device. the device may be controlled remotely to enable or disable electricity to flow to the appliance. a control unit may also be part of an appliance, heating or cooling system, and/or other electric or electronic devices. in embodiments the control units of other system may be controlled via a communication or control interface of the system. for example, the water heater temperature setting may be configurable and/or controlled via a communication interface of the water heater or home furnace. additionally, received telephone calls may be answered or pushed to voicemail in embodiments. the controllers, e.g., controller 443 , may include a remote control designed for association with the television receiver. for example, the receiver remote control device may be communicatively coupled with the television receiver, such as through interface 250 , or one or more of the monitoring and control modules for providing control or instruction for operation of the various devices of the system. the control may be utilized to provide instructions to the receiver for providing various functions with the automation system including suspending alert notifications during an event. for example, a user may determine prior to or during an event that he wishes to suspend one or more types of notifications until the event has ended, and may so instruct the system with the controller. sensors may be part of other devices and/or systems. for example, sensors may be part of a mobile device such as a phone. the telemetry readings of the sensors may be accessed through a wireless communication interface such as a bluetooth connection from the phone. as another example, temperature sensors may be part of a heating and ventilation system of a home. the readings of the sensors may be accessed via a communication interface of the heating and ventilation system. sensors and/or control units may be combined into assemblies or units with multiple sensing capabilities and/or control capabilities. a single module may include, for example a temperature sensor and humidity sensor. another module may include a light sensor and power or control unit and so on. in embodiments, the sensors and control units may be configurable or adjustable. in some cases the sensors and control units may be configurable or adjustable for specific applications. the sensors and control units may be adjustable by mechanical or manual means. in some cases the sensors and control units may be electronically adjustable from commands or instructions sent to the sensors or control units. for example, the focal length of a camera may be configurable in some embodiments. the focal length of a camera may be dependent on the application of the camera. in some embodiments the focal length may be manually set or adjusted by moving or rotating a lens. in some embodiments the focal length may be adjusted via commands that cause an actuator to move one or more lenses to change the focal length. in other embodiments, the sensitivity, response, position, spectrum and/or like of the sensors may be adjustable. during operation of the system 400 , readings from the sensors may be collected, stored, and/or analyzed in the television receiver 450 . in embodiments, analysis of the sensors and control of the control units may be determined by configuration data 424 stored in the television receiver 450 . the configuration data may define how the sensor data is collected, how often, what periods of time, what accuracy is required, and other characteristics. the configuration data may specify specific sensor and/or control unit settings for a monitoring and/or control application. the configuration data may define how the sensor readings are processed and/or analyzed. for example, for some applications, sensor analysis may include collecting sensor readings and performing time based analysis to determine trends, such as temperature fluctuations in a typical day or energy usage. such trending information may be developed by the receiver into charts or graphs for display to the user. for other applications, sensor analysis may include monitoring sensor readings to determine if a threshold value of one or more sensors has been reached. the function of the system may be determined by loading and/or identifying configuration data for an application. in embodiments, the system 400 may be configured for more than one monitoring or control operation by selecting or loading the appropriate configuration data. in some embodiments the same sensors and/or control units may be used for multiple applications depending on the configuration data used to process and analyze sensor readings and/or activate the control units. multiple monitoring and/or control applications may be active simultaneously or in a time multiplexed manner using the same or similar set of sensors and/or control units. for example, the system 400 may be configured for both exercise monitoring and temperature monitoring applications using the same set of sensors. in embodiments, both monitoring applications may be active simultaneously or in a time multiplexed manner depending on which configuration data is loaded. in both monitoring applications the same sensors, such as proximity sensors, or cameras may be used. using the same sensors, the system may be configured for space temperature monitoring. for temperature monitoring, the system may only monitor a specific subset of the sensors for activity. for temperature monitoring, sensor activity may not need to be saved or recorded. the sensor readings may be monitored for specific thresholds which may indicate a threshold temperature for adjusting the space temperature. in this example, the two different monitoring examples may be selected based on the active configuration data. when one configuration data is active, data from the sensors may be saved and analyzed. when the second configuration data is active, the system may monitor sensor readings for specific thresholds. of course, multiple or alternative sensors may be used as well. in embodiments, the results, status, analysis, and configuration data details for each application may be communicated to a user. in embodiments, auditory, visual, and tactile communication methods may be used. in some cases a display device such as a television may be used for display and audio purposes. the display device may show information related to the monitoring and control application. statistics, status, configuration data, and other elements may be shown. users may also save particular configuration data for devices, such as notification suspensions while the user is using the coupled display. a user may log in or be recognized by the system upon activation and the system may make adjustments based on predetermined or recorded configuration data. for example, a user may have instructed that when he is recognized by the system, either automatically or with provided login information, a notification suspension profile personal to the user be enacted. that profile may include that the user would like to continue to receive alarms, such as smoke, fire, or hazard alarms, but that received telephone call information is suspended. the user may access the profile and select to begin, the user may be recognized by the system, or a combination such as being recognized by the system such that the television operations are performed or are input by a remote control, while the user himself selects a particular activity to perform with the system. any number of additional adjustments or operations may be performed as well, as would be understood as encompassed by the present technology. for example, the space temperature may be monitored or adjusted as well. in one situation, after the user has been exercising for a period of time, generated heat may raise the space temperature above a threshold such that the home automation engine 211 additionally begins operation or adjustment of the hvac system to cool the space. additionally, configuration data for the user may include reducing the space temperature to a particular degree based on a preference of the user. thus, when the user loads a profile or begins exercising, the home automation system may automatically begin adjusting the space temperature as well in anticipation of heat generation or user preferences. in embodiments, the system may include additional notification and display devices 461 capable of notifying the user, showing the status, configuration data, and/or the like. the additional notification and display devices may be devices that are directly or indirectly connected with the television receiver. in some embodiments computers, mobile devices, phones, tablets, and the like may receive information, notifications, control signals, etc., from the television receiver. data related to the monitoring and control applications and activity may be transmitted to remote devices and displayed to a user. such display devices may be used for presenting to the user interfaces that may be used to further configure or change configuration data for each application. an interface may include one or more options, selection tools, navigation tools for modifying the configuration data which in turn may change monitoring and/or control activity of an application. modification to a configuration may be used to adjust general parameters of a monitoring application to specific constraints or characteristics of a home, user's schedule, control units, and/or the like. display interfaces may be used to select and/or download new configurations for monitoring and/or control applications. a catalog of pre-defined configuration data definitions for monitoring and control applications may be available to a user. a user may select, load, and/or install the applications on the television receiver by making a selection using in part the display device. for example, a user may load a profile based on notification suspension preferences as discussed above. in embodiments, configuration data may be a separate executable application, code, package, and/or the like. in some cases, the configuration data may be a set of parameters that define computations, schedules, or options for other processor executable code or instructions. configuration data may be a meta data, text data, binary file, and/or the like. in embodiments, notification and display devices may be configured to receive periodic, scheduled, or continuous updates for one or more monitoring and control applications. the notifications may be configured to generate pop-up screens, notification banners, sounds, and/or other visual, auditory, and/or tactile alerts. in the case where the display device is a television, some notifications may be configured to cause a pop-up or banner to appear over the programming or content being displayed, such as when a proximity monitor has been triggered in the home. such an alert may be presented in a centrally located box or in a position different from the fitness information to make it more recognizable. additionally the program being watched can be paused automatically while such an alert is being presented, and may not be resumed unless receiving an input or acceptance from the user. some notifications may be configured to cause the television to turn on if it is powered off or in stand-by mode and display relevant information for a user. in this way, users can be warned of activity occurring elsewhere in the system. the television receiver may also be configured to receive broadcast or other input 462 . such input may include television channels or other information previously described that is used in conjunction with the monitoring system to produce customizable outputs. for example, a user may wish to watch a particular television channel while also receiving video information of activities occurring on the property. the television receiver may receive both the exterior camera information and television channel information to develop a modified output for display. the display may include a split screen in some way, a banner, an overlay, etc. fig. 5 illustrates an embodiment 500 of a home automation engine using various communication paths to communicate with one or more mobile devices. embodiment 500 may include: home automation engine 210 , push notification server system 521 , sms server system 522 , email server system 523 , telephone service provider network 524 , social media 525 , network 530 , and mobile devices 540 ( 540 - 1 , 540 - 2 , 540 - 3 ). home automation engine 210 may represent hardware, firmware, and/or software that are incorporated as part of the home automation host system, such as television receiver 350 , communication device 352 , or overlay device 351 of fig. 3 . home automation engine 210 may include multiple components, which may be implemented using hardware, firmware, and/or software executed by underlying computerized hardware. home automation engine 210 may include: home automation monitoring engine 511 , defined notification rules 512 , user contact database 513 , notification engine 514 , and receipt monitor engine 515 . home automation monitoring engine 511 may be configured to monitor various home automation devices for events, status updates, and/or other occurrences. home automation monitoring engine 511 may monitor information that is pushed to home automation engine 210 from various home automation devices. home automation monitoring engine 511 may additionally or alternatively query various home automation devices for information. defined notification rules 512 may represent a storage arrangement of rules that were configured by a user. such defined notification rules may indicate various states, events, and/or other occurrences on which the user desires notifications to be sent to one or more users. defined notification rules 512 , which may be stored using one or more non-transitory computer readable mediums, may allow a user to define or select a particular home automation device, an event or state of the device, a user or group of users, and/or classification of the home automation state or event. for example, table 1 presents three examples of defined notification rules which may be stored as part of defined notification rules 512 . in some embodiments, it may be possible that the service provider provides home automation engine 210 with one or more default defined home automation notification rules. a user may enable or disable such default defined notification rules and/or may be permitted to create customized notification rules for storage among defined notification rules 512 . a user may be permitted to enable and disable such defined notification rules as desired. table 1second(fallback)homegroup ofautomationrulefirst group ofusers torule namedevicetriggeractionclassificationusers to notifynotify“person atdoorbelldoorbellsendclass 1defineddefaultdoor”sensoractuationnotificationcommunity 1event[text ofnotification][codednotification]“windowwindow[windowsendclass 2custom:noneopen?”sensorstate] =notificationthomas, jeff,open[text ofjason, andrewnotification][codednotification]“door leftdoor sensor[doorsendurgentdefineddefinedajar”state] =notificationcommunities 1community 4open >30[text ofand 3secondsnotification][codednotification] in table 1, a user (or service provider) has defined a rule name, the relevant home automation device, the trigger that causes the rule to be invoked, the action to be performed in response to the rule being triggered, the classification of the rule, a first group of users to send the notification, and a second group of users to notify if communication with the first group of users fails. to create a rule, home automation engine 210 may output a user interface that walks a user through creation of the rule such as by presenting the user with various selections. as an example, a user may first type in a name for rule. next, the user may be presented with a list of home automation devices that are present in the home automation network with which home automation engine 210 is in communication. the user may then be permitted to select among triggers that are applicable to the selected home automation device, such as events and states that can occur at the selected home automation device. for instance, home automation devices such as a doorbell sensor may only have a single possible event: a doorbell actuation. however, in other home automation devices, such as garage door controller 128 may have multiple states, such as open, shut, and ajar. another possible state or event may be a low battery state or event. next, the user may select the action that the home automation engine is to perform in response to the trigger event for the home automation device occurring. for the three examples of table 1, notifications are to be sent to various groups (called “communities”) of users. in some embodiments, a user may be permitted to select a classification for each rule. the classification may designate the urgency of the rule. depending on the classification, the communication channels tried for communication with the user and/or the amount of time for which home automation engine 210 waits for a response before trying another communication channel may be controlled. the user may also define one or more groups of users that are to receive the notifications. the first group of users may include one or more users and may indicate which users are to initially receive a notification. the second group of users may remain undefined for a particular rule or may specify one or more users that are to receive the notification if the notification failed to be received by one, more than one, or all users indicated as part of the first group of users. if a particular grouping of users is to collectively receive notifications, a user may be permitted to define a “community” rather than specifying each user individually. for instance, a user may select from among available users to create “defined community 1 ,” which may include users such as: “thomas,” “nick,” and “mary.” by specifying “defined community 1 ” the user may not have to individually select these three users in association with the rule. such a use of defined communities is exemplified in table 1. user contact database 513 may specify definitions of groups of users and orderings of communication paths for individual users and/or classifications. table 2 presents an exemplary embodiment of an ordering of communication paths for particular user. table 2firstsecondthirdfourthcommuni-communi-communi-communi-cationcationcationcationuser namepathpathpathpathandrewpushsms textemail (fail)social medianotificationmessagepost (fail)jeffsms textpushvoice callemail (fail)messagenotificationjasonpushsms textemail (fail)—notificationthomassms textvoice call—— for each user, one or more communication paths are defined. for example, for the user named andrew, the first communication path is a push notification. his second communication path is an sms text message. the sms text message may be used as the communication path if a receipt response is not received in response to transmission of a push notification within a defined period of time. similarly, if the second communication path fails to yield a receipt being received by receipt monitor engine 515 after a predefined period of time, an email, which is andrew's third communication path, may be used to send the notification. entries in table 2 labeled as “fail” may be indicative of a communication path that may receive the notification but from which a receipt is not expected and is treated as a failed communication attempt. for instance, an email sent to an email address associated with andrew may go through and may be accessible by andrew the next time he accesses his email account; however, notification engine 514 may send the notification via the fourth communication path without waiting a defined period of time since a receipt is not expected to be received in response to the email. for different users, different communication paths may be ordered differently. for instance, an sms text message is defined as jeff's first communication path while an sms text message is defined as andrew's second communication path. each user via an application on his or her mobile device, or by directly interacting with the home automation host system executing home automation engine 210 , may customize which communication paths are used for their notifications and the ordering of such communication paths. for each type of communication path, a default period of time to wait for a receipt response may be defined. for instance, for push notifications, a default wait period of time may be one minute, while the default wait period of time for an sms text message may be two minutes. such wait periods of time may be tied to the classification of the rule. for instance, a classification of urgent may cause the period of time to be halved. in some embodiments, a user can customize his wait periods of time. for users, various alternate orderings of communication paths may be created based on the classification of the rule and/or whether the user is part of the first group of users or the second, fallback group of users. when home automation monitoring engine 511 determines that a rule of defined notification rules 512 has been triggered, notification engine 514 , by accessing user contact database 513 , may begin transmitting one or more notifications to one or more users using one or more communication paths. notification engine 514 may be configured to try communicating with the user via a first communication path, then waiting a defined period of time to determine if a receipt is received in response notification. if not, notification engine 514 may use user contact database 513 to determine the next communication path for use in communicating with the user. notification engine 514 may then use such a communication path to try to communicate with the user. notification engine 514 may determine when communication with a particular user has failed and, if available, a second group of users, which can be referred to as a fallback group of users, should receive a notification instead. in such an instance, notification engine 514 may then use user contact database 513 in order to communicate with the second group of users via the ordering of defined communication paths. while notification engine 514 may cause notifications to be transmitted to users via various communication paths, receipt monitor engine 515 may monitor for received receipts that are indicative of delivery of the notification. receipt monitor engine 515 may inform notification engine 514 when a notification has been received and further notifications to that user are unnecessary. receipt monitor engine 515 may cause information to be stored by home automation engine 210 indicative of the circumstances under which the notification was received. for instance, receipt monitor engine 515 may create a database entry that is indicative of the user, the time of receipt (or of viewing by the user), and the communication path that was successful in causing the notification to reach the user. illustrated in embodiment 500 are various communication paths that may be used by notification engine 514 for communicating with various users' mobile devices. these communication paths include: push notification server system 521 , sms server system 522 , email server system 523 , telephone service provider network 524 , social media 525 , and network 530 . push notification server system 521 may be a system that causes a mobile device to display a message such that the message must be actively dismissed by the user prior to or otherwise interacting with the mobile device. as such, a push notification has a high likelihood of being viewed by user since the user is required to dismiss the push notification before performing any other functions, home automation related or not, with the mobile device. sms server system 522 may cause text messages to be sent to mobile devices. typically, a mobile device provides an alert, such as a sound of flashing light or vibration to user to indicate that a new text message has been received. however, it is possible for a user to interact with a mobile device that has received a new sms text message without viewing or otherwise interacting with the text message. other forms of messaging systems may additionally or alternatively be used, such as apple's imessage service. email server system 523 may serve as an email service provider for user. an email transmitted to a user, that is sent to email server system 523 may be viewed by the user the next time the user accesses email server system 523 . in some embodiments, emails are actively pushed by email server system 523 to an application being executed by a user's mobile device, thus increasing the likelihood that a user will look at the email shortly after it has been sent. in other embodiments, a user's mobile device may be required to be triggered by the user to retrieve emails from email server system 523 , such as by executing an application associated with the email server system or by logging in to the user's email account via a web browser being executed by the mobile device. telephone service provider network 524 may permit voice calls to be performed to a mobile device. a user operating such a mobile device may answer a telephone call to hear a recorded message that is transmitted by notification engine 514 or, if the user does not answer, a voicemail may be left for the user using telephone service provider network 524 . social media 525 may represent various social media networks through which notification engine 514 can try to communicate with the user. social media may for example include: twitter®, facebook®, tumblr®, linkedin®, and/or various other social networking websites. notification engine 514 may directly transmit a message to a user via social media 525 (e.g., facebook® messenger) or may create a post to one or more social media websites via a shared or dedicated social media account that could be viewed by the user. for example, notification engine 514 may have login credentials to a twitter® account that can be used to post a message indicative of the home automation notification. if the user is following the twitter® account associated with the notification engine, the notification would be listed in the user's twitter® feed. if such posts are public (that is, available to be viewed by members of the public, such as on twitter®), the social media post may be “coded” such that it would only make sense to the user. a user, by configuring an alternate notification text at home automation engine 210 (as indicated in table 1) may assign coded words or phrases to various home automation events that would be posted to public social media. for instance the door being left ajar may be assigned: “the cat is out of the bag” is a coded message to be posted to social media, while a direct message (e.g., sms text message) would not be coded, such as: “your home's front door is ajar.” while to a member of the public, a coded notification may be nonsensical, to the user who configured the notification, the coded notification may be quickly interpreted as meaning his home's front door has been left ajar. network 530 may represent one or more public and/or private networks through which notification engine 514 and receipt monitor engine 515 may communicate with a mobile device. for instance network 530 may represent a home wireless network, such as network 170 , and/or the internet. for instance, if notification engine 514 has an ip address of mobile device 540 - 1 , it may be possible for notification engine 514 to directly transmit a notification via network 530 to mobile device 540 - 1 . additionally or alternatively, mobile device 540 - 1 may be executing an application that can communicate directly with home automation engine 210 via network 530 . home automation engine 210 and a mobile device may alternatively or additionally communicate with service provider host system 550 , which is accessible via network 530 , and serves as an intermediary for communications between home automation engine 210 and mobile device. for instance, a message to be transmitted from mobile device 540 - 1 to home automation engine 210 may be transmitted by mobile device 540 - 1 to service provider host system 550 via network 530 . home automation engine 210 may periodically query service provider host system 550 via network 530 to determine if any messages are pending for home automation engine 210 . in response to such a query, the message transmitted by mobile device 540 - 1 destined for home automation engine 210 may be retrieved by home automation engine 210 . three mobile devices are illustrated in embodiment 500 . each of such mobile devices may be associated with a different user. in embodiment 500 , such mobile devices are shown as only being available via specific communication paths. this is for example purposes only. for instance, mobile device 540 - 1 can communicate with home automation engine 210 via push notification server system 521 (which may be unidirectional to mobile device 540 - 1 ), and network 530 (such as via communications coordinated by service provider host system 550 ). mobile device 540 - 2 may, for some reason, be unable to receive push notifications sent via push notification server system 521 but may be able to send and receive sms texts via sms server system 522 . mobile device 540 - 3 may be currently unavailable via any of the illustrated communication paths. for example, based on where mobile device 540 - 3 is located, it may be unable to communicate with a wireless network that enables access to one or more of the communication paths illustrated in fig. 5 or the mobile device may be turned off. it should be understood that the communication paths, components of home automation engine 210 , and the number of mobile devices 540 are intended to represent examples. for instance, notifications may be sent to types of devices other than mobile devices. for instance, for a user, while the first notification may be sent to the user's mobile device, a second communication path may communicate with the user's desktop computer. further various components of home automation engine 210 may be divided out into a greater number of components or may be combined into fewer components. fig. 6 illustrates an embodiment of a mobile device 600 executing an application that monitors various communication paths. mobile device 600 may represent each of mobile devices 540 or some other form of mobile device that is receiving notifications from a home automation engine via various possible communication paths. mobile device 600 , which may be a cellular phone, smart phone, smart television, smart watch, smart glasses, table computer, laptop, in-dash network-enabled navigation system, or other form of a wireless and/or mobile computerized device, may execute application 601 . application 601 may be executed in the background such that when a user is not interacting with application 601 , a process of application 601 can monitor various communication paths of mobile device 600 . a user may also bring application 601 to the foreground, such that the user can view a user interface of application 601 and generally interact with application 601 . application 601 may include: push notification monitor engine 611 , sms monitor engine 612 , email monitor engine 613 , social media monitor engine 614 , voice call monitor engine 615 , presentation engine 620 , and receipt response engine 640 . such modules may be implemented using software that is executed on underlying hardware. push notification monitor engine 611 may monitor for when a push notification is received by mobile device 600 that includes a notification from notification engine 514 of home automation engine 210 . the operating system of mobile device 600 may cause the push notification to be presented by a display of mobile device 600 such that a user is required to view and dismiss the push notification before performing any other function on mobile device 600 . the push notification, when displayed, may present text of the push notification indicative of the home automation event. for instance, returning to table 1 for the “person at door” event, the corresponding [text of notification] from the event may be presented as part of the push notification. additional information may include the time at which the event occurred and a location of the home automation engine (which may be useful if the user has home automation systems installed at multiple locations, such as a primary home, office building, and vacation home). push notification monitor engine 611 may determine 1) that the push notification has been received by mobile device 600 ; and 2) if the user has dismissed the push notification. sms monitor engine 612 may monitor for when a text message is received by mobile device 600 that includes a notification from notification engine 514 of home automation engine 210 . sms monitor engine 612 may monitor for a particular string of characters that is indicative of the home automation engine 210 or the source number from which the sms text message may be indicative of the home automation engine. the operating system of mobile device 600 may cause the text message to be stored and may cause the mobile device 600 to output vibration, sound, and/or light indicative of the received text message. the user may need to select the text message for presentation or the text message may be automatically displayed by mobile device 600 . the text of the sms message may present text indicative of the home automation event. for instance, as with the push message, returning to table 1 for the “person at door” event, the corresponding [text of notification] from the event may be presented as part of the sms message. additional information may include the time at which the event occurred and a location of the home automation engine. sms monitor engine 612 may determine 1) that the sms message containing the notification has been received by mobile device 600 ; and 2) if the user has viewed the sms text containing the notification. email monitor engine 613 may monitor for when an email is received by mobile device 600 that includes a notification from notification engine 514 of home automation engine 210 . email monitor engine 613 may monitor for a particular string of characters in either the body or subject line of the email that is indicative of the home automation engine 210 or the sender from which the email was received may be indicative of the home automation engine. the email may be added to an inbox of mobile device 600 and an operating system of mobile device 600 may cause vibration, sound, and/or light to be output that is indicative of the received email. the user may need to select an email application and the email for the email to be presented by mobile device 600 . the text of the email may present text indicative of the home automation event. for instance, as with the push message and the sms text message, returning to table 1 for the “person at door” event, the corresponding [text of notification] from the event may be presented as part of the sms message. additional information may include the time at which the event occurred and a location of the home automation engine. since an email can contain significantly more information than an sms text or push notification, more details regarding the home automation event and system may be presented as part of the email. email monitor engine 613 may determine 1) that the email message containing the notification has been received by mobile device 600 ; and 2) if the user has opened the email containing the notification. social media monitor engine 614 may monitor for when a social media post is made by home automation engine 210 that is indicative of a notification. as such, social media monitor engine 614 may periodically check one or more social media feeds for posts either privately sent to a user of mobile device 600 or publically posted. social media monitor engine 614 may monitor for a particular string of characters that is indicative of the home automation engine 210 or the username or account from which the post was made which is indicative of the home automation engine. the text of the social media post may present text indicative of the home automation event. for instance, as with the push message, returning to table 1 for the “person at door” event, the corresponding [text of notification] from the event may be presented as part of the social media post. if the post is made publically, a code message may be posted instead of the [text of notification]. for instance, referring to table 1, [coded notification] may be publically posted instead of [text of notification]. additional information posted may include the time at which the event occurred and a location of the home automation engine. social media monitor engine 614 may determine 1) mobile device 600 has received the social media post (e.g., in an updated twitter® feed); and 2) if the user has viewed the social media message containing the notification or the social media feed containing the notification. voice call monitor engine 615 may monitor for when a voice call or voicemail is received by mobile device 600 that includes a notification from notification engine 514 of home automation engine 210 . voice call monitor engine 615 may monitor for a particular phone number from which the call is originating to determine that a notification from the home automation engine has been received. the operating system of mobile device 600 may cause an indication of the voice message to be presented via output vibration, sound, and/or light. the user may need to answer the call or listen to the voicemail in order to receive the notification. voice call monitor engine 615 may determine 1) whether the notification has been received; and 2) if the user has listened to the voicemail or answered the call. the voice call or voicemail may include synthesized voice that reads the notification for the home automation event. additional information may include the time at which the event occurred and a location of the home automation engine. in some embodiments, it may not be possible to monitor various communication paths. for instance, a user may have his email only accessible via a specialized application (e.g., google's® gmail™ application). as such, the user may receive the email; however, email monitor engine 613 may not be able to determine that the email has been received. during an initial configuration, home automation engine 210 may test communication paths with application 601 when it is known or expected that such communication paths are functional. such a test may determine which communication paths of application 601 will be able to acknowledge receipt of notifications. when a notification cannot be acknowledged, notification engine 514 may still use such a communication path to send a notification but may assume transmission has failed and/or may only use such a communication path as a final attempt. for instance, such communication paths are noted in table 2 with the “(fail)” designation. a user may view the push notifications, sms texts, emails, social media posts and/or messages, and (listen to) voice calls directly. additionally, when one of the monitor engines ( 611 - 615 ) notes that a notification has been received, presentation engine 620 may be triggered to present an additional or alternate indication of the notification. for instance, if the user launches application 601 (such that it is displayed and no longer only executed in the background of mobile device 600 ), presentation engine 620 may cause information regarding the notification to be presented in a user friendly format and may allow the user to perform various actions in response to the notification. for instance, if the notification is “door left ajar,” the user may have the ability to select from “view security camera feed,” “call at-home user” (which may determine, such as based on geo-positioning, a user who is within the home) and “call 911 .” receipt response engine 640 may receive information from engines 611 - 615 that is indicative of a notification being received and/or of the notification being viewed, dismissed, or heard by the user. receipt response engine 640 may generate and cause a response to be transmitted by mobile device 600 to receipt monitor engine 515 of home automation engine 210 . the receipt response may indicate the time at which the notification was received and/or viewed/heard by the user. fig. 7 illustrates a structure 700 that includes a dwelling and an hvac system connected to the dwelling, according to embodiments of the present technology. the structure 700 includes three different rooms 760 , 762 and 764 . as shown in fig. 7 , room 760 is a bedroom, room 762 is a living room, and room 764 is a dining room. the structure is connected to an hvac system that includes hvac unit 766 . hvac unit 766 is configured to deliver heating, ventilation, and air conditioning to structure 700 . the physical connection between hvac unit 766 and structure 700 is not shown in fig. 7 . however, hvac unit 766 , along with venting and/or other devices, may deliver heating, ventilation, and air conditioning to a specific one or more than one room within structure 700 . for example, the hvac system may deliver heating, ventilation, or air conditioning to room 764 and not deliver to rooms 762 or 760 (or leaving the temperature and environment in those rooms the same). such hvac devices may include one or more of the following: fans, heating, cooling, window coverings, vent coverings (e.g. smart vent coverings), space heater, among others. as noted with respect to previous figures herein, an hvac system may be incorporated into a home automation system within a structure, such as structure 700 . the home automation system may include various sensors that may be distributed around the structure, such as sensors 770 a , 770 b , 772 , and 774 . sensors 770 a , 770 b , 772 , and 774 may be, for example, temperature sensors that record temperature readings of the current temperature of the room that the sensor is located in. sensors 770 a , 770 b , 772 , and 774 may compile recordings of temperature, or of other types of data, over a period of time. the recordings may be stored locally at each sensor, or may be transmitted from the different sensors to a central location, such as to a television receiver or other home automation processing unit for storage. an hvac system typically includes one or two thermostats, and includes only one or two sensors that detect the current temperature inside the structure. the hvac system may use temperature readings from those sensors to detect whether the hvac system needs to adjust the temperature inside the structure. for example, if a sensor records a temperature of 65 degrees, and the hvac system is set to keep the temperature inside the structure at 70 degrees, then the sensor reading may trigger the hvac system to turn on or turn up the heat. furthermore, temperature across different parts of the inside of a structure (e.g. different rooms, different floors, etc.) may vary greatly. for example, the temperature in a basement may vary greatly from the temperature in an upstairs bedroom at the same time. in another example, the temperature next to a window in a room may be different than the temperature on the other side of that same room. since the inside of a structure may only include one or two sensors to detect the temperature of the rooms inside the structure, the sensors may record temperatures that are not representative of the actual temperature in certain areas of the structure. adding additional sensors around the house (e.g. one in each room) may allow for more accurate temperature readings of the temperature in each room. using the home automation system and television receiver, a user may be able to control, based on user initiated settings, how the temperature recordings are used to customize the hvac system to the user. fig. 8 illustrates a block diagram of a system that includes an hvac system integrated into a home automation network, according to embodiments of the present technology. as shown in fig. 8 , the home automation system may include various sensors, such as sensors 840 , 842 , 844 , 846 and 848 . these sensors may be a part of or connected to home automation devices, or network devices, as shown in fig. 8 . for example, such devices may include garage door opener, heating and/or air conditioning, thermostat, lights, window or door sensors, motion detectors, video cameras, among others. however, sensors may also be stand-alone devices that are not a part of home automation devices. sensors 840 - 848 may record and collect data associated with the environment that the sensors are in, for example data associated with the device that the sensor is a part of. for example, sensor 840 may collect temperature data (e.g. the temperature of the room that the sensor is in) if device 880 is a thermostat. various types of data may be collected at each sensor, depending on the type of sensor. for example, for a temperature sensor, data may be collected regarding temperature in the room over a period of time, when the air conditioning and/or heat went on or off, the rate at which temperature dropped or rose, among other types of data. in another example, for a video camera, data may be collected regarding when motion was detected, for how long the motion persisted, who or what caused the motion (e.g. using facial recognition), when the video camera was turned on or off, among others. data from sensors 840 - 848 may be transmitted to control processor 810 . similar to processor 210 a , the control processor 810 may include a home automation engine that may permit a television receiver to provide home automation functionality. for example, control processor 810 may use the data it receives from sensors 840 - 848 to control the hvac system connected to it. control processor 810 may be, or may be a part of, a television receiver, such as a stb. for example, control processor 810 may be included as part of a stb, allowing for the received data to be used as part of the satellite television distribution system, such as satellite television distribution system 100 . control processor 810 may generate a profile based on the data it receives from the home automation devices. for example, the home automation profile may be the result of analysis done on the data regarding characteristics of one or more devices in the home automation system. for example, if a home automation device detects data in a certain pattern, or detects data that is representative of a certain characteristic associated with the device, the profile may reflect such a pattern or characteristic. for example, if device 882 is a motion detector in a basement, and sensor 842 in device 882 detects motion in the basement every day between 8:10 am and 8:20 am, then the home automation profile may include such a pattern. these patterns and/or characteristics may allow the home automation system to give advance warning of an upcoming action to a user, or may allow the home automation system to take an action automatically based on the event that it assumes will take place at a given time. in another example, if device 884 is a remote control associated with a television receiver, sensor 884 may collect data to control processor 810 that shows that a user of the remote control device turns on the television receiver every evening at 9:30 pm. such a characteristic may allow the home automation system to transmit a query to a user, for example via the user's mobile device, asking whether the user would like the home automation system to turn on the television receiver at 9:30 pm on a certain night. this data may also be used as part of a user profile since the data is reflective of a user's preferences and a user's interactions with the home automation system. in addition to data automatically detected and collected by the home automation sensors, a user profile may also include information inputted by the user. for example, a user may input preferences into a user interface directed to preferences about how the user would like the home automation system, specific home automation devices, or the hvac system to function. in one example, a user may enter an input into a television receiver via a remote control device regarding the temperature that the user would like in a certain room in the user's home. as shown in fig. 8 , control processor 810 may be connected to, or communicate with, an hvac system. for example, control processor 810 may transmit data it receives and/or generates to hvac control 868 . furthermore, control processor 810 may transmit instructions to hvac control 868 that include the results of analysis or profile generation at control processor 810 . hvac control 868 may be configured to control hvac unit 866 a and alternative hvac 866 b , and therefore may use the data, profiles, etc. received from control processor 810 (e.g. from a television receiver and/or stb) to adjust how the hvac system is working. as shown in fig. 8 , hvac unit 866 a and alternative hvac 866 b may be configured to send cool air or hot air to certain rooms in a structure based on instructions received from hvac control 868 . for example, hvac unit 866 a may transmit cold air to the room that device 888 is located in because sensor 848 detected that the room was too warm based on a user profile generated by control processor 810 . as noted, a user profile may include information inputted by the user. for example, a user may input information related to home automation devices into a remote control associated with the television receiver, into a mobile device, or other user interface such that the information inputted by the user is received by control processor 810 for processing. also as noted, an hvac system may include sensors in multiple rooms or areas within a structure that are configured to record data corresponding to the environment in which the sensors are in. a user may assign a priority/ranking, or weight, to each sensor in the hvac and home automation system so that certain sensors in certain areas of the structure have a higher priority than others. for example, a priority or weight may be given to a sensor in a room that is important to the user, or for which accuracy of a given characteristic (e.g. temperature) is especially important. in a more specific example, if a user spends a significant amount of time during the day in the user's office, and device 886 with sensor 846 is located in the user's office, then the user may assign a high weight or priority to sensor 846 . figs. 9a-d illustrate tables including data collected by, for example control processor 810 (e.g. within a television receiver of a satellite television distribution system), according to embodiments of the present technology. data tables may be stored at each respective sensor at which the data is collected, at the sensor's associated device, or at a central location, such as at a television receiver. fig. 9a shows a table 900 a that includes weight data associated with each of four sensors, each located in a different room of a dwelling. the weight and/or rankings data may be inputted by a user as user preferences, for example by typing the weights into a remote control or other mobile device, upon the prompting of a user interface on a display. table 900 a shows that the user has assigned a weight of 0.15 (or 15%) to sensor 1 in the living room, a weight of 0.10 (or 10%) to sensor 2, a weight of 0.40 (or 40%) to sensor 3, and a weight of 0.35 (or 35%) to sensor 4. similarly, table 900 b in fig. 9b assigned a ranking of “3” to sensor 1 in the living room, a ranking of “4” to sensor 2, a ranking of “1” to sensor 3, and ranking of “2” to sensor 4. there are a variety of reasons why a user may have assigned these example weights to the different sensors. for example, sensor 3 may be the most important sensor of the user. in another example, sensor 3 may be a part of or connected to a device that is most important to the user. in another example, sensor 3 may be located in a room where the user spends the most of the user's time as compared to the other rooms in the home. after such weights have been inputted and assigned by the user, the television receiver (or other central processing device) may assign the given weights to the respective sensors. for example, the television receiver may store the assigned weights, and may create instructions or a user profile based on the assigned weights. weights or rankings may also be generated or adjusted automatically by the home automation system. for example, the sensors in the home automation system may detect a level of importance, or another characteristic, of the different sensors based on the data it collects. for example, the television receiver may detect that a user is located in a room with sensor 3 about 40% of the time that the user is in the dwelling, and therefore may assign the 0.40 (or 40%) weight to sensor 3. the home automation system may also make this determination based on a variety of other characteristics or factors. for example, a sensor may be given a higher weight based on the type of device it is connected to, or how much the room is used during certain designated or predetermined important times of day, days of the week, times of year, etc., among others. a user may be able to choose which characteristics or factors that the home automation system uses to automatically determine weights for the different sensors. such a choice may be provided via a display device instead of, or in addition to, the user selecting or inputting the actual weights for each sensor. the weights assigned to the different sensors in the home automation system may be used to determine which room the user wants to prioritize for use of the user's hvac system. for example, the user may designate sensor 3 with the highest priority or weight because the user wants to make sure that the temperature in the left side of the bedroom is most accurate, even at the fault or risk of inaccuracy of other rooms in the home. this may provide both a more efficient hvac and home automation system where energy is not being used in certain rooms that are less important to the user, and also tailored to the user's specific needs or desires. fig. 9c shows a table 900 c that includes weight and energy (for example, in btu/h) data associated with each of four sensors, each located in a different room of a dwelling. the weight and/or energy data may be inputted by a user as user preferences, for example by typing the weights into a remote control or other mobile device, upon the prompting of a user interface on a display. in another example, the data may be generated automatically by the home automation system and/or hvac system based on historical data collected by the sensors or a control processor or other central processing engine. table 900 c shows that the user (or the system) has assigned a weight of 0.15 (or 15%) to sensor 1 and an energy level of 15,000 btu/h, a weight of 0.10 (or 10%) to sensor 2 and an energy level of 10,000 btu/h, a weight of 0.40 (or 40%) to sensor 3 and an energy level of 40,000 btu/h, and a weight of 0.35 (or 35%) to sensor 4 and an energy level of 35,000 btu/h. table 900 c is similar to tables 900 a and 900 b except table 900 c includes a listing of amounts of energy assigned to the sensors in each of the four rooms listed in the table. in the case of table 900 c , the amount of energy for each sensor corresponds to the weight that each sensor is assigned based on a total energy output of 100,000 btu/h. for example, room 1 sensor was assigned an energy of 15,000 btu/h based on an 0.15 (15% weight), room 2 sensor was assigned an energy of 10,000 btu/h based on an 0.10 (10% weight), room 3 sensor was assigned an energy of 40,000 btu/h based on an 0.40 (40% weight), and room 4 sensor was assigned an energy of 35,000 btu/h based on an 0.35 (35% weight). the amount of weight assigned to each sensor may be chosen directly by a user, or may be automatically chosen or updated based on the weight assigned to each sensor. the amount of energy assigned to each sensor may correspond to a certain metric assigned to each sensor. for example, the amount of energy assigned to each sensor may be a target amount of energy that the user (or the system) wants to use for the hvac system to send cooling or heating, for example, to the room that the corresponding sensor is in. in another example, the amount of energy assigned to each sensor may be a maximum (or minimum) amount of energy to be used for that sensor's corresponding room. in another example, the amount of energy assigned to each sensor/room may be the average amount of energy selected to be used for that sensor's corresponding room over a certain period of time. fig. 9d shows a table 900 d that includes weight and energy (for example, in btu/h) data associated with each of four sensors, each located in a different room of a dwelling, similar to table 900 c . table 900 d also includes a column of energy data that shows the maximum amount of energy needed at a particular point in time. the weight and energy data may be inputted by a user as user preferences, for example by typing the weights into a remote control or other mobile device, upon the prompting of a user interface on a display. in another example, the data may be generated automatically by the home automation system and/or hvac system based on historical data collected by the sensors or a control processor or other central processing engine. table 900 d shows that the user or the home automation system has assigned a weight of 0.10 (or 10%) to sensor 1 and an energy level of 10,000 btu/h, a weight of 0.05 (or 5%) to sensor 2 and an energy level of 5,000 btu/h, a weight of 0.55 (or 55%) to sensor 3 and an energy level of 55,000 btu/h, and a weight of 0.35 (or 35%) to sensor 4 and an energy level of 30,000 btu/h. unlike in table 900 c , table 900 d shows that a room with the lowest priority (or one or more rooms with lower priority than others) may not receive their maximum needed energy from the hvac system because the rooms with a higher priority used all of the available energy. for example, although the maximum needed energy for room 4 to be at its assigned temperature is 45,000 btu/h. however, since rooms 1, 2 and 3 used a total of 70,000 btu/h of the available 100,000 btu/h (for example) energy, only 30,000 btu/h was available for room 4. although tables 900 a - 900 d in figs. 9a-9d show data associated with an hvac system, including energy targets and maximum needed energy, for example, similar tables may be generated by the home automation system or other systems with data associated with sensors other than those used in such an hvac system. for example, weights and/or rankings (and other data) may be inputted, generated and/or compiled for video cameras, motion sensors, gas distribution system sensors, electricity sensors, water sensors, among others. furthermore, although embodiments described herein with respect to figs. 6-9d are described with respect to different sensors being located in different rooms of a structure, the embodiments and technology described herein may be applied to different sensors in different parts of the same room. for example, for a large room, one sensor may be located at one end of the room, and a second sensor may be located at the opposite end of the room. such an example set of sensors may vary inaccuracy with respect to the readings/recordings they take when collecting data, and therefore different weights may be given to the different sensors in the same room. for example, if one sensor is close to a window and another is not close to a window, the readings taken by the sensor that is close to a window may be affected by drafts from the window. weights, rankings, or other priority systems between different sensors and/or different rooms in a structure may change throughout different times of the day, different times or days of the week, different times of year, around holidays, etc. for example, as noted, the home automation may recognize or record data and analyze that data for patterns in user or home automation system behaviors. for example, while changes in day-to-day use of the home automation system and systems connected to the home automation system may be useful for one or more users who live in the structure, different changes may be more applicable to generate profiles for other types of users. for example, a different user may only stay in the house one time every three months. however, the home automation system may still be able to detect that user's preferences over a period of time (e.g. 1 year, 2 years, 5 years, 10 years, etc.) and make changes to the home automation system based on those patterns and generated user profiles. in one embodiment, certain sensors may be grouped together. for example, a group may be generated by the home automation system, or by a user, if the system or user believes that certain sensors should have similar characteristics and/or perform actions in a similar or same way. for example, if two rooms are situated in a similar place in a house and have similar properties (e.g. temperature, etc.), then the two sensors may be grouped together. such a grouping may cause the sensors in that group to have the same priority, for example. such a grouping may cause settings or characteristics to change on one sensor if they are changed on another sensor in that group. a user may create rules that apply to one or more sensors, or to one or more groups of sensors. for example embodiment, a rule may be created in a home automation system connected to an hvac system that the user would like every sensor in the home to read at a temperature of between 70 and 72 degrees. as noted, the home automation system and/or systems connected to the home automation system (e.g. hvac) may be connected to, or be a part of, a satellite television distribution system. integrating such systems may not only be convenient for users so that such systems may be controllable from one place or one display, but combining such systems may also cause the systems themselves to be more efficient. for example, if the home automation system integrated into a television receiver detects that the television has been left on for a certain period of time that is more than a threshold period of time, where the threshold period of time is more than the user usually leaves the television on for on an average night, then the home automation system may be able to automatically turn off the television, or at least put the television into energy saver or similar mode. in other words, the technology described herein may allow for the processors and computers used to control these systems, and communicate within each system and between systems, to be more efficient and more cost effective. fig. 10 illustrates a structure 1000 that includes a dwelling, according to embodiments of the present technology. the structure 1000 includes three different rooms 1060 , 1062 and 1064 . as shown in fig. 10 , room 1060 is a bedroom on the second floor of the dwelling, room 1062 is a living room on the first floor of the dwelling, and room 1064 is a dining room on the first floor of the dwelling. as noted, various features, such as an hvac system, a home security or surveillance system, a satellite or cable television system, among others, may be incorporated into a home automation system within a structure, such as structure 1000 . the home automation system may include various sensors that may be distributed around the structure, such as sensors 1070 a , 1070 b , 1072 , and 1074 . sensors 1070 a , 1070 b , 1072 , and 1074 may record readings of certain characteristics of the sensors' environments in the rooms that the sensors are located in. sensors 1070 a , 1070 b , 1072 , and 1074 may compile recordings of data over a period of time. the recordings may be stored locally at each sensor, or may be transmitted from the different sensors to a central location, such as to a television receiver or other home automation processing unit for storage. fig. 10 illustrates the transition over time of a user 1053 between room 1062 and room 1064 . as shown in fig. 10 , user 1053 is initially located in room 1062 . user 1053 is holding a network device 1055 , such as a mobile device, that may be connected to a wireless or wired network, such a as a local area network (lan). the sensors 1060 , 1062 and/or 1064 may also be connected to the same network. since user 1053 is located in room 1062 , the mobile device 1055 that the user is holding may communicate with sensor 1072 , which is also in room 1062 . mobile device 1055 may initiate a communication with sensor 1072 , or sensor 1072 may initiate a communication with mobile device 1055 . however, either way, the communication between mobile device 1055 and sensor 1072 may be due to the fact that both mobile device 1055 and sensor 1072 are in the same room, or are otherwise within a certain (e.g. close) proximity to each other. the mobile device 1055 and sensor 1072 may communicate with each other via one or more of a variety of communication protocols, such as wifi, bluetooth, zigbee, z-wave and/or the like. the mobile device and sensor may communicate on a continuous basis, on a periodic basis (e.g. communicate once every certain amount of time), on a random basis, on an as-needed basis (as determined by either the sensor or mobile device or both), or on a different schedule, predetermined or otherwise. since, as described herein, sensor 1072 collects data regarding its environment (e.g. whatever data the sensor is configured to record and collect), sensor 1072 may be configured to record data corresponding to the mobile device 1055 (and, in turn, user 1053 ). for example, sensor 1072 may be configured to collect data directed to when mobile device 1055 is in room 1062 , or within a certain distance of sensor 1072 (e.g. if sensor 1072 is a motion detector). in another example, if sensor 1072 is a video camera with face recognition capabilities, sensor 1072 may be configured to recognize which user from a list of users is user 1053 , and present in room 1062 (and, for example, where the user is located in room 1062 . as shown in fig. 10 , user 1053 may then physically move from room 1062 to room 1064 , and may transport mobile device 1055 from room 1062 to room 1064 with the user. in such a situation, mobile device 1055 may cease communicating with sensor 1072 because mobile device 1055 is not within a certain proximity or range of sensor 1072 (e.g. mobile device 1055 is not in room 1062 , the same room as sensor 1072 any longer). instead, mobile device 1055 may begin communicating with sensor 1074 , which is located in room 1064 , because mobile device 1055 is located in room 1064 , and/or because mobile device 1055 is within a certain proximity or distance range of sensor 1074 . mobile device 1055 may communicate in the same or similar way, or otherwise have the same or similar relationship, with sensor 1074 as it did with sensor 1072 . for example, sensor 1074 may collect data regarding its environment, and may be configured to record data corresponding to the mobile device 1055 (and, in turn, user 1053 ). for example, sensor 1074 may be configured to collect data directed to when mobile device 1055 is in room 1064 , or within a certain distance of sensor 1074 . the relationship between mobile device 1055 and the one or more sensors it communicates with within structure 1000 , such as which sensor(s) the mobile device may or should communicate with, may be determined based on the location of mobile device 1055 relative to the one or more sensors. the location of mobile device 1055 may be determined in a variety of ways. for example, the location of the mobile device 1055 may be determined using a global positioning system (gps) located within the mobile device. in another example, the location of the mobile device 1055 may be determined using communications with the sensors themselves. data may be collected by the sensors regarding the location of the mobile device (e.g. how long a message from the sensor to the mobile device takes to be returned to the sensor, using timestamps sent with communications sent by the mobile device, etc.), and the sensor(s) or a device in communication with the sensor(s) may determine where the mobile device is located relative to the one or more sensors using that data (e.g. using triangulation). in another example, the location of the mobile device 1055 may be determined using capabilities of certain sensors within the home automation system. for example, a video camera may recognize the mobile device and be able to determine the distance the mobile device is away from the camera based on that recognition. the location of the mobile device 1055 , and in some example instances a user carrying the mobile device, may be used to make changes or otherwise use the home automation system in a way that is beneficial to the user. for example, as noted, a security system within structure 1000 may be connected to or a part of a home automation system. more specifically, changes may be made to a home security system based on changes detected around the home by the home security system, such as, for example, where a user is located around a home. in one example embodiment, a user of a home automation system may want to activate an associated alarm system when the user is not close enough to the main doors, windows, or other openings to monitor them. in a situation where a user within a structure is near to, for example, the main door of the structure, it may be considered unlikely for someone to break into that door to the user's proximity to that door and the user's ability to stop the break-in or to alert the authorities of such a break-in. on the other hand, in a situation where a user within a structure is far away from the main door of the structure (e.g. on a different floor and/or on the opposite end of the structure, outside the structure, etc.), it may be considered difficult for that user to be alerted by someone entering the main door due to the user's far proximity away from that door. therefore, it may be beneficial for an alarm system to activate when a user is determined to be more than a certain predetermined distance away from the door so that the user can be alerted to activity at or near the door. these and other related embodiments are discussed further with respect to figs. 13-14 . fig. 11 illustrates a block diagram 1100 of a system that includes a home automation network of home automation devices and sensors, according to embodiments of the present technology. as shown in fig. 11 , the home automation system may include various sensors, such as sensors 1140 and 1142 . these sensors may be a part of or connected to home automation devices, or network devices, such as devices 1180 and 1182 as shown in fig. 11 . for example, such devices may include garage door opener, heating and/or air conditioning, thermostat, lights, window or door sensors, motion detectors, video cameras, among others. however, sensors may also be stand-alone devices that are not a part of home automation devices. sensors 1140 and 1142 may record and collect data associated with the environment that the sensors are in, for example data associated with the device that the sensor is a part of. various types of data may be collected at each sensor, depending on the type of sensor, as described with respect to fig. 8 . data from sensors 1140 and 1142 may be transmitted to television receiver 1150 , either directly (for example, via communication paths 1191 and/or 1199 ) or via one or more mobile devices 1190 and 1192 . similar to processor 210 a in fig. 2 and control processor 810 in fig. 8 , the television receiver 1050 may include a home automation engine that may provide home automation functionality. for example, television receiver 1050 may use the data it receives from sensors 1140 and 1142 to control devices 1180 and 1182 , sensors 1140 and 1142 , or other devices and/or systems connected to the home automation network. the system may include a separate control processor (not shown) that is separate from television receiver 1150 . however, such a control processor may be included as part of a stb, allowing for the received data to be used as part of the satellite television distribution system, such as satellite television distribution system 100 shown in fig. 1 . television receiver 1150 may generate a profile based on the data it receives from the home automation devices, as described herein with respect to fig. 8 . as shown in fig. 11 , devices 1180 and 1182 and/or sensors 1140 and 1142 may communicate with mobile devices 1190 and 1192 via any of a variety of communication paths, such as communication path 1193 , 1194 , 1195 , 1196 , 1197 and/or 1198 . for example, devices 1180 and 1182 and/or sensors 1140 and 1142 may communicate with mobile devices 1190 and 1192 in order for the home automation system, and devices 1180 and 1182 in particular, to record when a user, via a user mobile device (e.g. user mobile device 1190 and/or 1192 ) are in the same room, or within a certain distance from, the devices. since the home automation network of devices may be spread out across a room or structure, the proximity of a mobile device from one or more sensors a part of or connected to a home automation device may allow the home automation network to determine where a user, that may control the mobile device, is located within the room or structure. as noted, device 1180 , device 1182 , or any other device in the home automation network, may transmit the data it collects, directed to the relative location of a mobile device or otherwise, to television receiver 1150 . television receiver 1150 may use the data collected by devices 1180 and 1182 to adjust the home automation settings, or settings directed to other systems connected to or controlled by the home automation system, based on a user's inputs or other needs. television receiver 1150 may also communicate directly with mobile devices 1190 and/or 1192 . for example, television receiver 1150 may, upon determining a change that it intends to make within the home automation system or to one or more devices within the home automation system, transmit a query to one or more mobile devices asking whether the home automation system should make the change. for example, the television receiver may transmit a query to user mobile device 1190 to ask a certain user whether to make the change or not. the home automation system may determine which mobile device or user to transmit the query based on which user it detected in a room, or based on predetermined communication settings set by the one or more users. for example, the system may be set to always transmit queries related to changes in the home automation system or a system connected to the home automation system (e.g. hvac) to one particular user. figs. 12a-12b illustrate tables including data collected by sensors and used within a home automation system, according to embodiments of the present technology. fig. 12a shows a table 1200 a of time data associated with sensors in each of four rooms (living room, dining room, bedroom, and gym). for example, the times and/or time ranges in table 1200 a may be raw data collected by sensors for when a user (e.g. associated with a mobile device) is present in a certain room. for example, table 1200 a may indicate that a user was present in room 2 on day 1 between 4:52 pm and 5:33 pm. however, table 1200 a may also include data that represents results of analysis performed on raw data compiled by sensors or data otherwise generated from the raw data. for example, the data in table 1200 a may include average data compiled over a historical period of time that represents the average times that a user is present in the rooms. in another example, the data may include data that represents a pattern (e.g. the least common denominator of a set of data) of actions taken by a user. the timing data shown in table 1200 a may be used to make changes, via the home automation system, to certain devices within a structure. for example, if a user is detected as being located in a certain room, for example room 3 (bedroom), at a certain time, then the home automation system may make changes to devices in the bedroom, or to devices in other parts of the house that may have an effect on the bedroom, based on that collected data. for example, if a user is detected as being located in the bedroom, the home automation system may change the settings on the hvac system so that the bedroom is set to a temperature that the user has selected as the user's preferred temperature. in another example, the home automation system may change the settings of one or more lights in the bedroom so that the lights are set to the user's specifications (e.g. which lights are turned on, how much the lights are dimmed, etc.). the sensors may also detect not only the presence of a user, but also which user in particular is located in a certain room or in proximity of the sensor. such information may be detected using the communications with the one or more mobile devices known to the sensor or to the home automation system. for example, if a certain mobile device is known by the home automation system as being associated with a certain user, then the home automation system may use settings associated with that user when a sensor detects or communicates with the mobile device associated with that user. examples of such settings are shown in table 1200 b in fig. 12b . furthermore, the home automation system may change the settings when a second user has entered the room. if the first user has left the room, the home automation system may use the settings associated with the second user. if the first user has not left the room, then the home automation system may use a hybrid of the settings associated with the two users based on certain rules set by the user(s), or may use the settings associated with one of the users based on a predetermined prioritization of users within the home. for example, if a sensor in room 4 (gym) detects that a first user has entered the room, and the first user likes the lights to be turned “off” when that user is working out, then the home automation system may turn (or leave) the lights off when that user enters the gym. if a second user enters the gym, and the second user's settings indicate that the second user likes the lights on while working out, then the home automation system may make a determination, based on the settings and rules within the home automation system, which settings to follow while both users are in the room. for example, a priority of users may be set by the users such that the second user is prioritized over the first user (e.g. if the second user is a parent of the first user, and the second user set the home automation system to prioritize the second user over the first user). in such a case, the home automation system would turn the lights on. the rules with the home automation system may also be tailored to the set of users on a room-by-room basis, or even on the basis of a portion of a room to a portion of a room. for example, if two sensors are located in the gym, the sensors may be able to detect the exact or close to exact location of each user in the gym. therefore, if the first user is using a treadmill in one portion of the room, and the second user is using a treadmill in a second portion of the room as detected by the sensors, then the home automation system may turn off the lights located above or near the first user, but turn the lights on located above or near the second user. the home automation system may also make other changes in the room to account for both users being in the same room. in the above example, the home automation system may automatically lower a barricade (e.g. a moving wall or door) to separate the two users in the gym so as to block light from the second user's lights from reaching the first user's lights to allow both users to enjoy their chosen settings. after one of the users leaves the gym, the settings in the gym may be adjusted to tailor the gym to the environment and settings that the user remaining in the gym would want. furthermore, the settings for the user who left the gym may “follow” the leaving user to the next room or location within the structure and be applied to the next room or location that that user is located in. the settings used in that room or location may be the same or similar settings as those used in the gym (e.g. light dimness), or may be applied to devices (e.g. lights) that are of the same or similar type as those in the gym, or the settings/devices may be completely different. in another example, if a particular user (as determined, for example, by a video camera and facial recognition software) watches the same television channel at the same day and time of the week every week, then the home automation system may determine this pattern or routine and associate that pattern with that user. the home automation system may also make home automation decisions and make changes to certain devices based on these patterns. for example, one or more rules may be set so that the television receiver is set to take certain actions based on the detected patterns. more specifically, for example, the television receiver may turn on the television display (and, for example, the stb) at the day and time that the user watches that television program, and even tune the stb to the station that the television show is on. alternatively, the television receiver may transmit a query to the user to ask the user whether the user plans to watch that television show at that day and time so that the television receiver may turn on the television display only if it is sure, based on the user's response, that the user will watch that television show at that day and time. the home automation system may also make other changes to the home automation devices in the room where the television is located that also fit within the user's settings profile. for example, the home automation system may turn the lights to a certain dimness level, may set the hvac to a certain temperature, among other changes. the settings associated with a certain user may be generated by the home automation system (e.g. television receiver or other processing device) or may be set by the users themselves. for example, the home automation system may determine which settings should apply to which users, at which times and at which locations based on previous actions of the users. alternatively, users may engage with the television receiver (e.g. via a television display, remote control, mobile device, etc.) to input choices for such settings, either by selecting from a list of predetermined settings or by manually entering in values for those settings. fig. 12b shows a table 1200 b of other data associated with sensors in each of the four rooms. the data included in table 1200 b includes features that may be determined by the home automation system after receiving and analyzing data associated with one or more users over a period of time. for example, the home automation system may have determined, based on data collected by the sensors, that a certain user (or set of users) set the temperature for room 3 at 68 degrees, 69 degrees, and 67 degrees on 3 consecutive days (these temperatures may have been set during the times listed in fig. 12a associated with room 3, or not). in another example, the home automation system may have determined, based on data collected by the sensors, that a certain user (or set of users) turned the tv on and set it at channel 5 every day in room 1, but turned the light off while in room 1 on day 5. the fact that the lights were turned off may be explained by a different user in room 1 than on days 3 and 4, or by another characteristic or action taken by one or more users. the home automation system, for example a television receiver of a satellite distribution system a part of or connected to the home automation system, may use some or all of the data it has collected about one or more of the users to determine patterns in the users' behavior, associate settings with those behaviors over time, and adjust those associations over time as new data is received and analyzed. as noted, the home automation system may make changes to devices in the home automation system (e.g. hvac temperature, lights, satellite television system, etc.) based on one or more sensors in the home automation system detecting that a mobile device (e.g. and a user holding the mobile device) has moved from one location in a structure to a second location. however, a problem may exist if the devices or settings on the devices are changed multiple times over a short period of time. for example, settings on a device may be changed multiple times in a short period of time if a mobile device is detected as entering a room (e.g. in the proximity of one sensor) and leaving the room shortly thereafter (outside the proximity of the one sensor, and maybe in the proximity of another sensor). for example, if the device being changed is a set of lights, then the lights may be switched on and off multiple times in just a period of time of just a few seconds. such an occurrence may cause discomfort or displeasure to one or more users. for example, the rapid switching of lights on and off may scare a user. although the home automation system may use the location of a mobile device, and communication with that mobile device, to determine the location of a user, such a process may be inaccurate since the user may not be in the same place as the mobile device at all times. for example, the user may leave the mobile device on its charger or by itself in a room. therefore, the home automation system may use data from a different sensor of set of sensors to determine the location of a user. for example, the home automation system may use data compiled from motion detectors, video cameras (and, for example, facial or other recognition software), the television receiver itself, among other types of sensors. in another example, the home automation system may use a variety of different sensors, including a combination of sensors, to determine the location of a user. for example, the home automation system may use any interaction between the user and any home automation device as an indication that the user is in a certain location, and may use the user's mobile device or other personal device as a back-up to the network of home automation devices. therefore, the home automation system may be configured to cause a delay in making changes to devices in the home automation system where the changes are due to, for example, a detected change in location of a user. in other words, using such a delay, the home automation system can confirm that the change in location, or other change in status (e.g. change in characteristic(s)) causing the change in setting of the network device, will remain for at least a certain predetermined period of time. for example, if a user moves from a first room to a second room of a dwelling, as shown in fig. 10 , the home automation may ordinarily make an immediate change in settings within the second room, such as room 1064 . for example, the home automation system may make a change in the dimming of lights 1055 within room 1064 when user 1053 enters room 1064 due to sensor 1074 detecting the presence of user 1053 or mobile device 1055 . instead, the television receiver of the home automation system, such as television receiver 1050 , may delay making any changes to settings of home automation devices in room 1064 , or other devices that may have an effect on the user in room 1064 , by a period of time to confirm that the user will remain in room 1064 for enough time to make the home automation system sure that it is worth changing the settings in room 1064 for the user's period of presence in the room. after the home automation system has detected that a status change (e.g. change in location of the user) has occurred that may invoke a change in home automation device (e.g. turning the lights on), the home automation system may wait a certain predetermined period of time before invoking that change in the home automation device. during that period of time, the home automation system may do nothing. in other words, the home automation system may ignore the device or the status change that invoked the device setting change, until the predetermined period of time for delay has lapsed. in another example, the home automation system may continuously or periodically monitor the status of the user to determine if the status has changed again since the original change in status. for example, if the status change has reverted back to its original status (e.g. the user has moved back to its original location before the change in location) at any time during the predetermined delay period, then the home automation system may prevent the change in setting from occurring in the home automation devices in the new location (because, for example, the changes being made for the user are moot because the user is no longer at that location). if the status change reverts back temporarily, but then re-changes after the revert, then the home automation system may either proceed with the changes as scheduled, may re-start the predetermined period of time delay, among other options. it may be appropriate for the delay period of time to be different depending on the home automation device being changed, the setting being changed, the action performed by the user to cause the change, or other factors. for example, if the action performed by the user to cause the change is that the user walked from one room to another, it may be appropriate for the delay to be longer (e.g. 5-10 seconds) because the action of walking into a room is highly variable and there is a relatively high probability that the user may walk out of the new room within a short period of time after walking in. however, on the other hand, if the action performed by the user to cause the change is that the user turns on the television, it may be appropriate for the delay to be shorter (e.g. 1-2 seconds) because the action of turning on the television is not as variable. in other words, there may be a higher probability that a user will stay in a location after turning the television on (such that a change in settings based on the user's preferences is appropriate) than if the user just walks into the room. an event that may cause an even further reduction in the necessary delay time period is if the user turns on the television, and turns on a specific television show that the home automation system knows is a favorite television show of the user. to go even further, an even further reduction in the necessary delay time period may be appropriate if the home automation system, over time, has detected a pattern of the user watching television (or even that specific television show) at approximately the current day of the week and time of night. in another example, the television receiver may not turn the television on, but may change the channel to the correct channel for the user to watch the user's television show. in another example, the television receiver may begin playing a television show stored on the receiver's dvr feature, and then pause the show so that the show will be ready for the user to watch (just by pressing “play”, for example) once the user turns the television on. various other data collected by the home automation network that is associated with user actions around the structure and/or interacting with the home automation system may be used to assign the delay period of time. as noted, a change in settings based on the user's preferences may be deemed more or less “appropriate” to occur if it is determined that the settings will be kept, due to the user staying at that location or within a proximity of that location, for a certain predetermined amount of time. any of the changes in settings or actions taken by the home automation system in response to a trigger may also be presented, either individually or in groups (e.g. drop down menu), to the user for selection. as noted, a query may be transmitted from the television receiver (or another central processing device for the home automation system, if not the television receiver) to a mobile device of the user requesting user input. in another example, such a query may be displayed on a television display device for the user to view if/when the user watches television. the predetermined amount of time, or delay, for which the home automation system waits to implement a change in device setting may be changed over time. in one example, the delay period of time may be automatically adaptable based on data collected by the sensors in the home automation system from events that may occur, or data or events detected by other systems such as a satellite television distribution system. for example, the home automation system may use data associated with a user or with a home automation device to adjust the delay periods of time. for example, if a user walks into a room, and the home automation system determines that it should turn the dimmer of the lights in that room down due to the user's preferences, a delay may be set at 5 seconds to confirm that the user will remain in the room for enough time such that lowering the dimmer of the lights is appropriate. however, if the sensor in that room compiles data associated with the user such that the home automation system may determine that there is a high probability (e.g. 75% of the time) that the user will stay in the room for an extended period of time, then the home automation system may reduce the 5 second delay time period to a lower amount of time. to determine whether there is a high enough probability that the user will remain in the room for a certain amount of time, either or both of the probability and the amount of time may be compared to thresholds, predetermined or variable. such thresholds may be adjusted based on the specific situation including the user, the room, the home automation system, the device at issue, among others. the amount of the delay, whether the delay is lengthened or shortened, and whether the settings are changed based on a user action as a whole may also be adjusted in real time as the action is taking place. for example, if a room includes a video camera with facial or other types of recognition associated with it, the video camera may identify certain actions or sub-actions by the user that result in recorded data that may affect (e.g. immediately) the delay time period or other aspects of the home automation adjustments. referring back to a more specific example, the video camera may identify that the user, after walking into a room, never sits down or never stops moving throughout the room. such an action by the user may be used to indicate to the home automation system that the user does not plan to remain in the room for very long, which may cause the home automation system to increase the delay time period. on the other hand, if the user walks into the room and immediately sits down on a couch or lies down on a bed, then the home automation system may use data indicating that those actions took place to reduce the delay before making appropriate adjustments to the home automation devices in that room based on the user's preferences. in another example, if a user walks into a garage, the home automation system may be set to open the garage door so that the user may remove their car from the garage. however, if a sensor in the garage collects data that indicates that the user, after walking into the garage, walked towards a separate part of the garage than from where the car is located, the home automation system may determine that there is a low probability (e.g. lower than 50%, or lower than a threshold, among other reasons) that the user will remove the car from the garage and use this data to increase the delay time. any settings or actions taken by the home automation system at a structure, such as structures 700 and 1000 shown in figs. 7 and 10 , respectively, may be transmitted to one or more other home automation systems remote from that structure. for example, if a user has a second home and a second home automation system exists in that home, the home automation system in the user's dwelling may, via the internet or via the satellite television distribution system, transmit data, settings, or other aspects of the technology described herein either collected or generated, to the second home automation system for use. such data or settings may allow the second home automation system to be more efficient, and reduce the time it takes to develop profiles for the home automation devices and/or the users who occupy both structures at different times. for example, if the second home automation system knows that one or more users use the second home every weekend and arrive at the second home (with the second home automation system) at, on average, 8:30 pm every or most friday nights, then the second home automation system may download or receive updated settings and use those settings to tailor the home for the user(s) in advance in preparation for the users' arrival. if the satellite distribution system is used, the internet may not even be necessary for the home automation systems to communicate with one another, as described further with respect to fig. 1 herein. the home automation system may also transmit such data or settings to one or more vehicles of the user. for example, temperature settings for each user may be transmitted to the users' cars such that different temperature zones in those cars may be adapted to the user's preferences (for example, which may have been entered by the user in the home automation system in the structure, such as via the television receiver and television display device). such settings may be used any time the user gets into the user's car, or into any car used by the group of users that are known by the home automation system. fig. 13 illustrates a structure 1300 that includes a dwelling, according to embodiments of the present technology. the structure 1300 includes three different rooms 1360 , 1362 and 1364 . as shown in fig. 13 , room 1360 is on the second floor of the dwelling and room 1362 and 1364 are on the first floor of the dwelling. as noted, various features, such as an hvac system, a home security or surveillance system, a satellite or cable television system, among others, may be incorporated into a home automation system within a structure, such as structure 1300 . the home automation system may include various sensors that may be distributed around the structure, such as sensors 1370 a , 1370 b , 1372 , and 1374 . similar to as described with respect to figs. 7 and 10 , sensors 1370 a , 1370 b , 1372 , and 1374 may record readings of certain characteristics of the sensors' environments in the rooms that the sensors are located in. sensors 1370 a , 1370 b , 1372 , and 1374 may compile recordings of data over a period of time. fig. 13 illustrates the transition over time of a user 1353 between rooms 1362 and room 1360 and outside of structure 1300 . as shown in fig. 13 , user 1353 may initially be located in room 1362 , for example near door 1380 . user 1353 is holding a network device 1355 , such as a mobile device, that may be connected to a wireless or wired network. the sensors 1360 , 1362 and/or 1364 may also be connected to the same network. since user 1353 is located in room 1362 , the mobile device 1355 that the user is holding may communicate with sensor 1372 , which is also in room 1362 . however, user 1352 may move to room 1360 , or to a location 1390 that is outside of structure 1300 altogether. as noted, in one example embodiment, a user of a home automation system may want to activate an associated alarm system when the user is not close enough to an opening in the structure, such as door 1380 . for example, in a situation where a user within a structure is far away from the main door of the structure, such as in room 1360 on the second floor or outside the structure completely, it may be difficult for that user to be alerted by someone entering the main door due to the user's far proximity away from that door. therefore, it may be beneficial for an alarm system to activate when a user is determined to be more than a certain predetermined distance away from the door so that the user can be alerted to activity at or near the door. in addition to activating the security system, other changes may be made to the security system. for example, only a part of the security system may be activated (such as, for example, only the door/window sensors, and not the motion detectors, or other combinations). in another example, a setting may be changed on the security system when the home automation system determines that a user has walked away from the door beyond a certain distance. such settings may include the volume of the alarm when it rings, the type of alarm that rings, under what circumstances the alarm goes off, among other settings. the threshold for determining when a change should be made to the security system may be in a variety of different forms. as noted, a change may be automatically made to the security system upon a user moving to a location that is beyond a certain threshold distance away from a structure, a door of the structure, a home automation sensor, etc. in another example, a change may be made to the security system upon a user moving to a location that is beyond a certain threshold distance away from a structure and stays at least that far away for a predetermined amount of time. in another example, a change may be made to the security system upon a mobile device associated with a user moving beyond a certain threshold distance away from a structure (e.g. for a certain amount of time). in another example, a change may be made to the security system if a user walks into a certain room in the house (e.g. the basement) that is in a certain location far away from, for example, the front door of the house. in another example, a change may be made to the security system upon a user staying in the same position for a predetermined amount of time (e.g. if the user fell asleep). as noted, in an example, a change may be made to the security system upon a user moving to a location that is beyond a certain threshold distance away from a structure and stays at least that far away for a predetermined amount of time. in other words, as described in more detail with respect to figs. 12a-12b , the home automation system may be configured to cause a delay in making changes to devices in the home automation system where the changes are due to, for example, a detected change in location of a user. in other words, using such a delay, the home automation system can confirm that the change in location, or other change in status (e.g. change in characteristic(s)) causing the change in setting of the network device, will remain for at least a certain predetermined period of time. an example of such a situation is also described further with respect to fig. 14 herein. the threshold used to determine if a change is to be made to the home security system, which as noted may include a threshold distance, time, among others, or a combination of multiple thresholds, may also be generated or adjusted automatically by the home automation system. for example, the sensors in the home automation system may detect a level of importance, or another characteristic, of the different sensors based on the data it collects. the home automation system may also make this determination based on a variety of other characteristics or factors. for example, a threshold may be increased or decreased based on various factors, including important times of day, days of the week, times of year, etc. or data collected about the user that has moved the certain distance away from the structure for a certain amount of time, among others. in another example, the thresholds may be determined or adjusted based on specific information collected about a user. for example, if a user walks away from the structure at a certain time every day, and the user returns to the structure within 5 minutes each time, then the home automation system may determine that making changes to the home security system due to that user leaving at that time may not be necessary. on the other hand, the user may indicate to the home automation system that the user wants the structure to be extremely secure, which may prompt the home automation system to automatically make changes to the home security system at that time every day since it may predict that the user will walk away from the structure at that time. in other words, the home automation system may learn certain patterns or characteristics of a user or set of users, and may tailor the home automation system or related systems (e.g. home security system, hvac, etc.) based on those patterns and/or characteristics. a user may be able to choose which characteristics or factors that the home automation system uses to automatically determine the thresholds, or may be able to manually select the thresholds. such a choice may made via a television system, such as a satellite television system, including a television receiver or may be provided via a display device on a television or a mobile device, among others. fig. 14 illustrates a table 1400 including example stored data used within a home automation system, according to embodiments of the present technology. more specifically, table 1400 includes data associated with two sensors in a structure that shows a user's location and associated home automation and home security system actions taken due to the user's location. for the example data shown in table 1400 , it can be assumed that the distance threshold is approximately 30 feet, or at least somewhere between 26 and 36 feet. as shown in table 1400 , the user has not reached or passed the threshold at a determined/recorded distance away (e.g. away from a door, sensor, etc. of the structure) of 2 feet, 5 feet, 3.5 feet, and 10 feet. however, when the user has reached 45 feet, the user has crossed the threshold. as noted, a change may be made to the security system upon a user moving to a location that is beyond a certain threshold distance away from a structure for a predetermined amount of time. therefore, even though the user reached the threshold at 45 feet distance away, the alarm is not turned on (the example “change” to the home security system in this example) because the user has only been beyond the threshold for 10 seconds at that distance. the alarm system is not turned on at a distance of 48 fee either since the user has only been beyond the threshold for 20 seconds, and thereafter the user moves back within a distance range such that the user has not crossed the threshold any longer. however, at 36 feet, the user has crossed the threshold, and the user stays across the threshold for a longer period of time. more specifically, the user crosses the threshold and stays across for at least 40 seconds as shown in fig. 14 . in this case, the threshold (either set by the user or automatically determined by the home automation system) is 30 seconds, since the alarm turns on as soon as the user has been across the 30 foot threshold for 30 seconds. as further shown in table 1400 , the sensor never reaches the distance threshold (and therefore never reaches the time threshold) with regard to sensor 2 (the back door of the structure). therefore, the user's distance away from the back door never activates a change in the security system. fig. 15 is a flow chart of an example process used to control a home automation system based on a user's location, according to embodiments of the present technology. step 1502 includes receiving, by a television receiver connected to a home automation system, an input from a user including a set of preferences associated with an hvac system connected to the home automation system in a structure. step 1504 includes assigning, by the television receiver, a weight to each of two or more hvac sensors of the hvac system using the received set of preferences, wherein the hvac sensors are each distributed in different rooms of the structure. step 1506 includes generating, by the television receiver, an hvac profile using the set of preferences and the weights assigned to the hvac sensors, wherein the hvac profile includes settings associated with proportions of conditioned air to be distributed to a plurality of rooms of the structure. step 1508 includes transmitting, by the television receiver, the hvac profile to the hvac system, wherein when the hvac profile is received, the hvac profile is used to run the hvac system. step 1510 includes receiving, at the television receiver, hvac data recorded by the hvac sensors, wherein the hvac data includes temperature data recorded in the different rooms over a period of time. step 1512 includes updating, by the television receiver, the hvac profile using the received hvac data and the set of preferences. step 1514 includes transmitting, by the television receiver, the updated hvac profile, wherein when the updated hvac profile is received, at least a portion of the updated hvac profile is displayable on a television display device. fig. 16 is a flow chart of another example process used to control a home automation system based on a user's location, according to embodiments of the present technology. step 1502 includes receiving, at a television receiver of a satellite distribution system, an input from a user including a set of preferences associated with a home automation system connected to the satellite distribution system. step 1504 includes generating, by the television receiver, a user profile using the set of preferences, wherein the user profile includes settings associated with a user and a set of characteristics of the home automation system, and wherein the profile includes home automation settings associated with a first location and home automation settings associated with a second location. step 1506 includes receiving, at the television receiver, data indicating that the mobile device has moved from the first location to the second location. step 1508 includes transmitting, by the television receiver, the user profile to a mobile device associated with the user, wherein when the user profile is received, the settings associated with the first location are applied to the home automation system. step 1510 includes receiving, at the television receiver, data indicating that the mobile device has been at the second location for a period of time step 1512 includes comparing, by the television receiver, the period of time to a predetermined threshold period of time. step 1514 includes, in response to determining that the period of time exceeds the threshold period of time, applying the home automation settings associated with the second location to the home automation system. fig. 17 is a flow chart of another example process used to control a home automation system based on a user's location, according to embodiments of the present technology. step 1702 includes receiving data from a sensor in a home automation system, the data associated with a user. step 1704 includes determining, using the data, a location of the user, the location including an indication of a distance between the user and a structure. step 1706 includes comparing the distance with a predetermined threshold distance. step 1708 includes determining an amount of time for which the user has crossed the threshold distance. step 1710 includes comparing the amount of time to a threshold amount of time. step 1712 includes activating a change in a home security system associated with the home automation system based on the user crossing the threshold amount of time. fig. 18 illustrates an embodiment of a computer system 1800 . a computer system 1800 as illustrated in fig. 18 may be incorporated into devices such as an stb, a first electronic device, dvr, television, media system, personal computer, and the like. moreover, some or all of the components of the computer system 1800 may also be incorporated into a portable electronic device, mobile phone, or other device as described herein. fig. 18 provides a schematic illustration of one embodiment of a computer system 1800 that can perform some or all of the steps of the methods provided by various embodiments. it should be noted that fig. 18 is meant only to provide a generalized illustration of various components, any or all of which may be utilized as appropriate. fig. 18 , therefore, broadly illustrates how individual system elements may be implemented in a relatively separated or relatively more integrated manner. the computer system 1800 is shown comprising hardware elements that can be electrically coupled via a bus 1805 , or may otherwise be in communication, as appropriate. the hardware elements may include one or more processors 1810 , including without limitation one or more general-purpose processors and/or one or more special-purpose processors such as digital signal processing chips, graphics acceleration processors, and/or the like; one or more input devices 1815 , which can include without limitation a mouse, a keyboard, a camera, and/or the like; and one or more output devices 1820 , which can include without limitation a display device, a printer, and/or the like. the computer system 1800 may further include and/or be in communication with one or more non-transitory storage devices 1825 , which can comprise, without limitation, local and/or network accessible storage, and/or can include, without limitation, a disk drive, a drive array, an optical storage device, a solid-state storage device, such as a random access memory (“ram”), and/or a read-only memory (“rom”), which can be programmable, flash-updateable, and/or the like. such storage devices may be configured to implement any appropriate data stores, including without limitation, various file systems, database structures, and/or the like. the computer system 1800 might also include a communications subsystem 1830 , which can include without limitation a modem, a network card (wireless or wired), an infrared communication device, a wireless communication device, and/or a chipset such as a bluetooth™ device, an 802.11 device, a wifi device, a wimax device, cellular communication facilities, etc., and/or the like. the communications subsystem 1830 may include one or more input and/or output communication interfaces to permit data to be exchanged with a network such as the network described below to name one example, other computer systems, television, and/or any other devices described herein. depending on the desired functionality and/or other implementation concerns, a portable electronic device or similar device may communicate image and/or other information via the communications subsystem 1830 . in other embodiments, a portable electronic device, e.g. the first electronic device, may be incorporated into the computer system 1800 , e.g., an electronic device or stb, as an input device 1815 . in many embodiments, the computer system 1800 will further comprise a working memory 1835 , which can include a ram or rom device, as described above. the computer system 1800 also can include software elements, shown as being currently located within the working memory 1835 , including an operating system 1840 , device drivers, executable libraries, and/or other code, such as one or more application programs 1845 , which may comprise computer programs provided by various embodiments, and/or may be designed to implement methods, and/or configure systems, provided by other embodiments, as described herein. merely by way of example, one or more procedures described with respect to the methods discussed above might be implemented as code and/or instructions executable by a computer and/or a processor within a computer; in an aspect, then, such code and/or instructions can be used to configure and/or adapt a general purpose computer or other device to perform one or more operations in accordance with the described methods. a set of these instructions and/or code might be stored on a non-transitory computer-readable storage medium, such as the storage device(s) 1825 described above. in some cases, the storage medium might be incorporated within a computer system, such as computer system 1800 . in other embodiments, the storage medium might be separate from a computer system e.g., a removable medium, such as a compact disc, and/or provided in an installation package, such that the storage medium can be used to program, configure, and/or adapt a general purpose computer with the instructions/code stored thereon. these instructions might take the form of executable code, which is executable by the computer system 1800 and/or might take the form of source and/or installable code, which, upon compilation and/or installation on the computer system 1800 e.g., using any of a variety of generally available compilers, installation programs, compression/decompression utilities, etc., then takes the form of executable code. it will be apparent to those skilled in the art that substantial variations may be made in accordance with specific requirements. for example, customized hardware might also be used, and/or particular elements might be implemented in hardware, software including portable software, such as applets, etc., or both. further, connection to other computing devices such as network input/output devices may be employed. as mentioned above, in one aspect, some embodiments may employ a computer system such as the computer system 1800 to perform methods in accordance with various embodiments of the technology. according to a set of embodiments, some or all of the procedures of such methods are performed by the computer system 1800 in response to processor 1810 executing one or more sequences of one or more instructions, which might be incorporated into the operating system 1840 and/or other code, such as an application program 1845 , contained in the working memory 1835 . such instructions may be read into the working memory 1835 from another computer-readable medium, such as one or more of the storage device(s) 1825 . merely by way of example, execution of the sequences of instructions contained in the working memory 1835 might cause the processor(s) 1810 to perform one or more procedures of the methods described herein. additionally or alternatively, portions of the methods described herein may be executed through specialized hardware. the terms “machine-readable medium” and “computer-readable medium,” as used herein, refer to any medium that participates in providing data that causes a machine to operate in a specific fashion. in an embodiment implemented using the computer system 1800 , various computer-readable media might be involved in providing instructions/code to processor(s) 1810 for execution and/or might be used to store and/or carry such instructions/code. in many implementations, a computer-readable medium is a physical and/or tangible storage medium. such a medium may take the form of a non-volatile media or volatile media. non-volatile media include, for example, optical and/or magnetic disks, such as the storage device(s) 1825 . volatile media include, without limitation, dynamic memory, such as the working memory 1835 . common forms of physical and/or tangible computer-readable media include, for example, a floppy disk, a flexible disk, hard disk, magnetic tape, or any other magnetic medium, a cd-rom, any other optical medium, punchcards, papertape, any other physical medium with patterns of holes, a ram, a prom, eprom, a flash-eprom, any other memory chip or cartridge, or any other medium from which a computer can read instructions and/or code. various forms of computer-readable media may be involved in carrying one or more sequences of one or more instructions to the processor(s) 1810 for execution. merely by way of example, the instructions may initially be carried on a magnetic disk and/or optical disc of a remote computer. a remote computer might load the instructions into its dynamic memory and send the instructions as signals over a transmission medium to be received and/or executed by the computer system 1800 . the communications subsystem 1830 and/or components thereof generally will receive signals, and the bus 1805 then might carry the signals and/or the data, instructions, etc. carried by the signals to the working memory 1835 , from which the processor(s) 1810 retrieves and executes the instructions. the instructions received by the working memory 1835 may optionally be stored on a non-transitory storage device 1825 either before or after execution by the processor(s) 1810 . the methods, systems, and devices discussed above are examples. various configurations may omit, substitute, or add various procedures or components as appropriate. for instance, in alternative configurations, the methods may be performed in an order different from that described, and/or various stages may be added, omitted, and/or combined. also, features described with respect to certain configurations may be combined in various other configurations. different aspects and elements of the configurations may be combined in a similar manner. also, technology evolves and, thus, many of the elements are examples and do not limit the scope of the disclosure or claims. specific details are given in the description to provide a thorough understanding of exemplary configurations including implementations. however, configurations may be practiced without these specific details. for example, well-known circuits, processes, algorithms, structures, and techniques have been shown without unnecessary detail in order to avoid obscuring the configurations. this description provides example configurations only, and does not limit the scope, applicability, or configurations of the claims. rather, the preceding description of the configurations will provide those skilled in the art with an enabling description for implementing described techniques. various changes may be made in the function and arrangement of elements without departing from the spirit or scope of the disclosure. also, configurations may be described as a process which is depicted as a flow diagram or block diagram. although each may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. in addition, the order of the operations may be rearranged. a process may have additional steps not included in the figure. furthermore, examples of the methods may be implemented by hardware, software, firmware, middleware, microcode, hardware description languages, or any combination thereof. when implemented in software, firmware, middleware, or microcode, the program code or code segments to perform the necessary tasks may be stored in a non-transitory computer-readable medium such as a storage medium. processors may perform the described tasks. having described several example configurations, various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosure. for example, the above elements may be components of a larger system, wherein other rules may take precedence over or otherwise modify the application of the technology. also, a number of steps may be undertaken before, during, or after the above elements are considered. accordingly, the above description does not bind the scope of the claims. as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. thus, for example, reference to “a user” includes a plurality of such users, and reference to “the processor” includes reference to one or more processors and equivalents thereof known to those skilled in the art, and so forth. also, the words “comprise”, “comprising”, “contains”, “containing”, “include”, “including”, and “includes”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.
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079-460-792-698-64X
|
IT
|
[
"US",
"BR",
"WO",
"CN",
"CA",
"EP",
"NO",
"AR",
"AU"
] |
F03D9/00,F03D1/02,H02K7/18,F03D11/00
| 2006-12-22T00:00:00 |
2006
|
[
"F03",
"H02"
] |
multiple generator wind turbine
|
a multiple generator wind turbine employs a single blade arrangement to drive multiple generators. the multiple generators are preferably substantially tubular and can all be mounted on one side of the turbine support structure or can be divided, preferably symmetrically, on opposite sides of the support structure. preferably, a single drive blade arrangement drives a rotor of a first generator and a shaft connects the first generator to a rotor of a second generator. additionally, a clutch can be placed in the drive train between two generators to allow turbine operation at lower speeds. the substantially tubular nature of the turbine allows easy access by humans to the interior of the wind turbine and provides ready air flow through the wind turbine to the hub and blades for cooling of equipment therein and/or deicing of the blades.
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1 : a multiple generator wind turbine comprising: at least two generators mounted on a supporting structure, a first of the generators connected to and configured to be driven by a drive blade arrangement, and at least one clutch arranged between the first of the generators and a second of the generators, the first generator being selectively mechanically connected to the second of the generators via the at least one clutch and being configured to drive the second of the generators. 2 : the multiple generator wind turbine of claim 1 , wherein the first and the second of the generators each include at least one rotor and at least one stator, the rotor of the first of the generators being mechanically connected to the blade arrangement and selectively mechanically connected to the rotor of the second of the generators. 3 : the multiple generator wind turbine of claim 1 , wherein the first of the generators is mounted on a blade side of a supporting structure and the second of the generators is mounted on a side of the supporting structure opposite the blade side, and a main shaft is selectively mechanically connected to at least one of the first and the second of the generators to transfer drive from the first of the generators to the second of the generators. 4 : the multiple generator wind turbine of claim 3 , wherein the main shaft includes a first half shaft connected to and extending from the first of the generators toward the second of the generators and a second half shaft connected to and extending from the second of the generators toward the first of the generators, one of the first and second half shafts having a first end portion of a smaller outer diameter than an inner diameter of a second end portion of the other of the first and second half shafts such that the first end portion extends into the second end portion, the end portions being connected to form the main shaft. 5 : the multiple generator wind turbine of claim 4 , wherein the at least one clutch is arranged to connect the first and second end portions. 6 : the multiple generator wind turbine of claim 1 , wherein the first and the second of the generators are disposed on a blade side of a supporting structure. 7 : the multiple generator wind turbine of claim 3 , wherein each of the first and the second of the generators include at least one rotor and at least one stator, the rotor of the first of the generators being mechanically connected to and configured to be driven by the drive blade arrangement, the rotor of the second of the generators being selectively mechanically connected to the first of the generators via the main shaft, the main shaft extending through a connecting structure between the first and the second of the generators. 8 : the multiple generator wind turbine of claim 7 , wherein the first and the second of the generators are first and second generator clusters, the first generator cluster including at least first and second generators and the second cluster including at least third and fourth generators. 9 : the multiple generator wind turbine of claim 8 , wherein the first and second generators are concentrically arranged and the third and fourth generators are concentrically arranged, the rotors of the first and second generators being mounted on opposed sides of a first double rotor, the rotors of the third and fourth generators being mounted on opposed sides of a second double rotor, the stators of the first and second generators being mounted on facing surfaces of a first double stator, the stators of the third and fourth generators being mounted on facing surfaces of a second double stator. 10 : the multiple generator wind turbine of claim 2 , wherein one of the first and the second of the generators includes an annular generator and one of the first and the second of the generators includes a concentrically arranged double generator, the annular generator including a rotor with rotor elements on an outer surface of an inner annulus and facing stator elements on an inner surface of an outer annulus, the concentrically arranged double generator including a double-sided annular rotor with rotor elements on inner and outer annular surfaces thereof and facing respective stator elements mounted on outer and inner annular surfaces of the stator. 11 : a modular wind turbine comprising: a supporting structure, a first generator connected to and configured to be driven by a drive blade arrangement, a connector extending from a rotor of the first generator and terminating in a rotor flange, and a stator flange at an end of a stator opposite from the drive blade arrangement. 12 : the modular wind turbine of claim 11 , wherein the stator flange is attached to the supporting structure. 13 : the modular wind turbine of claim 11 , further including a second generator including a corresponding rotor connector and corresponding rotor and stator flanges, the rotor flange of the first generator being connected to the rotor flange of the second generator and the stator flange of the first generator being connected to the stator flange of the second generator. 14 : the modular wind turbine of claim 13 , wherein the second generator is arranged between the first generator and the supporting structure, the second generator being attached to the supporting structure at and end opposite the blade arrangement. 15 : the modular wind turbine of claim 13 , wherein the first and second rotor flanges are connected via a clutch such that the second rotor is configured to be driven by the first rotor when the clutch is engaged and is configured not to be driven by the first rotor when the clutch is disengaged. 16 : the modular wind turbine of claim 11 , wherein the stator flange can be detached from the supporting structure to allow installation of a second generator between the first generator and the supporting structure, the second generator including a corresponding rotor connector and corresponding rotor and stator flanges, the rotor flange of the first generator being connected to the rotor flange of the second generator and the stator flange of the first generator being connected to the stator flange of the second generator. 17 : a multiple generator wind turbine comprising: at least two generators, each of the at least two generators including at least one substantially tubular rotor and at least one substantially tubular stator, the at least one stator being supportable by a support tower, wherein each of the at least one rotor and the at least one stator carry one of mutually opposed magnetic field generators and windings, the at least one stator and the at least one rotor are substantially concentric such that one of the stator and rotor lies at least partly within the other of the stator and rotor and such that the mutually opposed magnetic field generators and windings face each other; a blade arrangement on a side of one of the at least two generators opposite the support structure, the blade arrangement including a hub attached to a rotor of the one of the at least two generators, and at least two blades extending radially from and supported by the hub; and a single bearing mounted diametrally between the stator and the rotor of the one of the at least two generators. 18 : the multiple generator wind turbine of claim 17 , wherein an inner race of the bearing is carried on a hub end of the inner of the stator and the rotor and an outer race of the bearing is carried on a hub end of the outer of the stator and the rotor, the single bearing handling both thrust and journal loading. 19 : the multiple generator wind turbine of claim 17 , wherein at least one generator is mounted between the support structure and the blade arrangement on one side of the support structure. 20 : the multiple generator wind turbine of claim 19 , wherein at least one generator is mounted on a side of the support structure opposite the blade arrangement. 21 : the multiple generator wind turbine of claim 17 , wherein the at least two generators are modular. 22 : the multiple generator wind turbine of claim 17 , wherein the support structure is substantially tubular, such that the at least one substantially tubular rotor and the at least one substantially tubular stator of each of the at least two generators and the substantially tubular support structure are configured to provide a passage through the at least one substantially tubular rotor and the at least one substantially tubular stator of each of the at least two generators and the substantially tubular support structure to allow ready access by humans to an interior portion of the wind turbine. 23 : the multiple generator wind turbine of claim 22 , wherein the at least one substantially tubular rotor and the at least one substantially tubular stator of each of the at least two generators and the substantially tubular support structure are configured to allow air flow through the at least one substantially tubular rotor and the at least one substantially tubular stator of each of the at least two generators and the substantially tubular support structure to the hub and the blades.
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priority claim this application is a national stage application of pct/it2006/000870, filed dec. 22, 2006, the entire contents of which is incorporated herein. technical field the present invention relates to a wind power generator or turbine. more particularly, embodiments relate to a large-scale wind powered machine including two or more power generators and that accommodates humans within the workings for easy access and maintenance while providing efficient cooling of components and/or de-icing of blades. embodiments are particularly suited to electrical power generation via wind power. wind powered machines, particularly large scale electrical generators, include blades mounted on a hub attached to a rotor that rotates when wind passes over the blades. the rotation of the rotor is then used to drive machinery, such as pumps or electrical generators. in the case of electrical generators, the rotor will typically carry conductor windings/coils or magnetic field generators that face magnetic field generators or conductor windings/coils, respectively, on a stator such that there is relative motion between the coils and the magnetic field generators, producing electricity. the magnetic field generators are typically field windings that are electromagnets powered by the electrical generator once it begins producing electricity, but that require electricity from a battery or the like before the electrical generator produces electricity. background large scale wind powered electrical generators are becoming more common, particularly in onshore and offshore wind farm applications. in such large scale generators, a tower supports a nacelle housing the stator, which supports the rotor, which supports the hub and blades. equipment required for controlling the generator, including controls for the blades and other machinery, can be housed in the tower, the nacelle, and/or in cavities within the stator and/or the rotor. as suggested by this description, such wind machines typically include a single rotor and a single stator. in the power generation industry, there is a constant demand for more power production and/or higher efficiency in power production. a difficulty associated with meeting these demands with single generator arrangements is that a high-power generator can be quite heavy, impeding assembly of the wind machine. as generators are built to produce more power, the quantity of magnets and coils must increase by increasing diameter of the generator, allowing more magnets and coils to be installed, increasing the length of the generator, allowing longer magnets and coils to be used, or both. increases in diameter and length present transportation and support-structure related problems in that the roads on which components will be transported can only handle so large an object and the structures involved in supporting a long object can be more complicated and expensive. additionally, such high-power generators tend to be more difficult to drive than lower-power generators, requiring higher initial operating wind speed and/or larger blades. some prior art wind machines attempt to overcome these difficulties by employing more than one rotor, more than one stator, or more than one of both rotor and stator. for example, u.s. published applications nos. 2006/0066110 and 2006/0071575 disclose wind turbines including at least one double-sided stator and at least one double-sided rotor. the stator and the rotor are concentrically arranged so that the rotor has both inner and outer magnetic sides that rotate with respect to respective faces of the stator. while the rotor and stator of this arrangement are both horizontally axially arranged, the support arrangement of this arrangement requires one single bearing and one double bearing to support the rotor on the stator. this arrangement does increase power output for a given diameter wind power generator, it does not overcome the weight issue described above in that the double-sided rotor and double-sided stator are both still single components. in fact, this arrangement might even worsen the weight issue since there is more material on each of the rotor and stator. u.s. pat. no. 6,278,197 discloses another wind power generator that employs a horizontally axially arranged first rotor and replaces the usual stator with a concentric, contra-rotating second rotor that is also horizontally axially arranged. the first rotor rotates opposite to the second rotor, thereby increasing power output by effectively increasing the speed of rotation of the rotor. while this is an interesting solution to the problem of obtaining more power from a given diameter generator, it introduces undesirable complexities in the support and wind harnessing structures of the device. u.s. pat. nos. 6,285,090 and 7,042,109, as well as pct application no. wo 01/06623 a1, disclose wind turbines each employing a double sided rotor within a double sided stator. unlike embodiments and the devices discussed above, the rotor and stator are radially arranged, presenting disc-like faces to each other rather than the annuli and/or cylinders of embodiments and the devices above, though the '109 patent includes an annular embodiment. the structure is analogous to those above in that each side of the inner disc carries magnets while each face of the outer discs carries windings/coils, or vice versa. multiple discs can be employed to create multiple generators within the turbine. because of the disc configuration, the length increase associated with the power increase seen by adding a disc set is reduced as compared to an annular configuration. however, while possibly increasing power output for a given turbine diameter, weight is still an issue. additionally, because the power generating components extend vertically in generators employing discoid rotors and stators, an increase in disc diameter is required for an increase in power output. u.s. pat. no. 6,504,260 discloses another disc-configured wind turbine, but in which contra-rotating rotors are powered by respective sets of blades. this contra-rotating arrangement differs from that of the u.s. pat. no. 6,278,197 in that each rotor has a respective stators instead of having oppositely-rotating rotors. thus, the turbine has two independent power generation and collection arrangements mounted on opposite sides of a support tower substantially symmetrically. while this allows the use of two smaller generators to create a high power wind turbine, the use of completely independent drive and power collection systems introduces undesirable cost and complexity into the device. additionally, because the power generating components extend vertically in generators employing discoid rotors and stators, an increase in disc diameter is required for an increase in power output. summary the various embodiments of the present invention avoid the shortcomings of conventional wind power generators by providing a multiple generator wind turbine with a simpler structure, yielding higher power output for a given turbine diameter while keeping component diameter, weight, length, and cost down. additionally, embodiments employ a largely hollow construction in which a maximum of ventilation possibilities is available for cooling and/or de-icing. in addition, embodiments afford a large degree of accessibility to the various components of the generator while providing a high level of structural stiffness. embodiments further allow for the use of standard components, particularly in embodiments in which modular arrangements are employed, which can result in easier manufacture, assembly, and production. by virtue of the mounting of generators on opposite sides of the support structure according to embodiments, optimization of loads on the wind turbine can be realized. in a preferred embodiment, the wind power generator is a multipolar, gearless, synchronous generator that extends substantially horizontally and is largely hollow by virtue of the use of modular coaxial tubular stator and rotor elements. for additional simplification, embodiments employ permanent magnets on one of stator and rotor, and windings/coils on the other of stator and rotor. in a first arrangement, a single set of blades is mounted on a side of a supporting structure. a first rotor is mounted on the blade side of the turbine, while a second rotor is mounted on the opposite side of the turbine in substantially symmetric arrangement. respective stators are mounted concentrically with the rotors to enable power generation when the rotors rotate relative to their respective stators. a shaft connects the two rotors, and the two are driven by the single set of blades. for example, the blade-side rotor can be driven by the blades and connected to the shaft, which drives the opposite rotor. in embodiments, the shaft includes two half shafts extending from the rotors toward the center of the turbine. the end of one half shaft is inserted into the end of the other and connected to form the shaft. in a second arrangement according to embodiments, multiple generators are coaxially arranged between the turbine blades and the support structure of the turbine. thus, the turbine blades drive a first rotor that is connected to and drives the second rotor, each having a respective concentric stator. embodiments of course allow use of more than two rotors. the first rotor serves simultaneously as a shaft that can be supported by bearings and as a structure for anchoring power generation elements. advantageously, the first and second arrangements can be used together such that multiple generators can be mounted on either side of the support structure of the turbine, the two generator clusters being connected by a shaft or other suitable connector between the two generators. thus, a first rotor can drive a second rotor in a first cluster on the blade side of the turbine and a third rotor can drive a fourth rotor in a second cluster on the opposite side of the turbine. a third arrangement employs a double-sided rotor within two concentric stators in a fashion similar to the annular arrangement discussed above. the double-sided rotor includes an annular portion with inner and outer surfaces extending substantially horizontally. one set of rotor elements is mounted on the inner surface and another set of rotor elements is mounted on the outer surface, each set of rotor elements facing a corresponding set of stator elements. the inner stator elements are preferably mounted on an outer surface of an annulus arranged within the double-sided rotor, while the outer stator elements are preferably mounted on the inner surface of the housing of the turbine. a fourth arrangement employs multiple generators with double-sided rotors and so is effectively a combination of the first and second arrangements described above. as with the second arrangement, the rotor of a first generator connected to the blades is connected to a second generator, such as to the rotor of the second generator, to drive the second generator. as should be apparent, embodiments can use an annular generator of the first arrangement with a concentric generator of the third arrangement. the order in which they are arranged will depend on the particular requirements of the wind turbine in which they are to be installed. thus, in some situations, the rotor of the simple annular generator could be connected to the blades and drive the rotor of the concentrically arranged generator, but in others, the double-sided rotor of the concentrically arranged generator will be connected to the blades and drive the rotor of the simple annular generator. in any arrangement, and in the combination, a clutch can be placed between a respective pair of generators to allow removal of the downstream generator(s) from the drive train. this allows the turbine to operate in a lower-power mode in which a lower wind speed is required for power generation, then, if demand or wind speed increases, reengage the downstream generator(s) to increase power output. conversely, if the turbine is operating with all generators engaged, the clutch(es) can be disengaged when the wind drops below the minimum speed for operation with all generators, allowing power generation at lower wind speeds. preferably, the clutch is automated mechanically or electrically so that rotational speed causes engagement. for example, a centrifugal clutch could be used so that the downstream generator(s) would be off line until the first rotor reached a predetermined speed, at which point the clutch would gradually engage the next rotor to bring the next rotor up to speed. the generator of embodiments is the integrating component of the supporting structure, and the loads are transferred directly from the hub onto the rotor shaft of the generator. the tubular rotor element transfers the loads into the tubular stator body by way of one bearing in each generator of the electrical machine. the largely hollow structure of embodiments provides several advantages over the structures of the prior art. for example, housing electrical and electronic subsystems inside the nacelle affords excellent protection from lightning since the structure employs the principle of the faraday cage. in addition, because the tubular structure is configured to accommodate the passage of adult humans, it permits easy access to the front portion of the nacelle and to the hub, which facilitates maintenance and repair work on other subsystems of the wind power generator. this also allows one to mount the hub from the inside. the substantially hollow structure also facilitates use of the heat given off by equipment, such as power electronics, housed in the tower, as well as heat released by the generator itself. the heat can promote the chimney effect to guide warm air into the hub and from there into and through the rotor blades. the warm air can thus be used as a particularly efficient de-icing system in cooler times of the year, and provides a cooling effect for equipment in the generator as cooler air is drawn into and passes through the hollow structure. no external energy needs to be supplied during operation to heat the rotor blades. thus, the heat given off by the generator and by the power electronics themselves is put to use in a simple fashion. additional cooling benefits are derived from the hollow structure since the components that produce heat are moved to the periphery of the generator. more specifically, the generator of embodiments places the windings on the inner periphery of the generator housing. heat produced by the windings during electricity generation is easily conducted to the outer surface of the generator. by adding cooling fins on the outer surface according to embodiments, the heat can be transferred from the generator to the air stream passing over the generator during electricity production. the cooling fins preferably project transversely from the outer surface and are substantially equally spaced apart. while the fins extend longitudinally along the outer surface, they can also have a sweep or profile that takes into account disturbances in the air stream introduced by motion of the blades and/or the fins themselves to enhance effectiveness. in embodiments, each generator has permanent magnets on an outer body and has windings/coils on an interior body. this yields a machine having a stator unit on the inside and a rotor on the outside. the magnets are preferably attached to the inner surface of the rotor in this arrangement, and the windings to the outer surface of the rotor shaft. the advantages of such a solution are a greater specific output, the possibility of using the total heat released by the generator for the de-icing system, and a simplification of the positioning of the power cables required to conduct the electric current from the generator to the tower. preferably, each rotor is supported via a single bearing, preferably of the tapered roller type. the single bearing arrangement provides simplification of the generator mounting structure since only one-side need accommodate a bearing. the single bearing arrangement also eliminates hazardous eddy currents in the generator that form temporary circuits between the stator wall, the rotor wall, and roller bodies of the bearings disposed at the ends of the active portion (windings/coils) of the two bearing arrangement. further, the single bearing arrangement simplifies adjustment processes of the bearing since the tapered rollers must be pre-stressed; embodiments with two bearings, one at each end of the generator, present design problems with respect to the construction tolerances and thermal deformation. the single bearing arrangement requires only one system of seals and lubrication concentrated in the front region of the generator. and the bearing typology used in the single bearing arrangement offers a high degree of rolling precision since pre-stressing the rollers substantially eliminates play in the bearing, as well as providing a low rolling resistance that increases generator productivity and efficiency. additional features and advantages are described in, and will be apparent from, the following detailed description and the figures. brief description of the drawings additional features and details are contained in the claims and in the description of a power generator actuated by wind, in its preferred embodiments as illustrated in the accompanying drawings, in which: fig. 1 shows a sectional view along a vertical axial plane of a multiple power generator wind turbine in which the generators are on opposed sides of a wind turbine support structure in accordance with embodiments. fig. 2 shows a sectional view along a vertical axial plane of a multiple power generator wind turbine in which the generators are in series on one side of a wind turbine support structure in accordance with embodiments. fig. 3 shows a sectional view along a vertical axial plane of a multiple power generator wind turbine in which the generators are concentric in accordance with embodiments. fig. 4 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that is similar to that of fig. 1 , but using multiple generators on each side of the support structure similar to the wind turbine shown in fig. 2 . fig. 5 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that is similar to that of figs. 2 and 3 , employing a multiple concentric generator of fig. 3 on each side of the support structure similar to the wind turbine shown in fig. 2 . fig. 6 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that is similar to that of figs. 2 and 3 , employing multiple concentric generators of fig. 3 in series on each side of the support structure similar to the wind turbine shown in fig. 2 . fig. 7 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that is similar to that of figs. 1 and 3 , employing multiple concentric generators of fig. 3 in series on one side of the support structure similar to the wind turbine shown in fig. 1 . fig. 8 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that is similar to that of fig. 7 , but employing a more modular form. fig. 9 shows a multiple power generator wind turbine as in fig. 1 , but also including at least one clutch in accordance with embodiments. fig. 10 shows a multiple power generator wind turbine as in fig. 2 , but also including at least one clutch in accordance with embodiments. fig. 11 shows a multiple power generator wind turbine as in fig. 4 , but also including at least one clutch in accordance with embodiments. fig. 12 shows a multiple power generator wind turbine as in fig. 5 , but also including at least one clutch in accordance with embodiments. fig. 13 shows a multiple power generator wind turbine as in fig. 6 , but also including at least one clutch in accordance with embodiments. fig. 14 shows a multiple power generator wind turbine as in fig. 7 , but also including at least one clutch in accordance with embodiments. fig. 15 shows a multiple power generator wind turbine as in fig. 8 , but also including at least one clutch in accordance with embodiments. fig. 16 shows a sectional view along a vertical plane of a multiple power generator wind turbine in accordance with embodiments that combines different types of generators. fig. 17 shows a multiple power generator wind turbine as in fig. 16 , but also including at least one clutch in accordance with embodiments. detailed description in fig. 1 a multiple power generator wind turbine is generally indicated by the reference number 1 . a support structure 2 of the wind turbine 1 includes a connecting structure 3 that rests atop a support tower 4 , preferably with a rotatable connection 5 allowing the single drive blade arrangement 6 to face the direction from which wind blows. the blade arrangement 6 includes a plurality of blades and drives two generators 110 , 120 . as shown in fig. 1 , the generators 110 , 120 can be arranged with one generator 110 on a blade side of the support structure 2 and another generator 120 on the opposite side of the support structure. the housings 111 , 121 of the generators 110 , 120 each preferably carry a plurality of circumferentially-distributed cooling fins 112 , 122 that draw heat away from the generators 110 , 120 , releasing the heat into the slipstream as air passes over the fins 112 , 122 . the blade side generator 110 includes a rotor 113 connected to the drive blade arrangement 6 , which rotates the rotor 113 within its housing 111 and within a stator 114 attached to the connecting structure 3 . preferably, the housings 111 , 121 are the outer surfaces of the stators 114 , 124 , which stators are a principal source of heat within the generators 110 , 120 . the rotor 113 of the first generator 110 in embodiments is mechanically connected to the rotor 121 of the second generator, thereby providing drive to the second generator 120 . each rotor 113 , 123 is supported by a bearing 7 that can be mounted in a respective stator 114 , 124 to allow rotation of the rotor 113 , 123 . preferably, the rotor 113 of the first generator 110 is selectively mechanically connected to the rotor 123 of the second generator via a clutch, thereby allowing operation of the turbine 1 with only one generator producing power when wind speed is too low to drive both generators. in an alternative embodiment seen in fig. 2 , the multiple power generator wind turbine 1 again includes two generators 110 , 120 , but they are both on one side of the supporting structure 2 . thus, the drive blade arrangement 6 is connected to the rotor 113 of the first generator 110 , which is connected to the second rotor 123 via a relatively short connector 230 , such as a short tube. in this arrangement, the two housings 111 , 121 can be combined into a single housing 200 , and the fins 112 , 122 can be combined to form one longer plurality of circumferentially-distributed cooling fins 210 extending from the housing 200 . as seen in fig. 3 , in another alternative embodiment, the first and second generators 110 , 120 can be concentrically arranged by using a double sided rotor 310 , one side of which, such as the inner side 311 , carries the first rotor 113 , and the other side of which, such as the outer side 312 , carries the second rotor 123 . the double sided rotor 310 rotates within a double stator 320 with the first rotor 113 facing the first stator 114 on the outer surface of an inner portion 321 of the double stator 320 and the second rotor 123 facing the second stator 124 on the inner surface of an outer portion 322 of the double stator 320 . the blade arrangement 6 thus drives the double sided rotor 310 within the double stator 320 to produce power. the additional alternative embodiment of a wind turbine 1 shown in fig. 4 employs two generators 110 , 120 arranged on opposite sides of the supporting structure 2 as in fig. 1 , but each generator 110 , 120 itself includes multiple generators, all driven by the single blade arrangement 6 . for convenience, the first and second generators 110 , 120 , will be called first and second generator clusters with respect to figs. 4-7 . on the blade side of the supporting structure 2 , the first generator cluster 110 includes at least two generators 410 , 420 arranged in series as in fig. 2 , while the second generator cluster 120 on the opposite side of the supporting structure 2 includes at least two generators 430 , 440 similarly arranged. the first rotor 413 is driven by the blades 6 to rotate within its stator 414 , the first rotor being connected to the second rotor via a relatively short shaft 415 . the second rotor 423 of the first cluster 110 is connected to the main shaft 130 , which is mechanically connected to the first rotor 433 of the second generator cluster 120 , providing drive to the second cluster 120 . the first rotor 433 of the second cluster 120 rotates within its respective stator 434 and is connected to the second rotor 443 of the second cluster 120 via a relatively short shaft 435 . the housings of the generators 410 , 420 of the first cluster 110 and the generators 430 , 440 of the second cluster can be merged into a single housing 450 on each side of the supporting structure 2 as in the turbine shown in fig. 2 . likewise, the fins can be combined into a single set of longer, circumferentially-distributed fins 460 on each housing 450 . the wind turbine 1 as shown in fig. 5 in another embodiment again employs two generator clusters 110 , 120 arranged on opposite sides of the supporting structure 2 and connected by a main shaft 130 as in figs. 1 and 4 , but the generators of each cluster are concentric as in fig. 3 . on the blade side of the supporting structure 2 , the first cluster 110 includes at least two generators 510 , 520 arranged concentrically as in fig. 3 , while the second cluster 120 on the opposite side of the supporting structure 2 includes at least two generators 530 , 540 similarly arranged. the first double sided rotor 550 , one side of which, such as the inner side 551 , carries the first rotor 513 , and the other side of which, such as the outer side 552 , carries the second rotor 523 . the double sided rotor 550 rotates within a double stator 560 with the first rotor 513 facing the first stator 514 on the outer surface of an inner portion 561 of the double stator 560 and the second rotor 523 facing the second stator 524 on the inner surface of an outer portion 562 of the double stator 560 . the first rotor 513 is driven by the blades 6 to rotate within its stator 514 , the first rotor 513 being connected to the first rotor 533 of the second cluster 120 via the main shaft 130 . fig. 6 shows a wind turbine according to another embodiment that combines the concentric multiple cluster arrangement of fig. 5 with the serial arrangement of fig. 2 . the blade arrangement 6 drives the first rotor, which drives the second rotor, which is mechanically connected to the second cluster via the main shaft 130 . in the second cluster 120 , a first rotor is connected to the main shaft 130 and the second rotor. fig. 7 shows a wind turbine that combines the serial multiple cluster arrangement of fig. 2 with the concentric multiple generator of fig. 3 . thus, drive blades 6 drive a first double rotor 71 within a first double stator 72 , the first double rotor being mechanically connected to a second double rotor 73 within a respective double stator 74 . fig. 8 shows a wind turbine very similar to that shown in fig. 2 , but which employs flanges 86 between generators to create a modular arrangement. as in the arrangement shown in fig. 2 , two generators 81 , 82 are both on one side of the supporting structure 2 . thus, the drive blade arrangement 6 is connected to the rotor 813 of the first generator 81 , which includes a relatively short connector 815 , such as a short tube, that terminates in a flange 816 . the flange 816 is connected to a corresponding flange 826 on a second connector 825 of the second generator 82 . thus, the first rotor 813 is connected to the second rotor 823 via connectors 815 , 825 , and flanges 816 , 826 . in this arrangement, the two housings 811 , 821 preferably also include corresponding flanges 817 , 827 . as shown, the two generators 81 , 82 are effectively modules. the modules can rely on the single bearing 7 of the first generator 81 , though additional bearings could be employed if necessary. the fins 112 , 122 of fig. 2 can be combined to form one longer plurality of circumferentially-distributed cooling fins 83 extending from the housing 80 , or can simply be left separate and aligned when the modules are assembled. as should be clear, the modular arrangement shown in fig. 8 can be employed in other arrangements, such as those shown in figs. 1-7 , to allow modular construction of wind turbines including multiple generators and/or generator clusters. as should be apparent, while one or two generators are shown in each cluster in figs. 1-7 , more generators could be combined in each embodiment as desired within each cluster or as additional clusters. in all embodiments, one or more clutches can be included between various of the generators to enable variable power output of the wind turbine and operation of the wind turbine at lower speeds than would be required if all generators were operating at the same time. some examples of arrangements that can be employed are shown in figs. 9-16 . fig. 9 shows the arrangement of fig. 1 , but with a clutch 910 schematically illustrated in the path between the first and second rotors. while the clutch is shown in the main shaft, it should be apparent that it could be in one of the rotors, between one of the rotors and the shaft, or embedded within the joint of the two half-shafts of the main shaft. any suitable type of clutch can be used. for a clutch between the half shafts, a centrifugal clutch can be particularly advantageous. in operation, the first generator would operate for all wind speeds over the minimum speed required to drive just the first generator. when the wind speed is below a minimum for using both generators, the clutch is not engaged and only the first generator is used. when the wind speed reaches a minimum for using both generators, the clutch is engaged to bring the second generator on line. figs. 12 , 14 , and 15 show clutched versions of figs. 5 , 7 , and 8 that operate in a manner similar to the clutched version of fig. 1 shown in fig. 9 . fig. 10 shows the arrangement of fig. 2 , but with a clutch 1010 schematically illustrated between the first and second rotors. it should be apparent that the clutch could be in any suitable location between the two rotors, and that any suitable type of clutch can be used. in operation, the first generator would operate for all wind speeds over the minimum speed required to drive just the first generator. when the wind speed is below a minimum for using both generators, the clutch is not engaged and only the first generator is used. when the wind speed reaches a minimum for using both generators, the clutch is engaged to bring the second generator on line. fig. 11 shows the arrangement of fig. 4 , but with clutches 1110 , 1120 , 1130 schematically illustrated between the first and second rotors 1110 , in the path between the first and second generator clusters 1120 , and between the third and fourth rotors 1130 . three clutches are shown, but not all are necessarily required. they are included for exemplary purposes. any one, any two, or all three clutches could be used, and additional clutches could be used as appropriate. it should be apparent that each clutch could be in any suitable location between, and that any suitable type of clutch can be used. for a clutch between the half shafts, a centrifugal clutch can be particularly advantageous. in operation with the three clutches shown, the first generator would operate for all wind speeds over the minimum speed required to drive just the first generator. when the wind speed is below a minimum for using both generators in the first cluster, the clutch 1110 is not engaged and only the first generator is used. when the wind speed reaches a minimum for using both generators in the first cluster, the clutch 1110 between the first and second rotors is engaged to bring the second generator on line. when the wind speed reaches a higher speed required to drive the first cluster and one of the generators from the second cluster, the clutch 1120 between the clusters can be engaged. and when a still higher wind speed required to drive all generators, the third clutch 1130 can be engaged. fig. 13 , showing a clutched version of fig. 6 , can operate in a very similar manner. fig. 16 is illustrative of the ability to mix different types of generators in the multiple generator turbine of embodiments. the particular example shown combines the simple annular generator of fig. 1 on the left with the double-sided concentric generator of fig. 3 on the right. fig. 17 illustrates that clutches can be used in the mixed generator turbines of embodiments. the combination shown in figs. 16 and 17 is an example of a combination that could be made. it should be apparent that other combinations of generator types, even within clusters, are within the scope of the invention. it will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. also, it should be noted that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.
|
080-150-483-852-81X
|
US
|
[
"US",
"CA",
"WO"
] |
A23F5/26,A23F3/18,A23F5/18,A23F3/20,A23L2/76,A23L3/36,A23F3/16,A23F5/24,A23F5/16
| 2010-05-17T00:00:00 |
2010
|
[
"A23"
] |
brewed beverages and methods for producing same
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methods for producing brewed beverages include brewing the beverage, degassing the beverage prior to storing the beverage in a sealed container, and freezing the beverage. a frozen brewed beverage is configured to be reheated prior to consumption and does not require reconstituting. a brewed beverage is in a sealed container, has a dissolved oxygen content less than about 2 ppm, is configured to be reheated prior to consumption, and does not require reconstituting.
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1 . a method for producing a brewed beverage comprising: brewing the beverage; degassing the beverage prior to storing the beverage in a sealed container; and freezing the beverage after degassing the beverage. 2 . the invention of claim 1 wherein the beverage comprises water and wherein the water is degassed prior to being used in the brewing. 3 . the invention of claim 1 wherein the beverage is degassed after the brewing and prior to sealing the container. 4 . (canceled) 5 . the invention of claim 1 further comprising substantially filling a headspace above the beverage with an inert atmosphere. 6 - 7 . (canceled) 8 . the invention of claim 1 wherein at least a portion of the container is microwavable. 9 . the invention of claim 1 wherein the degassing reduces dissolved oxygen content in the beverage by at least about 50 percent. 10 . (canceled) 11 . the invention of claim 1 wherein the degassing reduces dissolved oxygen content in the beverage by at least about 90 percent. 12 . (canceled) 13 . the invention of claim 1 wherein the degassing reduces dissolved oxygen content in the beverage by at least about 99 percent. 14 . (canceled) 15 . the invention of claim 1 wherein the brewed beverage is selected from the group consisting of coffee-based beverages and tea-based beverages. 16 . the invention of claim 15 wherein the coffee-based beverages are selected from the group consisting of affogato, caffè americano, café au lait, café bombón, caffè latte, café mélange, coffee milk, cafe mocha, ca phe sua da, cappuccino, cortado, eiskaffee, espresso, flat white, frappuccino, galão, greek frappé coffee, iced coffee, indian filter coffee, instant coffee, irish coffee, kopi susu, liqueur coffee, macchiato, mochasippi, naked coffee, turkish coffee, vienna coffee, yuanyang, and combinations thereof. 17 . the invention of claim 15 wherein the tea-based beverages are selected from the group consisting of white tea, yellow tea, green tea, oolong, tea, black tea, post-fermented tea, herbal tea, and combinations thereof. 18 . the invention of claim 1 wherein the degassing is achieved by purging with a gas selected from the group consisting of nitrogen, argon, helium, neon, sulfur hexafluoride, and combinations thereof. 19 . (canceled) 20 . the invention of claim 1 further comprising heating the beverage in a microwave oven prior to consumption. 21 . the invention of claim 8 wherein the beverage comprises a coffee concentrate. 22 . the invention of claim 21 wherein the method further comprises adding water to the container, such that the water and the beverage are configured to mix as the beverage begins to thaw. 23 - 33 . (canceled) 34 . the method of claim 1 wherein the sealed container is permeable to oxygen. 35 - 36 . (canceled) 37 . a method for producing a coffee beverage, comprising: brewing the coffee beverage to form a brewed coffee beverage; reducing a dissolved oxygen content of the brewed coffee beverage by degassing the brewed coffee beverage to form a degassed coffee beverage; storing the degassed coffee beverage in an oxygen-permeable container; and transitioning the degassed coffee beverage from a liquid state to a solid state by freezing the degassed coffee beverage after the brewed coffee beverage was degassed. 38 . the method of claim 37 wherein the degassing reduces the dissolved oxygen content in the degassed coffee beverage to less than 2.0 ppm, the method further comprising maintaining the degassed coffee beverage under an inert gas atmosphere while the degassed coffee beverage transitions from the liquid state to the solid state. 39 . the method of claim 38 where maintaining the degassed coffee beverage under the inert gas atmosphere comprises: filling a headspace of the oxygen-permeable container with an inert gas atmosphere; and applying a lid to the oxygen-permeable container before freezing the degassed coffee beverage to at least partially hold the inert gas atmosphere within the oxygen-permeable container while the degassed coffee beverage freezes. 40 . a method for producing a coffee beverage, comprising: reducing a dissolved oxygen content of a liquid by degassing the liquid to form a degassed liquid; brewing a coffee beverage using the degassed liquid to form a degassed coffee beverage; storing the degassed coffee beverage in an oxygen-permeable container; and transitioning the degassed coffee beverage from a liquid state to a solid state by freezing the degassed coffee beverage. 41 . a coffee product, comprising: a microwavable oxygen-permeable container; and a deoxygenated coffee beverage stored in the microwavable oxygen-permeable container in a solid frozen state with a dissolved oxygen content below 2 ppm. 42 . the coffee product of claim 41 , wherein the microwavable oxygen-permeable container comprises polypropylene, and wherein the deoxygenated coffee beverage does not require reconstitution prior to consumption.
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related applications this application claims the benefit of u.s. provisional application no. 61/345,455, filed may 17, 2010, the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. technical field the present invention relates generally to beverages—in some embodiments to coffee-based beverages—and to methods for the production thereof. background coffee is a popular beverage that can be enjoyed both hot and cold and in a variety of forms, including but not limited to espresso, lattes, iced coffees, and the like. a particularly popular form of coffee is brewed coffee in which hot water or steam is percolated through roasted coffee bean grounds in a process referred to as brewing. it has been shown that the most flavorful brewed coffee is achieved when freshly roasted coffee beans are ground and brewed, and consumed by a person within the first one hour of the brewing process. it is accepted that the optimal flavor for a coffee beverage is achieved by consuming the product within the first 30 minutes after brewing. such a short duration of time between brewing a coffee beverage and its consumption limits the exposure time of the coffee to heat and oxygen which can react with and/or otherwise cause the decomposition and/or polymerization of one or more of the many chemical compounds responsible for the coffee-based beverage's desirable tastes and aroma—chemical processes that can reduce the desired coffee flavors and introduce undesirable bitter and/or stale flavors. conventional wisdom has long held that coffee cannot be stored for extended periods of time without loss of flavor. in an effort to address this problem, instant coffee using the process of freeze-drying was developed and patented. although the freeze drying process does produce a form of coffee that can be stored for extended period of times, the freeze dried product must be reconstituted in hot water producing a beverage that has a taste and flavor that no longer resembles freshly brewed coffee. in short, it would be highly desirable to provide a coffee-based beverage and, indeed, other types of brewed beverages that can be stored for extended periods of time without exhibiting a concomitant loss of flavor and/or other undesirable deteriorations in taste, and which can be consumed without requiring reconstituting. summary the scope of the present invention is defined solely by the appended claims, and is not affected to any degree by the statements within this summary. by way of introduction, a method for producing a brewed beverage in accordance with the present teachings includes brewing the beverage, degassing the beverage prior to storing the beverage in a sealed container, and freezing the beverage. a first brewed beverage in accordance with the present teachings is produced according to methods of a type described above. a frozen brewed beverage in accordance with the present teachings is configured to be reheated prior to consumption and does not require reconstituting. a second brewed beverage in accordance with the present teachings is in a sealed container, has a dissolved oxygen content less than about 2 ppm, is configured to be reheated prior to consumption, and does not require reconstituting. brief description of the drawings fig. 1 shows a flowchart of a representative method for making a beverage in accordance with the present teachings. fig. 2 shows a flowchart of a representative method for consuming a beverage produced in accordance with the present teachings. detailed description beverages that can be stored for an extended period of time and later reheated without experiencing a degradation in flavor relative to the freshly brewed flavor that exists prior to packaging have been discovered and are described hereinbelow. in some embodiments, the beverage is obtained through a brewing process. in some embodiments, the beverage is coffee-based. in some embodiments, the beverage is tea-based. by way of introduction, the ability to maintain the flavor of freshly brewed beverages for extended periods of time provides a method for the long-term storage of beverages (including but not limited to coffee-based beverages) that requires no reconstitution—only reheating of the product. thus, the methods in accordance with the present teachings produce a product that allows the consumer the convenience of purchasing a frozen beverage product that can be stored in the freezer section of a refrigerator for an extended period of time and then taken out and reheated, so as to experience the taste and flavor of the beverage as if it were freshly brewed. in the case of a coffee-based beverage, the consumer is not required to purchase freshly roasted coffee beans, grind the beans with a grinding tool, have access to and/or operate a coffee brewing system, or have access to high quality water to add to the coffee brewer in order to enjoy a coffee flavored beverage having the flavor of freshly brewed coffee. on the contrary, the consumer need only have access to a freezer to store the containers containing the frozen coffee beverage and a heating source such as a microwave oven or a stove top cooking element to heat the frozen coffee beverage. moreover, the consumer does not need to add water to the frozen beverage in order to consume the beverage. the only step is to heat the frozen beverage to the desired temperature. of course, the consumer may also wish to add additional ingredients including but not limited to milk, cream, sugar, honey, or the like, although the number and amounts of any such optional ingredients will be determined by the consumer's taste. throughout this description and in the appended claims, the following definitions are to be understood: the term “brewed” refers to a process whereby one or more chemical constituents of a beverage's flavor base (e.g., seeds, herbs, tea leaves, coffee beans, and the like, and combinations thereof) are dissolved in a liquid (e.g., water) through a process of steeping, stewing, soaking, marinating, immersion or the like. in some embodiments, the liquid is hot (e.g., at or near its boiling point) at some point during its contact with the beverage's flavor base. the term “degassed” refers to the removal of dissolved atmospheric gasses (e.g., oxygen, carbon dioxide, etc.) from liquids. representative techniques for degassing include but are not limited to those described in an article entitled “removal of dissolved oxygen from water: a comparison of four common techniques” ( talanta, 1994, 41, no. 2, 211-215), the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. representative liquid degassing techniques for use in accordance with the present teachings include but are not limited to purging, boiling at atmospheric pressure, boiling under reduced pressure, sonication under reduced pressure, and the like, and combinations thereof. in some embodiments, degassing is achieved via purging (e.g., bubbling an inert gas—including but not limited to nitrogen, argon, and the like, and combinations thereof—into the liquid for a period of time). in some embodiments, a beverage in accordance with the present teachings is tea-based—in other words, a beverage derived from a brewing process in which one or more soluble compounds of tea leaves are extracted by hot water and/or steam. representative tea-based beverages in accordance with the present teachings can prepared from a variety of types of teas including but are not limited to white tea, yellow tea, green tea, oolong, tea, black tea, post-fermented tea, herbal tea (i.e., leaves, flowers, fruit, herbs or other plant material which, technically, are not teas inasmuch as they are devoid of camellia sinensis ), and the like, and combinations thereof. representative types of tea-based beverages in accordance with the present teachings include but are not limited to bata bata, bubble tea (foam tea), cha manao, cha yen (that tea), chai (masala chai), hong kong milk tea (pantyhose milk tea), iri ko, kashmiri chai, kombucha, matcha, obuku cha, sweet tea, tapioca pearl tea (boba tea), tea punch, the tarik (malaysian pulled tea), tibetan yak butter tea, and the like, and combinations thereof. in some embodiments, a beverage in accordance with the present teachings is coffee-based—in other words, a beverage derived from a brewing process in which one or more soluble compounds of coffee beans are extracted from ground coffee beans by hot water and/or steam. the coffee-based beverage may be produced from a specific type of coffee bean (e.g., the kona bean) or from a blend of different types of beans grown in different geographical areas. representative bean types include but are not limited to columbian, sumatra, jamaica blue mountain, panama, and the like, and combinations thereof. representative coffee-based beverages in accordance with the present teachings include but are not limited to affogato, cafè americano, café au lait, café bombón, caffè latte, café mélange, coffee milk, cafe mocha, ca phe sua da, cappuccino, cortado, eiskaffee, espresso, flat white, frappuccino, galão, greek frappé coffee, iced coffee, indian filter coffee, instant coffee, irish coffee, kopi susu, liqueur coffee, macchiato, mochasippi, naked coffee, turkish coffee, vienna coffee, yuanyang, and the like, and combinations thereof. in some embodiments, the preservation of freshly brewed coffee flavor involves the removal of dissolved oxygen gas from the coffee-based beverage solution prior to the freezing of the beverage into a solid state. the present inventor has discovered—surprisingly and unexpectedly—that without lowering the dissolved oxygen content within the brewed coffee-based beverage solution prior to freezing, there will be significant changes in the chemical composition of the beverage during storage, which result in a noticeable loss of desirable flavor when the coffee is reheated to a temperature of between 60° c. (140° f.) and 80° c. (176° f.) at which brewed coffee is typically drunk. this discovery is surprising and unexpected in view of the fact that some coffee brewers (e.g., the brewer sold under the tradename trifecta by bunn-o-matic corporation, the brewer sold under the tradename ru-1000 by the wilbur curtis company, etc.) deliberately inject air into the liquid as a way to aerate and agitate the liquid, thereby keeping solids dissolved. moreover, it has been reported that oxygen dissolved in water is responsible for drawing out the rich flavor of the coffee bean during the brewing process, such that oxygen enriched water—for example, the water sold by cielo (austin, tex.)—results in coffee having an enhanced flavor. in stark contrast to the implications of the above reports, the present inventor has discovered that freshly brewed coffee-based beverage samples in which the beverage was frozen at temperatures below its freezing point without prior elimination or reduction of the oxygen content dissolved in the beverage did not maintain the desired freshly brewed flavor for an extended period of time. it was further discovered that freshly brewed coffee-based beverages which were degassed and stored in a refrigerator between 0° c. (32° f.) and 5° c. (41° f.), such that the beverage was not frozen, did not maintain the original freshly brewed coffee flavor to the same extent achieved by a degassed sample that was also frozen. thus, in some embodiments, the combination of reducing dissolved oxygen content followed by freezing of the coffee-based beverage below its freezing point in a closed container immediately after brewing preserves the flavor of the freshly brewed coffee for an extended period of time ranging from one day to at least 12 months when stored below the beverage's freezing point. in some embodiments, the coffee-based beverage is an espresso, latte, iced coffee, or the like. by way of general introduction, a method for producing a brewed beverage in accordance with the present teachings includes brewing the beverage and degassing the beverage prior to storing the beverage in a sealed container. in some embodiments, the method further comprises freezing the beverage. in some embodiments, the beverage comprises water and the water is degassed prior to being used in the brewing. in other embodiments, the beverage is degassed after the brewing and prior to sealing the container. in some embodiments, the degassing is achieved by purging with a gas selected from the group consisting of nitrogen, argon, helium, neon, sulfur hexafluoride, and combinations thereof. in some embodiments, the method further comprises dispensing the beverage into a container. in some embodiments, the method further comprises substantially filling a headspace above the beverage with an inert atmosphere, which, in some embodiments, comprises a gas selected from the group consisting of nitrogen, argon, helium, neon, sulfur hexafluoride, and combinations thereof. in some embodiments, the method further comprises sealing the container. in some embodiments, the container is heat-sealed with a metal-containing seal (e.g., an aluminum-containing lid). in other embodiments, the container is sealed with a non-metal seal (e.g., a seal made from polypropylene, polycarbonate, polyethylene, polyethylene terephthalate, or the like, and combinations thereof). in some embodiments, at least a portion of the container (e.g., the portion that retains the beverage after the seal has been removed) is microwavable. in some embodiments, both the container and the seal are microwaveable. in embodiments in which the seal is microwavable, it may be desirable to puncture the seal prior to heating in the microwave in order to prevent the container from exploding. in some embodiments, the degassing reduces dissolved oxygen content in the beverage by at least about 50 percent, in some embodiments by at least about 75 percent, in some embodiments by at least about 90 percent, in some embodiments by at least about 95 percent, and in some embodiments by at least about 99 percent. in some embodiments, the degassing reduces dissolved oxygen content in the beverage to less than about 2.0 ppm, and in some embodiments to less than about 1.0 ppm. in some embodiments, the method further comprises heating the beverage in a microwave oven prior to consumption. in other embodiments (e.g., iced coffee), the beverage is heated in a microwave for a short duration of time, such that the beverage is thawed only partially (i.e., ice remains) at the time it is consumed. in some embodiments, the beverage comprises a coffee concentrate, which will be diluted prior to consumption. in such embodiments, the water used for dilution can be added to the container containing the frozen beverage before or after the container is sealed, such that mixing with the concentrate does not occur until the beverage and/or the water used for the dilution (e.g., the water and the beverage are both frozen in the container but separated by an interface) begin to thaw. brewed beverages in accordance with the present teachings can be prepared according to any of the methods described herein. although representative methods in accordance with the present teachings will now be described in reference to figs. 1 and 2 , it is to be understood that these representative schemes are merely illustrative and that certain steps can be omitted (e.g., freezing the beverage, heating the beverage in a microwave, etc.) and additional steps be performed (e.g., adding additional liquid to the beverage, etc.) as desired. in addition, it is to be understood that the sequence of steps shown in the schemes is merely representative and is not to be construed as limiting (e.g., the liquid can be degassed after the beverage has been brewed rather than before). it is to be further noted that while the embodiments described below relate to coffee-based beverages, the methods in accordance with the present teachings are also applicable to other beverages—particularly though not exclusively to brewed beverages, such as tea, herbal drinks, and the like. it is also to be understood that elements and features of the various representative methods described below may be combined in different ways to produce new embodiments that likewise fall within the scope of the present teachings. the drawings and the description below have been provided solely by way of illustration, and are not intended to limit the scope of the appended claims or their equivalents. in some embodiments, as shown in fig. 1 , brewing 101 is the first step in producing a frozen coffee-based beverage. those skilled in the art will recognize that while the base ingredient of this beverage is coffee, additional ingredients and flavors may also be added, including but not limited to dairy products, sugars, sweeteners, and the like, in a raw or pre-processed form. it is to be understood that a number of different formulations may be turned into coffee-based liquids in accordance with the present teachings. in some embodiments, as shown in fig. 1 , the second step of the process involves reducing the dissolved oxygen content of the coffee-based beverage by degassing 102 . the reduction of dissolved oxygen in coffee-based beverage solution prior to freezing reduces the exposure of sensitive flavor compounds in the coffee to the dissolved oxygen. without wishing to be bound by a particular theory or to in any way limit the scope of the appended claims or their equivalents, it is presently believed that degassing the brewed coffee-based beverage prior to freezing results in the formation of significantly fewer bubbles and voids in the resulting ice and, therefore, fewer channels through which any oxygen entering the package could penetrate into the frozen beverage and begin to chemically react with the flavor-inducing coffee compounds. therefore, having the coffee flavor compounds of the beverage encapsulated in ice with few or no defects—a benefit of having first removed the bubble-forming dissolved oxygen prior to freezing—allows for the storage of coffee-based beverages for extended periods of time. degassing of the coffee-based beverage prior to packaging and freezing can be accomplished by a variety of techniques. it is also envisioned that the degassing process can be performed at any point in the process up to the time the container is sealed. in some embodiments, degassing is performed prior to freezing of the product (if the product is to be frozen) by degassing the water to be used in the brewing process prior to the brewing step 101 . in other embodiments, degassing of the beverage solution is performed after the brewing process 101 is complete and prior to freezing (although, in some embodiments, degassing after brewing may not be desirable if there are volatiles that make desirable contributions to flavor and/or aroma that could potentially be driven out). in step 102 shown in fig. 1 , the degassing process occurs immediately prior to filling the disposable containers and before freezing. performing the degassing process immediately prior to freezing reduces the risk that oxygen can be re-introduced into the solution and reduces the time in which the beverage solution needs to be maintained under an inert atmosphere before it is packaged, sealed, and frozen. in some embodiments, the degassing of the coffee-based beverage shown in step 102 of fig. 1 is accomplished by the ultra-sonic agitation of the beverage solution in a vessel where the headspace is filled with an inert atmosphere such as nitrogen gas. other gases that could be chosen include but are not limited to argon, helium, neon, sulfur hexafluoride, and combinations thereof. in some embodiments, the ultra-sonic agitation may be performed for a period ranging from about 1 second to about 60 minutes depending on the size of the vessel holding the beverage, the power of the ultrasonic transducer, and the desired reduction of the dissolved oxygen concentration. in some embodiments, the ultra-sonic agitation can be stopped when the dissolved oxygen concentration in the beverage is less than about 10 percent of the concentration before the start of ultra-sonic agitation. in some embodiments, the degassing process 102 is achieved by connecting the closed vessel containing the beverage solution to a vacuum pump, which lowers the atmospheric pressure in the vessel and causes the release of dissolved gases in the beverage solution. agitation or stirring can also be performed during the vacuum pumping process to assist in the elimination of the dissolved gases. in some embodiments, the degassing process 102 is performed by passing the beverage solution through a polymeric semipermeable membrane tube surrounded by a vacuum. the polymeric membrane is designed such that dissolved gases in the beverage solution can permeate the membrane while water and other organic compounds in the beverage cannot. examples of representative degassing processes for solvents that can be used in accordance with the present teachings are described in u.s. pat. no. 5,340,384, the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. in some embodiments, the degassing process 102 is accomplished by vigorous agitation of the beverage in a closed container that has been purged with an inert gas such as nitrogen. other potential inert gases can be used instead of or in combination with nitrogen, including but not limited to argon, helium, neon, sulfur hexafluoride, and combinations thereof. the beverage is agitated for a time of between about 1 second and about 5 minutes after which the excess pressure in the container is released by opening a valve. the process is repeated until no noticeable pressure increase is observed. before each agitation cycle, the atmosphere above the beverage in the vessel can be purged with nitrogen for a period of time to remove any residual oxygen from the atmosphere. the amount of time for the purge process will be dependent on the size of the vessel and the desired reduction in the concentration of dissolved oxygen in the beverage. in some embodiments, the degassing process is accomplished by bubbling an inert gas such as nitrogen through the beverage in a container, such that dissolved oxygen in the beverage solution is displaced by the inert gas. in some embodiments, in addition to the bubbling, the headspace is also filled with an inert gas. in some embodiments, the bubbling process can proceed for a time ranging from minutes to several hours depending on the volume of beverage being degassed, the bubbling rate, and the desired reduction in the concentration of dissolved oxygen. the degassing by bubbling can also be assisted with stirring and/or with a vacuum applied to the headspace above the beverage. as will be appreciated by the skilled artisan, any combination of degassing techniques—both the techniques described above as well as all manner of additional degassing techniques—may be used to achieve the degassed beverage solution of 102 without deviating from the present teachings. it is to be understood that the particular degassing technique or techniques used in accordance with the present teachings is not restricted. in the third step 103 of the flowchart shown in fig. 1 , the degassed coffee-based beverage is dispensed into containers, which, in some embodiments, are disposable. the disposable containers can be designed such that the beverage can be drunk directly from the container after reheating in a microwave oven. in some embodiments, the container prior to sealing contains a headspace sufficient to allow for the expansion of water upon its conversion to ice (thereby minimizing stress to the container upon freezing of the beverage). in some embodiments, the disposable container can hold at least 236 ml (8 us fl. oz.). in some embodiments, the container is made from a recycled polymer in which air is injected into the core to create an insulating barrier, such that the container can still be held on the outer surface comfortably by a person's bare hand even when it contains a hot liquid. one such material is described in u.s. pat. no. 7,585,439, the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. in some embodiments, the container can hold a liquid volume of at least one fluid ounce. the coffee-based beverage will assume the shape of the container when the beverage is dispensed into it and frozen. in some embodiments, the container may have a slight wedge shape such that the diameter of the bottom portion of the container is smaller than the top portion. in such a design, the frozen coffee-based beverage can be easily removed from the container by the consumer and dropped into another container such as a ceramic mug. the frozen beverage block in the shape of the disposable container can be easily slid out when warmed by the consumer's hand for a few seconds. a thin layer of water forms at the plastic container/ice interface, such that the frozen beverage can easily slide out of the disposable container. some consumers may wish to drink the beverage from their own coffee mug rather than from the container in which it is packaged. thus, the frozen beverage can be transferred to the mug, and the mug can then be reheated in a microwave oven. although this choice is available to the consumer, it is not a requirement since the frozen coffee-beverage can be reheated and consumed directly in the disposable container in which the product was supplied. brewed beverages in accordance with the present teachings can be used to advantage both in the hospitality industry (e.g., restaurants, hotels, catering services, and the like) as well as by individual consumers in their homes. for example, with respect to the former, many high-end restaurants, hotels, and the like steer away from serving the highest quality coffees (e.g., jamaica blue mountain coffee beans) in view of the high cost of the beans and the fact that a considerable amount of the brewed coffee is ultimately left unconsumed by clientele and is eventually discarded. however, in accordance with the present teachings, individual cups of the high-end coffees can be prepared as requested without any compromise in fresh brewed flavor, without waste of product, and at the minimum of expense to the establishment. this is particularly true with respect to embodiments in which a frozen coffee-based beverage in accordance with the present teachings is easily removable from its container such that it can be transferred into another venue-specific container (e.g., a coffee cup emblazoned with a hotel's name) prior to being heated and served to a customer. from the point of view of an individual consumer, the brewed beverages in accordance with the present teachings are highly desirable since a product with a consistently good flavor can be prepared from a higher quality water (e.g., purified, micro-filtered, mineral-enhanced, etc.) than might otherwise have been available to the consumer, which does not require the consumer to experiment unnecessarily with varying proportions of coffee grounds to water in an effort to optimize the flavor and/or strength of the brewed beverage. in some embodiments, the frozen coffee-based beverage is packaged in a polymer container that does not have thermal insulating properties sufficient to prevent the outside of the container from becoming so hot after the reheating of the frozen coffee-based beverage as to make holding the container in a person's bare hands uncomfortable. in such cases, a paper-based insulating sleeve can be included in the packaging of the product so that the consumer can place the sleeve around the container to improve the comfort to the person holding the reheated beverage. such a representative paper sleeve is described in u.s. pat. no. 5,425,497, the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. representative polymer materials from which the container and/or its lid can be constructed include but are not limited to polypropylene (pp), polycarbonate (pc), low density polyethylene (ldpe), high density polyethylene (hdpe), polyethylene terephthalate (pet), and the like, and combinations thereof. in some embodiments, the choice of container can also be influenced by the oxygen transmission rate of the polymer material. materials that provide better oxygen barrier properties can help to prevent the reintroduction of oxygen into the coffee solution after the degassing and freezing steps. although pet provides a good barrier to oxygen and, in some embodiments, can be used to make the container, pet has a relatively low softening point that can render it an unsatisfactory container material if the container containing the frozen beverage is to be heated in, for example, a microwave. however, since the beverage stored in the container is already degassed—which results in a higher quality ice lacking many of the bubbles and voids found in ice prepared from oxygen-infused water, as noted above—a less effective oxygen barrier material (e.g., polypropylene) having a higher softening point than pet, which is suitable for use in a microwave, can be used instead. the reason that a material like pp can be used in place of pet without unduly subjecting the beverage in the sealed container to undesirable oxidation is that without the bubbles and voids of conventional oxygen-containing ice, any reaction involving oxygen permeating the container will largely be restricted to the surface of the frozen beverage since such oxygen cannot adequately penetrate the ice itself in the absence of bubbles and voids as explained, for example, in the article entitled “permeation of gases through ice” ( tellus xi, 1959, 3, 355-359), the entire contents of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present specification, the disclosure or definition herein shall be deemed to prevail. in some embodiments, at least some portion of the container comprises a flexible wall. in some embodiments, the choice of material for the container can be extended to non-polymer materials such as glass if sufficient room is left in the container during the filling process so as to accommodate the expansion of the beverage solution as it transitions from its liquid to solid state during the freezing process. another consideration in the choice of container material is the material's compatibility with microwave heating. in some embodiments, the material has a softening temperature greater than the temperature to which the beverage will be heated. one non-limiting example of such a representative material is polypropylene. as shown in fig. 1 , a lid is applied to the disposable container filled with the degassed coffee-based beverage, as shown in step 104 of fig. 1 . in some embodiments, the headspace above the degassed coffee-based beverage is controlled so that an inert atmosphere is trapped above the beverage after the lid seals the container. the headspace pressure of inert atmosphere can be controlled so that it can compensate for the drop in pressure in the headspace caused by freezing the beverage, thus preventing the lid and disposable container from deforming inwardly due to a lower internal pressure. in some embodiments, the lidding material contains an aluminum film to help prevent oxygen penetration into the container after it is sealed. in some embodiments, the lids are applied to the disposable containers filled with coffee-based beverage using standard hot stamping techniques and equipment available in the packaging industry. in some embodiments, as shown in step 105 of fig. 1 , the coffee-based beverage is frozen. the freezing process is accomplished by cooling the coffee-based beverage below the solution's freezing point. the freezing can be accomplished by a variety of methods and at a variety of different cooling rates. in some embodiments, the beverage can be dispensed into individual disposable containers that are ultimately purchased by the consumer. in some embodiments, the containers are then sent to a refrigeration system to cool the temperature of the beverage below its freezing point. the freezing process is performed as quickly as possible after the coffee-based beverage is dispensed into the disposable containers and sealed, preferably in less than 1 hour after the dispensing has occurred. in some embodiments, the freezing takes place in a large walk-in style freezer, such as that produced by manufacturers such as elliot-williams co., inc. in some embodiments, the refrigeration unit is an in-line unit such as the cryoline® series sold by linde, inc. other freezing techniques may also be employed including but not limited to the quick freezing techniques used for freezing shrimp, ice cream, and other foods, which employ cryogenic refrigerants. in such techniques, the food to be frozen is conveyed through a tunnel while being exposed to a cryogenic refrigerant. it is envisioned that the methods described herein can be performed in a modern food packaging facility in which the necessary equipment to brew a coffee-based beverage, degas the beverage, dispense the beverage into disposable containers, seal the containers under an inert atmosphere, and freeze the product are available such that the entire process can be performed rapidly and efficiently. in some embodiments, the completed coffee-based product is shipped frozen to retail stores, purchased by a consumer as a frozen beverage in a disposable cup, and stored at home or work in a freezer maintained at a temperature below the freezing point of the beverage. fig. 2 shows a flowchart outlining representative steps in the consumption of a coffee-based beverage prepared in accordance with the present teachings. when a coffee-based beverage is desired, the person retrieves a disposable container containing the beverage from the freezer as shown in step 201 of fig. 2 , removes the lidding material sealing the beverage as shown in 202 , and places the beverage into a microwave oven for a period of time sufficient to heat the beverage to a temperature of a warm cup of coffee as shown in 203 . typically, the frozen beverage will need to be heated for a period of about 120 to about 180 seconds in order to reach the desired temperature, typically between about 60° c. (140° f.) and about 80° c. (176° f.). of course, heating times will vary depending on the microwave's size, power settings, and desired beverage temperature. in some embodiments, the consumer wishes to consume black coffee and the beverage is ready to drink, as shown in 205 . alternatively, as shown in optional step 204 , milk or other dairy products (e.g., cream) and a sweetener (e.g., sugar) can be added after heating to adjust the taste to the consumer's desire. it is to be noted that in contrast to conventional methods, no reconstituting of the beverage is required prior to consumption. in short, the present teachings provide a beverage in which the taste of freshly brewed coffee is combined with the convenience of a ready-to serve coffee beverage after a short reheating step. the following example illustrates features in accordance with the present teachings, and is provided solely by way of illustration. it is not intended to limit the scope of the appended claims or their equivalents. example blind taste test experiments were performed with two subjects. in both instances, the subject was asked to taste two cups of coffee. one cup of coffee was freshly prepared and the other cup of coffee had been prepared one month earlier by a method in accordance with the present teachings and then maintained in a freezer at −10° c. prior to being heated for the tasting. both cups of coffee (i.e., freshly prepared and that obtained by heating frozen coffee in accordance with the present teachings) were prepared from the same type of coffee bean. in both instances, the subjects indicated the inability to distinguish any discernable taste difference between freshly brewed coffee and coffee prepared by heating frozen coffee in accordance with the present teachings. moreover, the subjects indicated that both samples tasted like freshly brewed coffee. the foregoing detailed description and accompanying drawings have been provided by way of explanation and illustration, and are not intended to limit the scope of the appended claims. many variations in the presently preferred embodiments illustrated herein will be apparent to one of ordinary skill in the art, and remain within the scope of the appended claims and their equivalents. it is to be understood that the elements and features recited in the appended claims may be combined in different ways to produce new claims that likewise fall within the scope of the present invention. thus, whereas the dependent claims appended below depend from only a single independent or dependent claim, it is to be understood that these dependent claims can, alternatively, be made to depend in the alternative from any preceding claim—whether independent or dependent—and that such new combinations are to be understood as forming a part of the present specification.
|
082-767-062-971-792
|
JP
|
[
"US",
"WO",
"CN",
"JP"
] |
B23P15/14,B21K1/30,B21D53/28,B21J5/08
| 2008-01-25T00:00:00 |
2008
|
[
"B23",
"B21"
] |
method of manufacturing metal member with plurality of projections
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projections of a bevel gear or a vibrating body are formed by bending a metal-made plate member having a plurality of projections so as to direct them in the same direction and make their projecting direction include a component of out-of-plane direction and subsequently applying a load to the bent plate member to crush the projections so as to reduce the height thereof and increase the plate thickness.
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1 . a method of manufacturing a metal member having a plurality of projections, comprising: a step of bending a plurality of projections of a metal-made plate member having the plurality of projections so as to make their projecting direction include a component of an out-of-plane direction; and a step of applying a load having the component of the out-of-plane direction to the plurality of projections to increase the plate thickness of the plurality of projections. 2 . the method according to claim 1 , wherein the metal-made plate member is a circular plate member with the plurality of projections formed along the inner periphery or the outer periphery thereof; and the plate member is bent to form a cylinder by the plurality of projections in the bending step. 3 . the method according to claim 2 , wherein the load is applied to the plurality of projections in a direction running along an axis of the cylinder to increase the thickness of the plurality of projections in a radial direction of the cylinder in the step of increasing the plate thickness of the plurality of projections. 4 . the method according to claim 1 , further comprising: a step of forming the metal-made plate member having a plurality of projections by punching out a metal-made plate. 5 . the method according to claim 1 , further comprising: a step of forming the metal-made plate member having the plurality of projections by shearing a metal-made plate. 6 . the method according to claim 1 , wherein the step of directing the projections to the projecting direction including a component of the out-of-plane direction is realized by drawing, burring, bulging or dibbling. 7 . the method according to claim 1 , wherein the step of increasing the plate thickness of the projections is realized by forging or heading.
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technical field this invention relates to a method of manufacturing a metal member having a plurality of projections such as a bevel gear or a vibrating body of an ultrasonic motor where the projections amplify vibrations. background art techniques for punching a metal plate member in order to form a sprocket wheel having radial projections are known. however, punching is not suited for forming a bevel gear having teeth projecting in a direction that crosses radial directions, although a bevel gear is also a gear. grinding and cutting are known as techniques for cutting grooves to produce teeth in order to form a bevel gear. forging and sheet metal stamping using a press device are also known as techniques for forming a bevel gear (refer to, e.g., japanese patent application laid-open nos. h11-188449 and 2001-205385). the process of forming teeth of a bevel gear can be simplified by using the forging or sheet metal stamping technique to reduce the manufacturing cost if compared with the process of forming such teeth by using the grinding or cutting technique. therefore, sheet metal stamping or forging is advantageous relative to grinding or cutting for forming bevel gears on a mass production basis from the viewpoint of manufacturing cost. members having a plurality of projections that look like teeth projecting in the same direction include, besides a bevel gear, a vibrating body of an ultrasonic motor having projections for amplifying vibrations. an ultrasonic motor has a vibrating body equipped with a piezoelectric element, which is a sort of electro-mechanical transducer, and is designed to generate a traveling wave on the surface of the vibrating body by supplying an alternating signal to the piezoelectric element and drive a moving body held in contact with the vibrating body by utilizing the traveling wave. projections are formed on the surface of the vibrating body in order to boost the amplitude of the traveling wave generated on the surface of the vibrating body. sheet metal stamping and forging using a press device are known as techniques for forming projections for amplifying the vibrations of the vibrating body (refer to, e.g., japanese patent application laid-open no. h07-135785). a press die having fins for forming grooves has to be provided in order to form a large number of teeth or projections projecting in the same direction on the surface of a metal object to be worked by forging or sheet metal stamping. fig. 21 is a schematic illustration of forming grooves on an object to be worked by sheet metal stamping. fig. 21 illustrates a metal object 93 to be worked and fins 97 a of a metal die. grooves are formed by applying a load on the metal object 93 to be worked by means of the fins 97 a . in other words, the fins 97 a are subjected to a heavy load. when narrow grooves are to be formed, thin fins 97 a need to be used to form such narrow grooves. then, the strength of the fins 97 a is reduced so that the fins 97 a may highly possibly be damaged when they are used for forging or sheet metal stamping. therefore, the width of the grooves to be formed needs to have a certain large value in order to make the fins 97 a show a certain degree of strength. thus, the width of the projections of a bevel gear or a vibrating body to be formed in this way is subjected to a certain limitation. even if the metal die has a strength that is sufficient for bearing a single compression forming process, it is clear that the load to be applied in a single compression forming process is preferably small from the viewpoint of repeatedly using the metal die for compression forming. for this reason, the projections of a bevel gear or a vibrating body to be formed on a mass production basis are subjected to limitations in terms of their profile in order to reduce the load to be applied to the metal die. thus, the currently available methods of manufacturing a metal member having a plurality of projections have much room for improvement from the viewpoint of easily forming a plurality of projections projecting in the same direction with a desired width and reducing the load to be applied to the metal die in a compression forming process. disclosure of the invention according to the present invention, the above-identified problem is dissolved by providing a method of manufacturing a metal member having a plurality of projections that includes: a step of bending a plurality of projections of a metal-made plate member having the plurality of projections so as to make their projecting direction include the component of out-of-plane direction; and a step of applying a load having the component of out-of-plane direction to the plurality of projections to increase the plate thickness of the plurality of projections. thus, according to the present invention, the load applied to the metal die at the time of compression forming can be suppressed and the grooves among the projections can be formed with a desired width without resorting to grinding and/or cutting when forming a metal member having a plurality of projections. brief description of the drawings fig. 1 is a schematic illustration of the step of punching out a sprocket-shaped member from a plate member in a first embodiment of the present invention. fig. 2 is a schematic illustration of the step of deforming a sprocket-shaped member to produce a crown-shaped member by press-drawing in the first embodiment. fig. 3 is a schematic illustration of a crown-shaped member produced in the first embodiment, illustrating an appearance thereof. fig. 4 is a schematic illustration of punching out a bottom part of the crown-shaped member of fig. 3 . fig. 5 is a schematic illustration of the step of forging a crown-shaped member in the first embodiment. fig. 6 is a schematic cross-sectional view of a punch, a die and a crown-shaped member before the crown-shaped member is forged in the first embodiment. fig. 7 is a schematic cross-sectional view of a vibrating body formed by forging by the first embodiment of the present invention. fig. 8 is a schematic illustration of the relationship between the profile of the fins of a die and that of the projections of a crown-shaped member in the forging step of the first embodiment. fig. 9 is a schematic perspective view of a vibrating body by compression forming in the forging step of the first embodiment. fig. 10 is a schematic illustration of the first forging step of forging a crown-shaped member in a second embodiment of the present invention. fig. 11 is a schematic illustration of the second forging step of forging a crown-shaped member in the second embodiment. fig. 12 is a schematic illustration of a flat ring member of stainless steel sheared by sheet metal stamping in a third embodiment of the present invention. fig. 13 is a schematic illustration of a ring member produced by burring in the third embodiment. fig. 14 is a schematic illustration of punching out an outer peripheral part of the crown-shaped member of fig. 13 . fig. 15 is a schematic illustration of a flat ring member sheared from a stainless steel plate by sheet metal stamping in a fourth embodiment of the present invention. fig. 16 is a schematic illustration of a crown-shaped member obtained by drawing a ring member in the fourth embodiment. fig. 17 is a schematic illustration of a crown-shaped member produced by pushing and spreading out front end parts of the projections thereof by means of a tapered punch in the fourth embodiment. fig. 18 is a schematic perspective view of a vibrating body formed by forging in the fourth embodiment. fig. 19 is a schematic perspective view of a bevel gear that can be produced by applying any of the embodiments of forming method according to the present invention. fig. 20 is a schematic perspective view of a hypoid gear that can be produced by applying any of the embodiments of forming method according to the present invention. fig. 21 is a schematic illustration of a known step of forming a plurality of projections by sheet metal stamping. best mode for carrying out the invention now, exemplary embodiments of the present invention will be described in greater detail by referring to the accompanying drawings. first embodiment the first embodiment of a method of manufacturing a metal member having a plurality of projections projecting in the same direction will be described in terms of a vibrating body having projections on the surface thereof for amplifying vibrations that is to be used for an ultrasonic motor. the ultrasonic motor has a vibrating body equipped with a piezoelectric element, which is a sort of electro-mechanical transducer, and is designed to generate a traveling wave on the surface of the vibrating body by supplying an alternating signal to the piezoelectric element and drive a moving body held in contact with the vibrating body by utilizing the traveling wave. now, this embodiment of method of forming projections for amplifying vibrations on a vibrating body will be described below by referring to figs. 1 through 7 . fig. 1 is a schematic illustration of the step of punching out a sprocket-shaped member from a metal plate member. fig. 1 illustrates a stainless steel plate member 10 that is conveyed gradually in a longitudinal direction. the plate member may be made of spc material, low alloy steel, high alloy steel or a non-ferrous metal alloy. pilot holes 1 are punched through the plate member 10 at regular intervals by means of an apparatus that is not illustrated here. the pilot holes 1 operate as positioning holes in a subsequent sheet metal stamping step. then, inner holes 2 are punched out for a centering operation that takes place in a subsequent press-drawing step. each inner hole 2 is positioned by referring to a positioning punch put into a pilot hole 1 . thereafter, a punching position is determined by referring to the pilot hole 1 by means of the punch and a circular sprocket-shaped plate member 3 having a ring-like base section 3 b and a plurality of projections 3 a respectively along the inner periphery and the outer periphery thereof is punched out. as a result, the sprocket-shaped plate member 3 and the inner hole 2 are made to be highly coaxial. the plate member has a profile having projections projecting in different in-plane directions. fig. 2 is a schematic illustration of the step of deforming the sprocket-shaped member 3 to produce a crown-shaped member 13 by press-drawing. fig. 2 illustrates a punch 4 and a die 5 . the punch 4 has a stepped section at the front end thereof to be engaged with the inner hole 2 of the sprocket-shaped member 3 . as the stepped section of the punch is engaged with the inner hole 2 , the sprocket-shaped member 3 can be positioned correctly for press-drawing. however, the sprocket-shaped member 3 may not be provided with an inner hole 2 when the die 5 has a member for positioning the sprocket-shaped member 3 . as the punch 4 that is engaged with the inner hole 2 is lowered, the sprocket-shaped member 3 is drawn into the gap between the punch 4 and the die 5 until the outer peripheral part of the sprocket-shaped member 3 where the projections are formed is bent orthogonally along a line slightly inner relative to the bases of the projections to produce a crown-shaped member 13 showing a cylindrical profile. the projections are directed in an out-of-plane direction without grinding and/or cutting by bending the plate member having projections. fig. 3 is a schematic illustration of such a crown-shaped member 3 , illustrating an appearance thereof. as a sprocket-shaped member 3 is subjected to press-drawing, the projections 13 a that are arranged circularly around the central axis of the crown-shaped member 13 are made to project from the base section 13 b in a same and identical direction running along the central axis of the member 13 . an inner hole 12 is the same as the inner hole 2 of the sprocket-shaped member 3 . since the outer peripheral part of the sprocket-shaped member 3 is made to shrink by the press-drawing, the intervals of the projections 13 a of the crown-shaped member 13 are made smaller than the intervals of the projections 3 a of the sprocket-shaped member 3 . this is advantageous from the viewpoint of forming a vibrating body having projections with circumferential narrow grooves that separate the projections because the load of formation in a subsequent forging step is reduced when the grooves are narrowed in advance. then, the ring-like crown-shaped member 13 is made to show a profile as illustrated in fig. 4 by punching out the bottom of the crown-shaped member 13 . the operation of punching out the bottom of the crown-shaped member 13 may not be necessary depending on the desired profile of the vibrating body to be produced. the crown-shaped member 13 whose bottom is punched out is then subjected to an annealing heat treatment so as to be softened for the purpose of reducing the load of formation and making it easy to plastically deform the crown-shaped member 13 in a subsequent forging step. the annealing heat treatment may be omitted depending on the degree of drawing particularly when the material is not hardened excessively and the resistance of the material against deformation is not so large. the surface of the crown-shaped member 13 that is softened by the annealing heat treatment is then lubricated. then, the crown-shaped member 13 is subjected to forging. fig. 5 is a schematic illustration of the step of forging a crown-shaped member 13 . in this embodiment, the crown-shaped member 13 is turned upside down and a load is applied thereto for forging, or compression forming, in the projecting direction of the projections 13 a along the axis of the crown-shaped member 13 . the lower metal die to be used for the forging is provided with a plurality of fins 7 a , which fins 7 a define the profile of the grooves separating the projections of a vibrating body for amplifying vibrations of the vibrating body. fig. 6 is a schematic cross-sectional view of a punch 6 , a die 7 and a crown-shaped member 13 before being forged. fig. 7 is a schematic cross-sectional view of a vibrating body 23 formed by forging. in this embodiment, the lower metal die 7 is provided with circularly arranged grooves into which the projections 13 a of the crown-shaped member 13 are inserted respectively. fins 7 a are arranged at regular intervals in the respective grooves that are circularly arranged. both the outer peripheral walls and the inner peripheral walls of the grooves are sloped such that the radial width of the grooves is reduced toward the bottoms of the grooves and the width of the grooves at the bottoms thereof is smaller than the plate thickness of the projections 13 a . a base section 13 b of a projection 13 a is located between the base of the projection 13 a and the part thereof that is bent by drawing. since the inner peripheral walls and the outer peripheral walls of the die 7 are sloped, center position of the crown-shaped member is automatically aligned with that of the die 7 to secure a high degree of dimensional precision of the formed product. after circumferentially positioning the crown-shaped member 13 so as to place each of the projections 13 a of the crown-shaped member 13 between a pair of adjacently located fins 7 a of the die 7 , the punch 6 is lowered to compression-forming the crown-shaped member 13 . due to the forging and the resultant compression forming, the radial width and hence the plate thickness of the projections 13 a and the base sections 13 b of the crown-shaped member 13 are increased so that the crown-shaped member 13 is deformed so as to show a profile with a thickness as large as the gaps between the outer peripheral walls and the inner peripheral walls. then, as a result, a vibrating body 23 having projections 23 a and base sections 23 b is produced with a profile as illustrated in fig. 7 . since the volume of the crown-shaped member 13 may show a variance, the metal die is so designed in this embodiment that the excessive thickness, if any, produced by the compression forming is allowed to exist at the inner peripheral side. as a result of the forging step, the projections are deformed to become thick in radial directions due to the compression so that the thin fins 7 a are not subjected to a heavy load. additionally, substantially equal loads are applied to the fins 7 a from the opposite lateral sides. therefore, fins 7 a will not be damaged if they do not show a very high strength. with a vibrating body 23 having such a profile, a mass sufficient for satisfactorily securing energy of vibration can be secured for the projections of the vibrating body and the grooves formed between adjacent projections can be made to show a minimal width to improve the abrasion-resistance of the projections that are brought into contact with the vibrating body. the profile of the vibrating body 23 produced after the forging step may not necessarily be same as the one illustrated in fig. 7 so long as the radial width, or the plate thickness, of the projections 13 a is raised by the forging step. alternatively, for example, the radial width of the projections 13 a and those of the base sections 13 b of the crown-shaped member 13 may be equally increased or the radial width of only the projections 13 a may be increased. fig. 8 is a schematic illustration of the relationship between the profile of the fins 7 a of a die 7 and that of the projections 13 a of a crown-shaped member 13 in the forging step, where some of the circularly arranged fins 7 a are extended on a straight line. before the forging step, the projections of the crown-shaped member 13 are made higher than the fins 7 a of the die 7 to secure a sufficient volume for the projections 23 a after the forging step. fig. 9 is a schematic perspective view of a vibrating body 23 compressed and formed by forging. a piezoelectric element that is an electro-mechanical transducer is rigidly fitted to the bottom surface of the vibrating body 23 and an electrode pattern that matches the form of vibrations produced to the vibrating body by excitation is formed on the piezoelectric element. a plurality of standing waves are generated in the vibrating body as an alternating voltage is applied to the electrode pattern and a traveling wave is formed on the surface of the vibrating body 23 when the plurality of standing waves are generated simultaneously. the amplitude of the traveling wave generated on the surface of the vibrating body 23 can be boosted by arranging projections 23 a along the circumferential end facet of the vibrating body 23 . thus, outputs as ultrasonic motor can be improved. the projections 23 a that are arranged to appear like a ring are held in contact with a ring-like rotating body (not illustrated) and the rotating body is driven to rotate by the traveling wave that is generated on the surface of the vibrating body 23 and whose displacement is boosted by the projections 23 a. increasing the width of the projections produced by compression forming on the vibrating body of an ultrasonic motor is advantageous not only for improving the abrasion-resistance but also for suppressing unnecessary vibrations. the profile of the projections of the vibrating body is preferably such that it provides a large volume to the projections relative to the surface area thereof because the projections have few proper vibration modes and the frequencies of the proper vibration modes are high with such a profile so that unnecessary vibrations can hardly occur due to the projections themselves. if a crown-shaped member 13 produced as a result of the drawing is used as a vibrating body without any subsequent process, the projections 13 a show a small radial width. if an alternating voltage is applied to the piezoelectric element to generate vibrations in the vibrating body under this condition, proper vibrations are generated in the projections 13 a to make it vibrate in radial directions like so many cantilevers, which are unnecessary vibrations. thus, increasing the radial width of the projections 13 a by compression forming to raise the radial rigidity thereof against vibrations provides an advantage of suppressing unnecessary vibrations attributable to the projections 13 a. now, some of the results obtained by comparing the known method of forming projections on an object to be worked having no projections by forming grooves, using a die having fins, as illustrated in fig. 21 and this embodiment of method according to the present invention will be described below. with this embodiment, the final profile of the vibrating body to be formed is a ring-like vibrating body having an outer diameter of 62 mm and the radial width and the height of the base section thereof is 5 mm and 5.4 mm respectively while the radial width and the height of the front end sections of the projections are 1 mm and 2.7 mm respectively. the die and the punch are made of high-speed steel and the circumferential width and the height of each of the fins of the die prepared by electric discharge machining are 0.6 mm and 2.7 mm respectively. in an experiment, a ring-like object to be worked having the above-cited dimensions including the outer diameter and the widths was forged to form grooves separating projections by means of a punch and a die having fins as illustrated in fig. 21 . however, it was not possible to satisfactorily produce projections and the metal die was broken in the course of the process of producing projections having rounded front end sections. with the method illustrated in fig. 21 , the object to be worked is sheared by the fins so that fresh surfaces newly appear on the sheared sites to give rise to a lubricant shortage and make the pushing process a difficult one. when an object to be worked that is apt to give rise to a phenomenon of plastic flow is forged without a special arrangement for making lubricant follow the deformation of the object that is being worked, a lubricant shortage takes place as the object is deformed to give rise to seizure and/or some other trouble. therefore, a process of integrally producing a chemical conversion coating film and a lubricant ingredient that reacts with the coating film is generally executed on the surface of the object to be worked in order to secure lubricant for the forging process. however, a chromium passive coating film that contributes to raise the degree of anti-corrosiveness is formed on the surface of stainless steel to make it difficult to produce a uniform chemical conversion coating film on the surface thereof. additionally, many different types of stainless steel show a high strain hardening coefficient and hence are hardened when subjected to compression deforming to increase the deformation resistance thereof and make it difficult to produce a complex profile by forging. to the contrary, with this embodiment, stainless steel is not sheared by compression forming and no site where any local deformation is boosted appears to make it easy to execute a compression forming process on stainless steel, although it has been difficult to make stainless steel show a desired profile by forging. for example, for a compression forming process for forming a vibrating body made of martensite-based stainless steel sus420j2 and showing the above-described final profile, the known method illustrated in fig. 21 requires a load of 300 tons or more while this embodiment requires only a load of 120 tons. furthermore, some of the fins of the die were broken when an object to be worked is pushed down by a punch on the die by means of the former method. when manufacturing a product from an object to be worked by compression forming such as forging, not only the load of the metal die is reduced and the service life of the metal die is prolonged but also seizure due to a lubricant shortage can be prevented from taking place by minimizing the load necessary for the compression forming. additionally, an effect of reducing the extent of springing back and improving the dimensional accuracy of the formed product is also achieved by reducing the load necessary for the compression forming. furthermore, the compression forming process can be executed by means of a small press machine when the load necessary for the compression forming is reduced. with the known manufacturing method illustrated in fig. 21 , all the load applied to the die is concentrated to the fine fins that are held in contact with the object to be worked so that the stress there becomes very large to eventually damage the fins. additionally, this process is a sort of extrusion process and a lubricant shortage is likely to take place at the areas of the surface of the object to be worked that contact the fins so that so-called fresh surfaces appear there to give rise to seizure at the fins. to the contrary, when projections are formed on the object to be worked in advance before the object is forged according to the present invention, the projections are crushed to fill the inside of the die and the process of forming the parts other than the projections proceeds simultaneously so that no large local stress may appear in the metal die. thus, unlike the known method illustrated in fig. 21 , this embodiment of the present invention does not require any load for pushing the projections to remarkably reduce the load necessary for compression forming. alternatively, for the purpose of accurately determine the positions of the bottoms of the grooves between the projections 13 a , the volume of the projections 13 a of the crown-shaped member 13 may be made smaller than that of the projections 23 a of the vibrating body 23 and the projections 23 a may be formed to a small extent after bringing the tops of the fins 7 a into contact respectively with the bottoms of the grooves between the projections 13 a . note that, if the volume of the projections 13 a of the crown-shaped member 13 is too large, the projections 13 a may fill the spaces between fins 7 a firstly to give rise to insufficiently bent fins. therefore, the volume of the projections 13 a of the crown-shaped member 13 is preferably made smaller than that of the projections 23 a of the vibrating body 23 . with this arrangement, the compression forming is completed with a relatively small load in the forging step and no heavy load is applied to metal die to make the metal die practically free from troubles such as damage and/or seizure. additionally, the crown-shaped member may preferably have such a profile that the process of forming the projections and that of forming the base sections are completed substantially at the same time so that no heavy load is applied to the fins of the metal die and the entire forming process is completed in a state where the top end facets of the fins are respectively held in tight contact with the bottoms of the grooves. as described above, with this embodiment, firstly a plate member processed to show a profile having plurality of projections is prepared and the plate member is then bent so as to direct the projections in the same direction. in other words, the plate member is bent so as to make the projecting direction of the plurality of projections include a component in an out-of-plane direction. subsequently, the plate thickness of the plurality of projections of the plate member is raised and a load is applied to the projections in the standing direction of the projections (namely in the direction including a component in an out-of-plane direction) for compression forming so as to make the projections, which are now projecting in the same direction, show a desired profile. to the contrary, when a gear or a vibrating body having a plurality of projections projecting in the same direction is manufactured from an object to be worked by grinding or cutting so as to make the projections show a desired width, the grinding or cutting process will be time consuming and it may not be suited for mass production. when projections are formed by forming grooves on an object to be worked only by sheet metal stamping or forging, the width of the projections will have to be limited because of the limit that needs to be imposed to the load to be applied to the metal die as pointed out earlier. still additionally, when a crown-shaped member is manufactured simply by bending a plate member having a plurality of projections projecting in radial directions so as to direct the projections in the same direction, the plate thickness of the projections should necessarily be made small. this embodiment dissolves the above-identified problems and is remarkably advantageous relative to the known methods because it requires neither grinding nor cutting and the grooves separating the projections can be made to have any desired width, the load applied to the metal die in the compression forming process is reduced. while the above-described embodiment employs punching for processing a plate member having a plurality of projections projecting in radial directions in the above description, the present invention is by no means limited to punching. for example, a plurality of grooves may be formed on the outer periphery of a disk-shaped member by wire cutting. in such a case, a high efficiency can be achieved by laying a large number of disk-shaped members one on the other for a wire cutting process. alternatively, a rod-shaped member or a tubular member having a plurality of axially extending grooves may be sliced. still alternatively, a plate member having a plurality of projections projecting in radial directions that is prepared in advance may be brought in. while the above-described embodiment employs drawing for bending a plate member and making the projecting direction of the projections include a component in an out-of-plane direction, the present invention is by no means limited thereto. for example, a plate member may be bent alternatively by burring, bulging or dibbling (for forming a conic shape). while the above-described embodiment employs forging for applying a load to the projections of a metal member whose projecting direction includes a component in an out-of-plane direction to increase the plate thickness of the projections of metal member, the present invention is by no means limited therefore. for example, the plate member may be processed by hot forging, warm forging or heading. second embodiment now, the second embodiment of method of manufacturing a metal member having a plurality of projections according to the present invention will be described in terms of a vibrating body having projections on the surface thereof for amplifying vibrations. this embodiment differs from the first embodiment in terms of the process of compression forming a crown-shaped member 13 after a drawing step. fig. 10 is a schematic illustration of the first forging step of forging a crown-shaped member 13 by the second embodiment. fig. 11 is a schematic illustration of the second forging step of forging a crown-shaped member. the crown-shaped member 13 is formed by means of a punch 36 and a die 37 . in this embodiment, the crown-shaped member 13 is turned upside down and a load is applied thereto for forging, or compression forming, just as in the first embodiment but this embodiment differs from the first embodiment in that the die 37 that is employed in this embodiment does not have any fins 37 . with this embodiment, the radial width (plate thickness) of the crown-shaped member 13 is raised at the projections 13 a and the base sections 13 b and the crown-shaped member 13 is deformed to show a profile of having a thickness extending between the outer peripheral wall and the inner peripheral wall of the groove of the die 37 in the first forging step that employs a die 37 having no fins. then, the crown-shaped member 13 that is forged in the first forging step is subjected to the second forging step by means of a metal die having fins 37 a , where the grooves separating the projections 13 a are broadened by the respective fins 37 a to produce a vibrating body 23 showing a final profile. a more accurately processed product may be obtained by crushing the projections in advance in order to raise their width and then broadening the grooves to a desired width. the front end parts of the fins 37 a are preferably rounded in order to allow the fins 37 a to smoothly get into the respective grooves. third embodiment now, the third embodiment of method of manufacturing a metal member having a plurality of projections according to the present invention will be described in terms of a vibrating body having projections on the surface thereof for amplifying vibrations. this embodiment differs from the first and second embodiments in the process preceding the forging. fig. 12 is a schematic illustration of a flat ring member 43 sheared by sheet metal stamping. more specifically, the ring member 43 is sheared by sheet metal stamping at an inner peripheral part thereof to deform the inner peripheral part and produce a plurality of sheared sections out of the inner peripheral part that are bent alternately in opposite directions. thus, a plurality of cut and bent sections 43 a are arranged in radial directions as viewed from the axis, or the center, of the ring member. the cut and bent sections 43 a are projections projecting in different directions as viewed from the in-plane direction of the plate member. fig. 13 is a schematic illustration of a ring member 43 produced by burring. the ring member 43 having the cut and bent sections 43 a produced by sheet metal stamping is then subjected to a burring process to obtain a crown-shaped member 53 where the cut and bent sections 43 a extend in the same direction running along the axis of the ring member 43 and are separated from each other as illustrated in fig. 13 . the ring member 43 may be subjected to a process of turning all the deformed directions of the cut and bent sections 43 a in the same direction before the burring process. then, the crown-shaped member 53 having projections 53 a that are directed in the same direction is subjected to a press-punching process to cut out an outer part of the crown-shaped member 53 along a circular line located outside the positions where the cut and bent sections 43 a are bent in the burring process. since the cut and bent sections 43 a of the ring member 43 are tapered in terms of width, the gaps separating adjacent ones of the projections 53 a increases toward the front ends of the projections 53 a of the crown-shaped member 53 . therefore, the crown-shaped member 53 can be aligned with ease with the fins arranged at the metal die for the forging process. since the cut and bent sections 43 a are produced by shearing with this embodiment, no circumferential gaps are produced between adjacent ones of the cut and bent sections 43 a . therefore, a large volume can be secured for the projections with this embodiment if compared with the first embodiment with which projections are formed by notching a plate member. additionally, a large number of cut and bent sections 43 a can be formed if compared with projections formed by punching. furthermore, such cut and bent sections 43 a can be made long if compared with projections formed by punching. as described above, each of the above-described embodiments utilizes a plate member where a plurality of projections extending in radial directions are formed in advance and executes a compression forming process after a bending process so that it requires neither grinding nor cutting. additionally, the plurality of projections that are made to project in the same direction can be made to show a desired width, although the load applied to the metal die in the compression forming process is reduced. fourth embodiment now, the fourth embodiment of method of manufacturing a metal member having a plurality of projections will be described in terms of a vibrating body having projections on the surface thereof for amplifying vibrations. this embodiment differs from the above-described third embodiment in that a plurality of cut and bent sections are formed in an outer peripheral part of a plate member by shearing. fig. 15 is a schematic illustration of a flat ring member 63 sheared from a stainless steel plate by sheet metal stamping. more specifically, the ring member 63 is sheared by sheet metal stamping at an outer peripheral part thereof to deform the outer peripheral part and produce a plurality of sheared sections out of the outer peripheral part that are bent alternately in opposite directions. thus, a plurality of cut and bent sections 63 a are arranged in radial directions as viewed from the axis, or the center, of the ring member. fig. 15 illustrates an inner hole 62 for centering the ring member 63 for the shearing process. fig. 16 is a schematic illustration of a crown-shaped member 73 obtained by drawing a ring member 63 . the ring member 63 having the cut and bent sections 63 a produced by sheet metal stamping is then subjected to a drawing process to obtain a crown-shaped member 73 where the cut and bent sections 63 a extend in the same direction running along the axis of the ring member 63 as illustrated in fig. 13 . since the cut and bent sections are arranged at an outer peripheral part of the ring member 63 unlike the third embodiment, the cut and bent sections have a width that increases toward the front ends thereof. therefore, when a crown-shaped member is produced by drawing, the gaps separating the projections 73 a are not broadened but the projections remain in a state where adjacent ones adhere to each other. or, rather, the height of the projections is increased by the drawing process. fig. 17 is a schematic illustration of the crown-shaped member 73 produced by pushing and spreading out front end parts of the projections thereof by means of a tapered punch. as described above, after the drawing process, the projections 73 a of the crown-shaped member 73 remain in a state where adjacent ones adhere to each other so that the gaps separating the front end parts of the projections 73 a are preferably broadened by pushing and spread out the front end parts of the projections 73 a by means of a punch having tapered fins. then, the crown-shaped member 73 , the gaps separating the projections 73 a thereof are broadened, is forged, while the plate thickness is being raised, to obtain a vibrating body 83 as illustrated in fig. 18 . the preferred embodiments are described above in terms of forming projections for amplifying vibrations of a vibrating body. however, the present invention is by no means limited thereto. those skilled in the art will easily realize that a forming method according to the present invention can find applications in bevel gears as illustrated in fig. 19 , hypoid gears as illustrated in fig. 20 and other similar metal-made objects so long as they are formed from a metal object to be worked that has a plurality of projections projecting in the same direction. this application claims the benefit of japanese patent application no. 2008-014459, filed jan. 25, 2008, which is hereby incorporated by reference herein in its entirety.
|
083-307-709-016-788
|
JP
|
[
"KR",
"CN",
"US",
"JP",
"TW",
"EP",
"WO"
] |
B31F1/26,B31F1/28,B29C53/24,B65H19/12,B31F1/00,B31F1/20
| 2017-01-23T00:00:00 |
2017
|
[
"B31",
"B29",
"B65"
] |
corrugating roll unit conveyance apparatus and apparatus and method for replacing corrugating roll unit
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a corrugating roll unit conveyance apparatus and an apparatus and a method for replacing a corrugating roll unit comprise: a mounting base (111) having a first accommodation part (n1) for accommodating a corrugating roll unit (40) to be removed and a second accommodation part (n2) for accommodating a corrugating roll unit (40) to be installed; and a movement device (112) for moving the mounting base (111) to a first replacement position at which the first accommodation part (n1) faces the existing corrugating roll unit (40), a second replacement position at which the second accommodation part(n2) faces a space (n3) from which the existing corrugating roll unit (40) has been removed, and a retracted position separated from the first replacement position and the second replacement position.
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1. a corrugating roll unit conveyance apparatus comprising: a mounting base having a first accommodation part for accommodating a corrugating roll unit to be removed and a second accommodation part for accommodating a corrugating roll unit to be mounted; and a movement device for moving the mounting base to a first replacement position where the first accommodation part faces an existing corrugating roll unit, a second replacement position where the second accommodation part faces a space where the existing corrugating roll unit has been removed, and a retracted position separated from the first replacement position and the second replacement position, wherein the first replacement position and the second replacement position are arranged side by side in a second horizontal direction orthogonal to a first horizontal direction which is a mounting direction and a removal direction of the corrugating roll unit, and the movement device is adapted to move the mounting base in a sequential manner to a vertical position of the first replacement position along a vertical direction, to the first replacement position along the second horizontal direction, to the second replacement position along the second horizontal direction, and to the retracted position. 2. the corrugating roll unit conveyance apparatus according to claim 1 , wherein the movement device includes a first traveling device which allows the mounting base to travel along the first horizontal direction, a second traveling device which allows the mounting base to travel along the second horizontal direction, and a switching device which switches the first traveling device and the second traveling device so as to be selectively used. 3. the corrugating roll unit conveyance apparatus according to claim 2 , wherein the switching device is a lifting device for lifting and lowering second traveling wheels of the second traveling device. 4. the corrugating roll unit conveyance apparatus according to claim 1 , wherein the movement device includes a first movement device for moving the mounting base in the vertical direction, and a second movement device for moving the mounting base along the second horizontal direction. 5. the corrugating roll unit conveyance apparatus according to claim 1 , wherein the mounting base is provided with a guide member for moving the corrugating roll unit along the removal direction and the mounting direction in the first accommodation part and the second accommodation part. 6. an apparatus for replacing a corrugating roll unit comprising: the corrugating roll unit conveyance apparatus according to claim 1 ; and a unit replacement mechanism for removing and mounting the corrugating roll unit between a single facer and the corrugating roll unit conveyance apparatus. 7. an apparatus for manufacturing a cardboard sheet, comprising: the apparatus for replacing the corrugating roll unit according to claim 6 ; and the single facer, wherein the single facer includes upper and lower corrugating rolls for nipping medium paper to perform corrugating on the medium paper, an endless pressurizing belt which is wound around a plurality of support rolls and configured to pressurize and join the corrugated medium paper and a liner along with one of the upper and lower corrugating rolls, and a belt support mechanism for preventing lowering of the endless pressurizing belt at the time of replacement of the upper and lower corrugating rolls, and the endless pressurizing belt is disposed above the upper and lower corrugating rolls. 8. the apparatus according to claim 7 , wherein the belt support mechanism includes a support member for supporting the endless pressurizing belt between the plurality of support rolls. 9. the apparatus according to claim 8 , wherein the belt support mechanism includes a support member moving device for moving the support member to a retracted position where the support member is separated from the endless pressurizing belt by a predetermined distance and a support position where the support member supports the endless pressurizing belt. 10. the apparatus according to claim 9 , wherein the support member is a support rod for supporting the endless pressurizing belt between the plurality of support rolls from below in the vertical direction, and the support member moving device is capable of moving the support rod. 11. the apparatus according to claim 9 , wherein the support member is a suction member for suctioning the endless pressurizing belt between the plurality of support rolls from above in the vertical direction, and the support member moving device is capable of lifting and lowering the suction member. 12. the apparatus according to claim 7 , wherein the belt support mechanism is an adjustment device for adjusting a distance between the plurality of support rolls. 13. an apparatus for replacing a corrugating roll unit comprising: the corrugating roll unit conveyance apparatus according to claim 3 ; a stopper for blocking a movement of the mounting base when the mounting base is moved along the mounting direction of the corrugating roll unit by the first traveling device; and a unit replacement mechanism for removing and mounting the corrugating roll unit between a single facer and the corrugating roll unit conveyance apparatus. 14. the apparatus for replacing the corrugating roll unit according to claim 13 , further comprising: a minute movement mechanism for moving the mounting base in a direction opposite to the mounting direction of the corrugating roll unit by a minute distance set in advance, from a contact position with the stopper. 15. the apparatus for replacing the corrugating roll unit according to claim 14 , wherein the lifting device is capable of lifting and lowering the second traveling wheels, and the minute movement mechanism has first inclined surfaces having a convex shape and formed on one of each of the second traveling wheels and a floor surface, and second inclined surfaces having a concave shape and formed on the other of each of the second traveling wheels and the floor surface. 16. a method of replacing a corrugating roll unit comprising: mounting a corrugating roll unit on a second accommodation part of a mounting base with a first accommodation part of the mounting base empty; moving the mounting base to a vertical position of a first replacement position where the first accommodation part faces an existing corrugating roll unit along a vertical direction; moving the existing corrugating roll unit to the first accommodation part at the first replacement position; moving the mounting base to the first replacement position along a second horizontal direction orthogonal to a first horizontal direction which is a mounting direction and a removal direction of the corrugating roll unit; moving the mounting base to a second replacement position where the second accommodation part faces a space where the existing corrugating roll unit has been removed, the first replacement position and the second replacement position being arranged side by side in the second horizontal direction; moving the mounting base to the second replacement position along the second horizontal direction; moving a corrugating roll unit of the second accommodation part to the space at the second replacement position; and retracting the mounting base from the second replacement position.
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related applications the present application is a national phase of international application number pct/jp2017/037595 filed oct. 17, 2017 and claims priority to japanese application number 2017-009443 filed jan. 23, 2017. technical field the present invention relates to a corrugating roll unit conveyance apparatus and apparatus and method for replacing the corrugating roll unit, which are used to replace a corrugating roll unit composed of upper and lower corrugating rolls which form a medium by corrugating medium paper, in a single facer for manufacturing a single-faced cardboard sheet by bonding a liner to a corrugated medium. background art a corrugating machine as a cardboard sheet-manufacturing apparatus includes a single facer which forms a single-faced cardboard sheet and a double facer which forms a double-faced cardboard sheet by bonding bottom liner paper to the single-faced cardboard sheet. in the single facer, medium paper (a medium) is processed into a corrugated shape, a top liner is bonded to the corrugated medium paper to form the single-faced cardboard sheet, and in the double facer, a bottom liner is bonded to the single-faced cardboard sheet to form the double-faced cardboard sheet. the continuous double-faced cardboard sheet manufactured by the double facer is cut to a predetermined width by a slitter scorer and cut to a predetermined length by a cutoff device, so that cardboard sheets are formed. in the single facer of the corrugating machine, the top liner heated by a preheater is transferred to a nip portion between a pressurizing belt and the upper corrugating roll, and on the other hand, the medium paper heated by a preheater is processed into a corrugated shape at a meshing portion between the upper corrugating roll and the lower corrugating roll, whereby a medium is formed, and after an adhesive is applied to a top portion of each corrugation of the medium, the medium is transferred to the nip portion. then, at the nip portion, the medium is bonded to the top liner, whereby the single-faced cardboard sheet is formed. in the single facer, in order to manufacture a plurality of types of mediums having different waveform shapes, a plurality of types of upper and lower corrugating rolls are set according to the types of mediums to be manufactured and made to be able to be replaced with respect to the single facer. as an apparatus for replacing a corrugating roll unit, there are apparatuses disclosed in the following patent literatures. in the apparatus for replacing a corrugating roll unit disclosed in ptl 1, a corrugating roll unit is loaded on a carriage and conveyed, and the corrugating roll unit is replaced at a predetermined position. further, in the apparatus for replacing a corrugating roll unit disclosed in ptl 2, a pair of guide rails is laid adjacent to a single facer, a carriage on which a corrugating roll unit is mounted is moved to a predetermined position by the pair of guide rails, and the corrugated roll unit is replaced. citation list patent literature [ptl 1] japanese unexamined patent application publication no. 2009-196331 [ptl 2] u.s. pat. no. 7,617,856 summary of invention technical problem in the apparatus for replacing a corrugating roll unit disclosed in ptl 1, an empty carriage is moved to a predetermined position, a corrugating roll unit is removed from the single facer, loaded on the carriage, and recovered, and thereafter, a carriage on which a corrugating roll unit to be replaced is loaded is moved to a predetermined position, the corrugating roll unit is mounted to the single facer, and the carriage is recovered. this replacement work is performed by a worker, it is necessary to frequently move the carriage to a predetermined position, and thus a replacement work time becomes long and the burden on workability is also large. further, in the apparatus for replacing a corrugating roll unit disclosed in ptl 2, the guide rails laid on a floor surface adjacent to the single facer become permanently installed members, and in a case where the guide rails are installed on the operation side of the corrugating machine, the guide rails interfere with a work line in a worker. for example, at the time of paper splicing work by a splicer, the time of maintenance work of the single facer, or the like, the guide rails interfere with the movement of the worker, thereby interfering with various types of quick work by the worker. further, in most cases, the guide rails cannot be installed on the driving side of the corrugating machine due to limitations of space of a building. the present invention is for solving the problem described above and has an object to provide a corrugating roll unit conveyance apparatus and apparatus and method for replacing a corrugating roll unit, in which improvement in the workability of replacement work of the corrugating roll unit is achieved without disturbing various types of work by a worker. solution to problem a corrugating roll unit conveyance apparatus for achieving the above object includes a mounting base having a first accommodation part for accommodating a corrugating roll unit to be removed and a second accommodation part for accommodating a corrugating roll unit to be mounted, and a movement device which moves the mounting base to a first replacement position where the first accommodation part faces an existing corrugating roll unit, a second replacement position where the second accommodation part faces a space where the existing corrugating roll unit has been removed, and a retracted position separated from the first replacement position and the second replacement position. therefore, first, if the mounting base is moved from the retracted position to the first replacement position by the movement device, the first accommodation part faces the existing corrugating roll unit. here, the existing corrugating roll unit is moved to the first accommodation part. next, the mounting base is moved from the first replacement position to the second replacement position where the second accommodation part faces the space where the existing corrugating roll unit has been removed, by the movement device. here, the corrugating roll unit in the second accommodation part is moved to the space where the existing corrugating roll unit has been removed. then, the mounting base is moved from the second replacement position to the retracted position by the movement device, whereby the replacement work is completed. as a result, it is possible to perform the replacement work of the corrugating roll unit with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit without disturbing various types of work by the worker. in the corrugating roll unit conveyance apparatus according to the present invention, the movement device includes a first traveling device which allows the mounting base to travel along a first horizontal direction which is a mounting direction and a removal direction of the corrugating roll unit, a second traveling device which allows the mounting base to travel along a second horizontal direction orthogonal to the first horizontal direction, and a switching device which switches the first traveling device and the second traveling device so as to be selectively used. therefore, if the first traveling device is selected by the switching device and the first traveling device is operated, it is possible to allow the mounting base to travel along the first horizontal direction, and if the second traveling device is selected by the switching device and the second traveling device is operated, it is possible to allow the mounting base to travel along the second horizontal direction. for this reason, it is possible to smoothly move the mounting base to the first replacement position and the second replacement position. in the corrugating roll unit conveyance apparatus according to the present invention, the switching device is a lifting device which lifts and lowers first traveling wheels of the first traveling device or second traveling wheels of the second traveling device. therefore, the first traveling wheels of the first traveling device or the second traveling wheels of the second traveling device are lifted and lowered by the lifting device, whereby the use of the first traveling device and the second traveling device can be switched, and thus it is possible to simplify a structure. in the corrugating roll unit conveyance apparatus according to the present invention, the movement device includes a first movement device which lifts and lowers the mounting base, and a second movement device which moves the mounting base along a second horizontal direction orthogonal to a first horizontal direction which is a removal direction and a mounting direction of the corrugating roll unit. therefore, if the first movement device is operated, it is possible to lift and lower the mounting base, and if the second movement device is operated, it is possible to allow the mounting base to travel along the second horizontal direction. for this reason, it is possible to smoothly move the mounting base to the first replacement position and the second replacement position. in the corrugating roll unit conveyance apparatus according to the present invention, the mounting base is provided with a guide member for moving the corrugating roll unit along a removal direction and a mounting direction in the first accommodation part and the second accommodation part. therefore, since the guide members are provided in the first accommodation part and the second accommodation part of the mounting base, the corrugating roll unit can be moved in the removal direction by the guide member and easily accommodated in the first accommodation part, and the corrugating roll unit in the second accommodation part can be moved in the mounting direction by the guide member and easily mounted at a predetermined position. further, an apparatus for replacing a corrugating roll unit according to the present invention includes the corrugating roll unit conveyance apparatus, and a unit replacement mechanism which performs removal and mounting of the corrugating roll unit between a single facer and the corrugating roll unit conveyance apparatus. therefore, first, if the mounting base is moved from the retracted position to the first replacement position by the movement device, the first accommodation part faces the existing corrugating roll unit. here, the existing corrugating roll unit is moved to the first accommodation part by the unit replacement mechanism. next, the mounting base is moved from the first replacement position to the second replacement position where the second accommodation part faces the space where the existing corrugating roll unit has been removed, by the movement device. here, the corrugating roll unit in the second accommodation part is moved to the space where the existing corrugating roll unit has been removed, by the unit replacement mechanism. then, the mounting base is moved from the second replacement position to the retracted position by the movement device, whereby the replacement work is completed. as a result, it is possible to perform the replacement work of the corrugating roll unit with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit without disturbing various types of work by the worker. in the apparatus for replacing a corrugating roll unit according to the present invention, the single facer includes upper and lower corrugating rolls which nip medium paper and perform corrugating on the medium paper, an endless pressurizing belt which is wound around a plurality of support rolls and pressurizes and joins the corrugated medium paper and a liner along with one of the upper and lower corrugating rolls, and a belt support mechanism which prevents lowering of the pressurizing belt at the time of replacement of the upper and lower corrugating rolls. therefore, since lowering of the pressurizing belt is blocked by the belt support mechanism at the time of the replacement of the upper and lower corrugating rolls, the upper corrugating roll does not come into contact with the pressurizing belt, and thus damage to the pressurizing belt can be prevented. as a result, it is possible to improve the workability of the replacement work of the corrugating roll unit. in the apparatus for replacing a corrugating roll unit according to the present invention, the belt support mechanism includes a support member for supporting the pressurizing belt between the plurality of support rolls. therefore, since the pressurizing belt between the plurality of support rolls is supported by the support member at the time of the replacement of the upper and lower corrugating rolls, it is possible to easily prevent the contact between the upper corrugating roll and the pressurizing belt with a simple configuration. in the apparatus for replacing a corrugating roll unit according to the present invention, the belt support mechanism includes a support member moving device which moves the support member to a retracted position where the support member is separated from the pressurizing belt by a predetermined distance and a support position where the support member supports the pressurizing belt. therefore, the support member is normally located at the retracted position where the support member is separated from the pressurizing belt, so that the operation of the single facer is not hindered. then, at the time of the replacement of the upper and lower corrugating rolls, the support member is moved to the support position where the support member supports the pressurizing belt, by the support member moving device, and therefore, the support member easily supports the pressurizing belt with a simple configuration, whereby it is possible to prevent the contact between the upper corrugating roll and the pressurizing belt. in the apparatus for replacing a corrugating roll unit according to the present invention, the support member is a support rod for supporting the pressurizing belt between the plurality of support rolls from below in a vertical direction, and the support member moving device is capable of moving the support rod. therefore, at the time of the replacement of the upper and lower corrugating rolls, the support rod is moved to the support position by the support member moving device and supports the pressurizing belt from below, and therefore, it is possible to prevent the contact between the upper corrugating roll and the pressurizing belt by easily supporting the pressurizing belt with a simple configuration. in the apparatus for replacing a corrugating roll unit according to the present invention, the support member is a suction member which suctions the pressurizing belt between the plurality of support rolls from above in a vertical direction, and the support member moving device is capable of lifting and lowering the suction member. therefore, at the time of the replacement of the upper and lower corrugating rolls, the pressurizing belt is suctioned from above by the suction member, and therefore, it is possible to prevent the contact between the upper corrugating roll and the pressurizing belt by easily supporting the pressurizing belt with a simple configuration. in the apparatus for replacing a corrugating roll unit according to the present invention, the belt support mechanism is an adjustment device which adjusts a distance between the plurality of support rolls. therefore, at the time of the replacement of the upper and lower corrugating rolls, the distance between the plurality of support rolls is adjusted by the adjustment device, and therefore, it is possible to prevent the contact between the upper corrugating roll and the pressurizing belt by easily supporting the pressurizing belt with an existing device. further, an apparatus for replacing a corrugating roll unit according to the present invention includes the corrugating roll unit conveyance apparatus, a stopper which blocks a movement of the mounting base when the mounting base is moved along the mounting direction of the corrugating roll unit by the first traveling device, and a unit replacement mechanism which performs removal and mounting of the corrugating roll unit between a single facer and the corrugating roll unit conveyance apparatus. therefore, first, if the first traveling device is operated to allow the mounting base to travel along the first horizontal direction, the mounting base comes into contact with the stopper, whereby the movement thereof is blocked, and next, the second traveling device is operated to allow the mounting base to travel along the second horizontal direction, thereby moving the mounting base to the first replacement position or the second replacement position. then, at the first replacement position, the existing corrugating roll unit is moved to the first accommodation part by the unit replacement mechanism. further, at the second replacement position, the corrugating roll unit in the second accommodation part is moved to the space where the existing corrugating roll unit has been removed, by the unit replacement mechanism. then, the mounting base is moved from the second replacement position to the retracted position by the movement device, whereby the replacement work is completed. as a result, it is possible to perform the replacement work of the corrugating roll unit with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit without disturbing various types of work by the worker. the apparatus for replacing a corrugating roll unit according to the present invention further includes a minute movement mechanism which moves the mounting base in a direction opposite to the mounting direction of the corrugating roll unit by a minute distance set in advance, from a contact position with the stopper. therefore, when the mounting base has come into contact with the stopper, the mounting base is moved in the opposite direction by the minute distance from the contact position by the minute movement mechanism, and therefore, it is possible to allow the mounting base to travel in the second horizontal direction in a state of being separated from the stopper, and thus it is possible to allow the mounting base to smoothly travel. in the apparatus for replacing a corrugating roll unit according to the present invention, the lifting device is capable of lifting and lowering the second traveling wheels, and the minute movement mechanism has first inclined surfaces having a convex shape and formed on one of each of the second traveling wheels and a floor surface, and second inclined surfaces having a concave shape and formed on the other of each of the second traveling wheels and the floor surface. therefore, when the mounting base has come into contact with the stopper, if the lifting device lowers the second traveling wheels, the second traveling wheels are grounded to the floor surface, and at this time, since the first inclined surfaces and the second inclined surfaces come into contact with each other and the mounting base moves in the opposite direction by the minute distance from the contact position with the stopper, it is possible to allow the mounting base to travel in the second horizontal direction in a state of being separated from the stopper, and thus it is possible to allow the mounting base to smoothly travel. further, a method of replacing a corrugating roll unit according to the present invention includes a step of moving an existing corrugating roll unit to the first accommodation part at the first replacement position, a step of moving the mounting base to a second replacement position where the second accommodation part faces a space where the existing corrugating roll unit has been removed, a step of moving a corrugating roll unit of the second accommodation part to the space at the second replacement position, and a step of retracting the mounting base from the second replacement position. therefore, it is possible to perform the replacement work of the corrugating roll unit with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit without disturbing various types of work by the worker. advantageous effects of invention according to the corrugating roll unit conveyance apparatus and the apparatus and method for replacing corrugating roll unit according to the present invention, it is possible to perform the replacement work of the corrugating roll unit with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit without disturbing various types of work by the worker. brief description of drawings fig. 1 is a schematic diagram showing a corrugating machine as a cardboard sheet-manufacturing apparatus. fig. 2 is a schematic configuration diagram showing a single facer. fig. 3 is a plan view showing a corrugating roll unit replacement carriage of a first embodiment. fig. 4 is a side view showing the corrugating roll unit replacement carriage. fig. 5 is a schematic diagram showing a traveling device in the corrugating roll unit replacement carriage. fig. 6a is a side view showing an operation of the corrugating roll unit replacement carriage. fig. 6b is a side view showing the operation of the corrugating roll unit replacement carriage. fig. 6c is a side view showing the operation of the corrugating roll unit replacement carriage. fig. 7 is a schematic front view showing a support device of a pressurizing belt for a corrugating roll unit of the first embodiment. fig. 8 is a schematic plan view showing a support device of a pressurizing belt for a corrugating roll unit according to a first modification example of the first embodiment. fig. 9 is a schematic front view showing the support device of a pressurizing belt for a corrugating roll unit. fig. 10 is a schematic plan view showing a support device of a pressurizing belt for a corrugating roll unit according to a second modification example of the first embodiment. fig. 11 is a schematic front view showing the support device of a pressurizing belt for a corrugating roll unit. fig. 12 is a schematic plan view showing a support device of a pressurizing belt for a corrugating roll unit according to a third modification example of the first embodiment. fig. 13 is a schematic front view showing a support device of a pressurizing belt for a corrugating roll unit according to a fourth modification example of the first embodiment. fig. 14 is a schematic front view showing a support device of a pressurizing belt for a corrugating roll unit according to a fifth modification example of the first embodiment. fig. 15 is a plan view showing an apparatus for replacing a corrugating roll unit of the first embodiment. fig. 16 is a plan view showing a method of replacing a corrugating roll unit. fig. 17 is a plan view showing the method of replacing a corrugating roll unit. fig. 18 is a plan view showing the method of replacing a corrugating roll unit. fig. 19 is a plan view showing an apparatus for replacing a corrugating roll unit of a second embodiment. fig. 20 is a front view showing the apparatus for replacing a corrugating roll unit. fig. 21 is a plan view showing a method of replacing a corrugating roll unit of the second embodiment. fig. 22 is a plan view showing the method of replacing a corrugating roll unit. fig. 23 is a plan view showing the method of replacing a corrugating roll unit. description of embodiments hereinafter, preferred embodiments of a corrugating roll unit conveyance apparatus and apparatus and method for replacing a corrugating roll unit according to the present invention will be described in detail with reference to the accompanying drawings. the present invention is not limited by these embodiments, and in a case where there are a plurality of embodiments, the present invention also includes configurations made by combining the respective embodiments. first embodiment fig. 1 is a schematic diagram showing a corrugating machine as a cardboard sheet-manufacturing apparatus. as shown in fig. 1 , a corrugating machine 10 as a cardboard sheet-manufacturing apparatus is for manufacturing a single-faced cardboard sheet d by bonding, for example, a top liner c as a second liner to a corrugated medium (medium paper) b, and manufacturing a sheet-like double-faced cardboard sheet f by bonding, for example, a bottom liner a as a first liner to the medium b side of the manufactured single-faced cardboard sheet d, thereby forming a double-faced cardboard sheet e, and cutting the continuous double-faced cardboard sheet e to a predetermined length. the corrugating machine 10 includes a mill roll stand 11 for the medium b, a preheater (preheating device) 12 , a mill roll stand 13 for the top liner c, a preheater (preheating device) 14 , a single facer 15 , a bridge 16 , a mill roll stand 17 for the bottom liner a, a preheater (preheating device) 18 , a glue machine 19 , a double facer 20 , a rotary shear 21 , a slitter scorer 22 , a cutoff 23 , a defective sheet rejecting device 24 , and a stacker 25 . in the mill roll stand 11 , rolls of paper, in each of which the medium paper from which the mediums b is formed is wound in a roll shape, are respectively mounted on both sides, and a splicer (a paper splicing device) 11 a which performs paper splicing is provided on the upper side thereof. in a case where paper is being fed from the roll of paper on one side, the roll of paper on the other side is mounted and paper splicing is prepared. if the remaining of the base paper of the roll of paper on one side is a small amount, the splicer 11 a performs paper splicing of the base paper of the roll of paper on the other side. then, while the base paper is being supplied from the roll of paper on the other side, the roll of paper on one side is mounted and paper splicing is prepared. in this way, the base paper is sequentially spliced and continuously fed toward the downstream side from the mill roll stand 11 . on the other hand, in the mill roll stand 13 , rolls of paper, in each of which the top liner c is wound in a roll shape, are respectively mounted on both sides, and a splicer 13 a which performs paper splicing is provided on the upper side thereof. in a case where paper is being fed from the roll of paper on one side, the roll of paper on the other side is mounted and paper splicing is prepared. if the remaining of the base paper of the roll of paper on one side is a small amount, the splicer 13 a performs paper splicing of the base paper of the roll of paper on the other side. then, while the base paper is being supplied from the roll of paper on the other side, the roll of paper on one side is mounted and paper splicing is prepared. in this way, the base paper is sequentially spliced and continuously fed toward the downstream side from the mill roll stand 13 . the preheaters 12 and 14 are for preheating the medium b and the top liner c, respectively. the preheaters 12 and 14 each have a heating device in which steam is supplied to the interior thereof, and convey the base paper (the medium b and the top liner c) which is continuously fed from the mill roll stands 11 and 13 while heating the base paper by the heating device, thereby heating the medium b and the top liner c to a predetermined temperature. the single facer 15 forms the single-faced cardboard sheet d by processing the medium b heated by the preheater 12 in a corrugated shape, then applying an adhesive to a top portion of each corrugation, and bonding the top liner c heated by the preheater 14 to the corrugated medium b. in the single facer 15 , a pickup conveyor 31 is provided obliquely upward on the downstream side in a transfer direction. the pickup conveyor 31 is composed of a pair of endless belts and has a function of nipping the single-faced cardboard sheet d formed in the single facer 15 and conveying it to the bridge 16 . the bridge 16 functions as a retaining part for temporarily retaining the single-faced cardboard sheet d in order to absorb a difference in speed between the single facer 15 and the double facer 20 . in the mill roll stand 17 , rolls of paper, in each of which the bottom liner a is wound in a roll shape, are respectively mounted on both sides, and a splicer 17 a which performs paper splicing is provided on the upper side thereof. in a case where paper is being fed from the roll of paper on one side, the roll of paper on the other side is mounted and paper splicing is prepared. if the remaining of the base paper of the roll of paper on one side is a small amount, the splicer 17 a performs paper splicing of the base paper of the roll of paper on the other side. then, while the base paper is being supplied from the roll of paper on the other side, the roll of paper on one side is mounted and paper splicing is prepared. in this way, the base paper is sequentially spliced and continuously fed toward the downstream side from the mill roll stand 17 . the preheater 18 has a heating roll (hereinafter, a single-faced sheet heating roll) 32 for the single-faced cardboard sheet d and a heating roll (hereinafter, a bottom liner heating roll) 33 for the bottom liner a. the single-faced sheet heating roll 32 has a winding amount adjusting device, is heated to a predetermined temperature by steam which is supplied to the interior thereof, and can preheat the single-faced cardboard sheet d by winding the top liner c side of the single-faced cardboard sheet d around the circumferential surface thereof. on the other hand, the bottom liner heating roll 33 also likewise has a winding amount adjusting device, is heated to a predetermined temperature by steam which is supplied to the interior thereof, and can preheat the bottom liner a by winding the bottom liner a around the circumferential surface thereof. the glue machine 19 has adhesive equipment and a pressurizing device. the single-faced cardboard sheet d heated by the single-faced sheet heating roll 32 is guided along the inside of the glue machine 19 on the way, and when the single-faced cardboard sheet d passes between a rider roll and an adhesive applicator roll, an adhesive is applied to a top portion of each of the corrugations of the medium b. the single-faced cardboard sheet d with an adhesive applied thereto by the glue machine 19 is transferred to the double facer 20 of the next process. further, the bottom liner a heated by the bottom liner heating roll 33 is also transferred to the double facer 20 through the glue machine 19 . the double facer 20 is divided into a heating section 20 a on the upstream side and a cooling section 20 b on the downstream side along a traveling line of the single-faced cardboard sheet d and the bottom liner a. the single-faced cardboard sheet d with an adhesive applied thereto by the glue machine 19 is carried in between a pressurizing belt 34 and a hot plate 35 in the heating section 20 a , and the bottom liner a is carried in between the pressurizing belt 34 and the hot plate 35 so as to overlap the medium b side of the single-faced cardboard sheet d. then, the single-faced cardboard sheet d and the bottom liner a are carried in between the pressurizing belt 34 and the hot plate 35 , and then transferred toward the cooling section 20 b in an integrated manner in a state of being overlapped up and down. during this transfer, the single-faced cardboard sheet d and the bottom liner a are heated while being pressurized, whereby they are bonded to each other to form the continuous double-faced cardboard sheet e. the double-faced cardboard sheet e is naturally cooled in the cooling section 20 b when being nipped and conveyed by the pressurizing belt 34 and a conveyance belt 36 . the double-faced cardboard sheet e manufactured in the double facer 20 is transferred to the rotary shear 21 . the rotary shear 21 is for cutting the entire width of the double-faced cardboard sheet e in the width direction or partially cutting the double-faced cardboard sheet e before the bonding is stabilized in an operation initial stage. the slitter scorer 22 is for cutting the wide double-faced cardboard sheet e along the transfer direction so as to have a predetermined width, and forming creasing lines extending in the transfer direction. the slitter scorer 22 is composed of a first slitter scorer unit 22 a and a second slitter scorer unit 22 b having substantially the same structure, which are arranged along the transfer direction of the double-faced cardboard sheet e. each of the first slitter scorer unit 22 a and the second slitter scorer unit 22 b has a plurality of sets of upper creasing line rolls and lower creasing line rolls, which are disposed to face each other with the double-sided cardboard sheet e interposed therebetween, in the width direction, and has a plurality of sets of slitter knives, which are disposed on the lower side of the double-sided cardboard sheet e, in the width direction. the cutoff 23 is for cutting the double-faced cardboard sheet e cut in the transfer direction by the slitter scorer 22 along the width direction to form a plate-shaped double-faced cardboard sheet f having a predetermined length. the defective sheet rejecting device 24 is for rejecting the double-faced cardboard sheet f determined to be a defective sheet by a defect detection device (described later) from a conveyance line. the stacker 25 is for stacking the non-defective double-faced cardboard sheets f and discharging them as products to the outside of the machine. here, the single facer 15 will be described in detail. fig. 2 is a schematic configuration diagram showing the single facer. as shown in fig. 2 , the single facer 15 includes a belt roll (a support roll) 41 , a tension roll (a support roll) 42 , a pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 , an upper corrugating roll 44 having a surface formed in a corrugated shape and being in contact with the pressurizing belt 43 in a pressurized state, and a lower corrugating roll 45 having a surface likewise formed in a corrugated shape and engaged with the upper corrugating roll 44 . the top liner c heated by the preheater 14 (refer to fig. 1 ) is preheated by being wound around a liner preheating roll 46 , and then transferred to a nip portion between the pressurizing belt 43 and the upper corrugating roll 44 together with the pressurizing belt 43 which is guided by the belt roll 41 . on the other hand, the medium b heated by the preheater 12 is processed into a corrugated shape at a meshing portion between the upper corrugating roll 44 and the lower corrugating roll 45 and then transferred to the nip portion between the pressurizing belt 43 and the upper corrugating roll 44 while being guided by the upper corrugating roll 44 . adhesive equipment 51 is disposed in the vicinity of the upper corrugating roll 44 . the adhesive equipment 51 is composed of an adhesive dam 52 in which an adhesive is stored, an adhesive applicator roll 53 which applies the adhesive to the medium b which is conveyed by the upper corrugating roll 44 , a meter roll 54 for adjusting the amount of the adhesive which is stuck to the circumferential surface of the adhesive applicator roll 53 , and an adhesive scraping blade 55 for scraping the adhesive from the meter roll 54 . the medium b corrugated at the meshing portion between the upper corrugating roll 44 and the lower corrugating roll 45 is applied with the adhesive at the top portion of each corrugation by the adhesive applicator roll 53 and then bonded to the top liner c at the nip portion between the pressurizing belt 43 and the upper corrugating roll 44 , whereby the single-faced cardboard sheet d is formed. all the belt roll 41 , the tension roll 42 , the upper corrugating roll 44 , and the lower corrugating roll 45 are heated by steam which flows in the interior thereof. for this reason, the medium b is heated when it is processed into a corrugated shape by being pressurized at the meshing portion between the upper corrugating roll 44 and the lower corrugating roll 45 . then, the medium b is applied with the adhesive at the top portion of each corrugation by the adhesive applicator roll 53 and then pressurized and heated when being overlapped with the top liner c, by the pressurizing belt 43 and the upper corrugating roll 44 . the adhesive receives a predetermined amount of heat, so that the adhesive force thereof increases, and thus the adhesive is solidified, and the medium b and the top liner c are bonded to each other due to the adhesive being solidified by receiving heat from the upper and lower corrugating rolls 44 and 45 and the pressurizing belt 43 . further, although not shown in the drawings, a pressurizing force adjusting device capable of adjusting a pressurizing force to the medium b and the top liner c by the upper corrugating roll 44 and the pressurizing belt 43 is provided. the pressurizing force adjusting device has a hydraulic cylinder, and a tip portion of a drive rod thereof is connected to a support shaft of the tension roll 42 . therefore, the tension of the pressurizing belt 43 is adjusted by moving the tension roll 42 toward and away from the belt roll 41 by the hydraulic cylinder, and thus the pressurizing force to the medium b and the top liner c which are conveyed between the upper corrugating roll 44 and the pressurizing belt 43 can be adjusted. in the single facer 15 configured in this manner, it is necessary to form a plurality of types of mediums b having different waveform shapes, and therefore, a plurality of types of upper and lower corrugating rolls 44 and 45 are provided according to the types of the mediums b to be formed, and a corrugating roll unit composed of the upper corrugating roll 44 , the lower corrugating roll 45 , and the like is made to be able to be replaced with respect to the single facer 15 . a corrugating roll unit 40 is composed of the upper corrugating roll 44 , the lower corrugating roll 45 , the adhesive equipment 51 , and the like. hereinafter, a corrugating roll unit replacement carriage (a corrugating roll unit conveyance apparatus), a support device of the pressurizing belt for the corrugating roll unit, and apparatus and method for replacing a corrugating roll unit of the first embodiment will be described. fig. 3 is a plan view showing the corrugating roll unit replacement carriage of the first embodiment, fig. 4 is a side view showing the corrugating roll unit replacement carriage, fig. 5 is a schematic diagram showing a traveling device in the corrugating roll unit replacement carriage of the first embodiment, and figs. 6a to 6c are side views showing an operation of the corrugating roll unit replacement carriage. further, fig. 15 is a plan view showing the apparatus for replacing a corrugating roll unit of the first embodiment. in the first embodiment, as shown in fig. 15 , an apparatus for replacing a corrugating roll unit 100 includes a corrugating roll unit replacement carriage 101 , a support device 102 of the pressurizing belt for the corrugating roll unit, and a unit replacement mechanism 103 . here, a first horizontal direction which is a removal direction and a mounting direction of the corrugating roll unit 40 is set as being an x direction, and a second horizontal direction orthogonal to the first horizontal direction x is set as being a y direction. further, the mounting direction of the corrugating roll unit 40 is a direction x 1 in which the corrugating roll unit replacement carriage 101 approaches the single facer 15 along the first horizontal direction x, and the removal direction of the corrugating roll unit 40 is a direction x 2 in which the corrugating roll unit replacement carriage 101 is separated from the single facer 15 along the first horizontal direction x. first, the corrugating roll unit replacement carriage 101 will be described. as shown in figs. 3 to 5 , the corrugating roll unit replacement carriage 101 of the first embodiment includes a mounting base 111 and a movement device 112 . the mounting base 111 has a rectangular plate shape and has a first accommodation part n 1 for accommodating the corrugating roll unit 40 to be removed from the single facer 15 and a second accommodation part n 2 for accommodating the corrugating roll unit 40 to be mounted to the single facer 15 . then, in the mounting base 111 , guide rails (guide members) 121 and 122 which support the corrugating roll unit 40 so as to be able to move the corrugating roll unit 40 along the first horizontal direction x in the first accommodation part n 1 and the second accommodation part n 2 , respectively, are provided at an upper surface portion thereof. further, the mounting base 111 is provided with contact parts 123 and 124 at the upper surface portion on one end portion side in a longitudinal direction in the guide rails 121 and 122 . when the corrugating roll unit 40 moves in the removal direction x 2 by the guide rails 121 and 122 of the mounting base 111 , the corrugating roll unit 40 is positioned by coming into contact with the contact parts 123 and 124 . the movement device 112 is composed of a first traveling device 125 , a second traveling device 126 , and a lifting device (switching device) 127 . the first traveling device 125 is for traveling the mounting base 111 along the first horizontal direction x, and the second traveling device 126 is for traveling the mounting base 111 along the second horizontal direction y. in the first traveling device 125 , as four first traveling wheels, two front wheels 128 a and two rear wheels 128 b are provided to be integrally rotatable by axles 129 a and 129 b , and drive devices 130 a and 130 b are provided on the axle 129 a for the front wheels 128 a and the axle 129 b for the rear wheels 128 b . for this reason, the front wheels 128 a and the rear wheels 128 b are driven and rotated through the axles 129 a and 129 b by the drive devices 130 a and 130 b , whereby the mounting base 111 can travel along the first horizontal direction x on a floor surface g. a steering device 131 may be provided on the axle 129 a for the front wheels 128 a. in the second traveling device 126 , as four second traveling wheels, two wheels 132 a on the front side and two wheels 132 b on the rear side are provided, and drive devices 133 a and 133 b are provided on the wheels 132 a and 132 b , respectively. for this reason, the mounting base 111 can travel along the second horizontal direction y on the floor surface g by driving and rotating the wheels 132 a and 132 b by the drive devices 133 a and 133 b. the lifting device 127 is for lifting and lowering the wheels 132 a and 132 b of the second traveling device 126 , thereby switching between the first traveling device 125 and the second traveling device 126 such that the first traveling device 125 and the second traveling device 126 can be selectively used. for this reason, if the wheels 132 a and 132 b are lifted by the lifting device 127 , the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 are grounded to the floor surface g and the wheels 132 a and 132 b of the second traveling device 126 are separated from the floor surface g, whereby the first traveling device 125 can be used. on the other hand, if the wheels 132 a and 132 b are lowered by the lifting device 127 , the wheels 132 a and 132 b of the second traveling device 126 are grounded to the floor surface g and the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 are separated from the floor surface g, whereby the second traveling device 126 can be used. the first traveling device 125 and the second traveling device 126 may be switched so as to be able to be selectively used by lifting and lowering the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 by the lifting device 127 . for this reason, the movement device 112 can move the mounting base 111 to a first replacement position (a position shown in fig. 16 (described later)) where the first accommodation part n 1 faces the existing corrugating roll unit 40 , a second replacement position (a position shown in fig. 17 (described later)) where the second accommodation part n 2 faces a space where the existing corrugating roll unit 40 has been removed, and a retracted position separated from the first replacement position and the second replacement position, by the first traveling device. further, the mounting base 111 is provided with an operating handle 134 at one end portion in the longitudinal direction, and the operating handle 134 is provided with an operating panel 135 for driving and stopping the movement device 112 . further, as shown in fig. 6a , in the single facer 15 , a stopper 142 for the mounting base 111 is provided at a frame 141 . when the mounting base 111 is moved along the mounting direction x 1 by the first traveling device 125 , the mounting base 111 comes into contact with the stopper 142 , so that the movement thereof is blocked. further, a minute movement mechanism 143 is provided, and when the mounting base 111 has come into contact with the stopper 142 , the minute movement mechanism 143 moves the mounting base 111 in the removal direction x 2 opposite to the mounting direction x 1 by a minute distance s set in advance, from the contact position. in the minute movement mechanism 143 , each of the wheels 132 a of the second traveling device 126 has a convex shape and is provided with two first inclined surfaces 144 a and 144 b inclined in the opposite directions with respect to the horizontal direction and a flat surface 144 c along the horizontal direction between the first inclined surfaces 144 a and 144 b . on the other hand, the floor surface g adjacent to the stopper 142 is provided with a guide rail 145 , and the guide rail 145 has a concave shape and is provided with two second inclined surfaces 146 a and 146 b inclined in the opposite directions with respect to the horizontal direction. here, the first inclined surfaces 144 a and 144 b of each of the wheels 132 a and the second inclined surfaces 146 a and 146 b of the guide rail 145 are set to have substantially the same inclination angle. each of the wheels 132 a of the second traveling device 126 may be formed so as to have a concave shape and the guide rail 145 may be formed so as to have a convex shape. for this reason, as shown in fig. 6a , in a state where the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 are grounded to the floor surface g and the wheels 132 a and 132 b of the second traveling device 126 are separated from the floor surface g, the mounting base 111 is traveled in the mounting direction x 1 by the first traveling device 125 and comes into contact with the stopper 142 to stop. at this time, the wheels 132 a are located above the guide rail 145 . however, the wheels 132 a are located at a position shifted to the stopper 142 side by the minute distance s. here, as shown in figs. 6a and 6b , if the wheels 132 a and 132 b are lowered by the lifting device 127 , only the first inclined surface 144 a of each of the wheels 132 a comes into contact with only the second inclined surface 146 a of the guide rail 145 . then, if the wheels 132 a and 132 b are further lowered by the lifting device 127 , as shown in figs. 6b and 6c , the first inclined surface 144 a of each of the wheels 132 a is guided by the second inclined surface 146 a of the guide rail 145 to move in the removal direction x 2 and the first inclined surfaces 144 a and 144 b of each of the wheels 132 a come into contact with the second inclined surfaces 146 a and 146 b of the guide rail 145 . at this time, the wheels 132 b of the second traveling device 126 are also grounded to the floor surface g and the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 are separated from the floor surface g. then, the minute distance s is secured between the mounting base 111 and the stopper 142 , and thus when the mounting base 111 is moved in the second horizontal direction y by the second traveling device 126 , the mounting base 111 can travel without coming into contact with the stopper 142 . next, the support device of the pressurizing belt for the corrugating roll unit will be described. fig. 7 is a schematic front view showing the support device of the pressurizing belt for the corrugating roll unit of the first embodiment. as shown in fig. 7 , the support device 102 of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is provided with a support member for supporting an upper belt 43 a or a lower belt 43 b of the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 . further, the belt support mechanism is provided with a support member moving device which moves the support member to a retracted position where the support member is separated from the pressurizing belt 43 by a predetermined distance and a support position where the support member supports the pressurizing belt 43 . specifically, the support member is a suction member 151 which suctions the lower belt 43 b of the pressurizing belt 43 from above in the vertical direction, and a suction device (not shown) is connected to the suction member 151 . further, the support member moving device is an air cylinder lifting device (not shown) capable of lifting and lowering the suction member 151 . during the operation of the single facer 15 , that is, when the pressurizing belt 43 is being moved by the belt roll 41 and the tension roll 42 , the pressurizing belt 43 is in contact with the upper corrugating roll 44 . at this time, the suction member 151 is located at a retracted position (a position shown by a two-dot chain line in fig. 7 ) where the suction member 151 is separated from the pressurizing belt 43 , between the upper belt 43 a and the lower belt 43 b . then, when the operation of the single facer 15 is stopped and the corrugating roll unit 40 is replaced, the suction member 151 is lowered to move to a support position (a position shown by a solid line in fig. 7 ) where the suction member 151 supports the lower belt 43 b , and the suction member 151 suctions the lower belt 43 b by operating the suction device. here, the existing corrugating roll unit 40 composed of the upper corrugating roll 44 , the lower corrugating roll 45 , and the like is lowered as shown by a two-dot chain line in fig. 7 , and then moved in the removal direction x 2 and removed. subsequently, another corrugating roll unit 40 is moved in the mounting direction x 1 to the space where the existing corrugating roll unit 40 has been removed, and then lifted as shown by the solid line in fig. 7 . at this time, since the lower belt 43 b is suctioned by the suction member 151 , the pressurizing belt 43 does not hang down. for this reason, even if the corrugating roll unit 40 is moved in the removal direction x 2 or the mounting direction x 1 at the time of the replacement of the corrugating roll unit 40 , the corrugating roll unit 40 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 is prevented. the support device of the pressurizing belt for the corrugating roll unit is not limited to that described above. fig. 8 is a schematic plan view showing a support device of the pressurizing belt for the corrugating roll unit according to a first modification example of the first embodiment, and fig. 9 is a schematic front view showing the support device of the pressurizing belt for the corrugating roll unit. as shown in figs. 8 and 9 , a support device 102 a of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is provided with support rods 152 a and 152 b as support members for supporting the lower belt 43 b of the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 . further, the belt support mechanism is provided with air cylinders 153 a and 153 b as support member moving devices which move the support rods 152 a and 152 b to a retracted position where the support rods 152 a and 152 b are separated from the pressurizing belt 43 by a predetermined distance and a support position where the support rods 152 a and 152 b support the pressurizing belt 43 . specifically, the air cylinders 153 a and 153 b are disposed further on the removal direction x 2 side than the corrugating roll unit 40 and below the pressurizing belt 43 , and can move the support rods 152 a and 152 b in the mounting direction x 1 . during the operation of the single facer 15 , that is, when the pressurizing belt 43 is being moved by the belt roll 41 and the tension roll 42 , the pressurizing belt 43 is in contact with the upper corrugating roll 44 (a solid line state in fig. 7 ). at this time, the support rods 152 a and 152 b are located at a retracted position (a position shown by a two-dot chain line in fig. 8 ) where the support rods 152 a and 152 b are separated from the pressurizing belt 43 , further on the removal direction x 2 side than the existing corrugating roll unit 40 . then, when the operation of the single facer 15 is stopped and the corrugating roll unit 40 is replaced, the support rods 152 a and 152 b are moved to the mounting direction x 1 side by the air cylinders 153 a and 153 b and located at a support position (a position shown by a solid line in fig. 8 ) where the support rods 152 a and 152 b can support the lower belt 43 b . here, the existing corrugating roll unit 40 is lowered as shown by a solid line in fig. 9 , and then moved in the removal direction x 2 and removed. subsequently, another corrugating roll unit 40 is moved in the mounting direction x 1 to the space where the existing corrugating roll unit 40 has been removed, and then lifted. at this time, since the lower belt 43 b is supported by the support rods 152 a and 152 b , the pressurizing belt 43 does not hang down. for this reason, even if the corrugating roll unit 40 is moved in the removal direction x 2 or the mounting direction x 1 at the time of the replacement of the corrugating roll unit 40 , the corrugating roll unit 40 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 is prevented. further, fig. 10 is a schematic plan view showing a support device of the pressurizing belt for the corrugating roll unit according to a second modification example of the first embodiment, and fig. 11 is a schematic front view showing the support device of the pressurizing belt for the corrugating roll unit. as shown in figs. 10 and 11 , a support device 102 b of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is provided with a support rod 154 as a support member for supporting the lower belt 43 b of the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 . further, the belt support mechanism is provided with a rotation device 155 as a support member moving device which moves the support rod 154 to a retracted position where the support rod 154 is separated from the pressurizing belt 43 by a predetermined distance and a support position where the support rod 154 supports the pressurizing belt 43 . specifically, the rotation device 155 is provided coaxially with the belt roll 41 and the support rod 154 is connected to the rotation device 155 through a pair of connection rods 156 from the respective axial end portions of the belt roll 41 , and the support rod 154 is disposed substantially in parallel to the belt roll 41 on the outside of the belt roll 41 . for this reason, the support rod 154 is moved around the rotation center of the belt roll 41 by the rotation device 155 through the connection rods 156 , thereby being able to support the lower belt 43 b of the pressurizing belt 43 from below. during the operation of the single facer 15 , that is, when the pressurizing belt 43 is being moved by the belt roll 41 and the tension roll 42 , the pressurizing belt 43 is in contact with the upper corrugating roll 44 (the solid line state in fig. 7 ). at this time, the support rod 154 is located at a retracted position (a position shown by a two-dot chain line in figs. 10 and 11 ) where the support rod 154 is separated from the pressurizing belt 43 , further on the upper side than the belt roll 41 . then, when the operation of the single facer 15 is stopped and the corrugating roll unit 40 is replaced, the support rod 154 is moved by the rotation device 155 through the connection rods 156 to be located at a support position (a position shown by a solid line in figs. 10 and 11 ) where the support rod 154 support the lower belt 43 b from below. here, the existing corrugating roll unit 40 is lowered as shown by the solid line in fig. 11 , and then moved in the removal direction x 2 and removed. subsequently, another corrugating roll unit 40 is moved in the mounting direction x 1 to the space where the existing corrugating roll unit 40 has been removed, and then lifted. at this time, since the lower belt 43 b is supported by the support rod 154 , the pressurizing belt 43 is prevented from hanging down as shown by a two-dot chain line in fig. 11 . for this reason, even if the corrugating roll unit 40 is moved in the removal direction x 2 or the mounting direction x 1 at the time of the replacement of the corrugating roll unit 40 , the corrugating roll unit 40 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 is prevented. further, fig. 12 is a schematic plan view showing a support device of the pressurizing belt for the corrugating roll unit according to a third modification example of the first embodiment. as shown in fig. 12 , a support device 102 c of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is provided with a support rod 157 as a support member for supporting the lower belt 43 b of the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 . further, the belt support mechanism is provided with a rotation device 158 as a support member moving device which moves the support rod 157 to a retracted position where the support rod 157 is separated from the pressurizing belt 43 by a predetermined distance and a support position where the support rod 157 supports the pressurizing belt 43 . specifically, the rotation device 158 is provided coaxially with the belt roll 41 and the support rod 157 is connected to the rotation device 158 through a connection rod 159 from an axial end portion of the belt roll 41 , and the support rod 157 is disposed substantially in parallel to the belt roll 41 on the outside of the belt roll 41 . in this case, the support rod 157 is cantilevered and extends toward the mounting direction x 1 side from further the removal direction x 2 side than the pressurizing belt 43 . for this reason, the support rod 157 is rotated around the rotation center of the belt roll 41 by the rotation device 158 through the connection rod 159 and moved from a retracted portion (a position shown by a two-dot chain line in fig. 12 ) to a support position (a position shown by a solid line in fig. 12 ), thereby being able to support the lower belt 43 b of the pressurizing belt 43 from below. the operation of the support device 102 c of the pressurizing belt for the corrugating roll unit is substantially the same as the support device 102 b of the pressurizing belt for the corrugating roll unit described above, and therefore, description thereof is omitted. further, fig. 13 is a schematic front view showing a support device of the pressurizing belt for the corrugating roll unit according to a fourth modification example of the first embodiment. as shown in fig. 13 , a support device 102 d of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is provided with a support rod 160 as a support member for supporting the upper belt 43 a of the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 . further, the belt support mechanism is provided with a support member moving device which moves the support rod 160 to a retracted position where the support rod 160 is separated from the pressurizing belt 43 by a predetermined distance and a support position where the support rod 160 supports the pressurizing belt 43 , and is, for example, the rotation device 155 or 158 and the connection rod 156 or 159 described above. the support rod 160 is disposed substantially in parallel to the belt roll 41 between the upper belt 43 a and the lower belt 43 b in the belt roll 41 . for this reason, if the support rod 160 is rotated and lifted by the rotation device, the support rod 160 can lift and support the upper belt 43 a of the pressurizing belt 43 from below. during the operation of the single facer 15 , that is, when the pressurizing belt 43 is being moved by the belt roll 41 and the tension roll 42 , the pressurizing belt 43 is in contact with the upper corrugating roll 44 (the solid line state in fig. 7 ). at this time, the support rod 160 is located between the upper belt 43 a and the lower belt 43 b and at a retracted position where the support rod 160 is separated from the pressurizing belt 43 . then, when the operation of the single facer 15 is stopped and the corrugating roll unit 40 is replaced, the support rod 160 which is located at a position shown by a two-dot chain line in fig. 13 is lifted to a position shown by a solid line in fig. 13 and located at a support position where the support rod 160 supports and lifts the upper belt 43 a from below. here, the existing corrugating roll unit 40 is lowered as shown by the solid line in fig. 13 , and then moved in the removal direction x 2 and removed. subsequently, another corrugating roll unit 40 is moved in the mounting direction x 1 to the space where the existing corrugating roll unit 40 has been removed, and then lifted. at this time, since the upper belt 43 a is lifted and supported by the support rod 160 , the pressurizing belt 43 is prevented from hanging down as shown by a two-dot chain line in fig. 13 . for this reason, even if the corrugating roll unit 40 is moved in the removal direction x 2 or the mounting direction x 1 at the time of the replacement of the corrugating roll unit 40 , the corrugating roll unit 40 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 is prevented. further, fig. 14 is a schematic front view showing a support device of the pressurizing belt for the corrugating roll unit according to a fifth modification example of the first embodiment. as shown in fig. 14 , a support device 102 e of the pressurizing belt for the corrugating roll unit is provided with a belt support mechanism which prevents lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 . the belt support mechanism is a pressurizing force adjusting device capable of adjusting the tension of the pressurizing belt 43 by adjusting the distance between the belt roll 41 and the tension roll 42 . the pressurizing force adjusting device has a hydraulic cylinder 161 , and a tip portion of a drive rod is connected to a support shaft of the tension roll 42 . during the operation of the single facer 15 , that is, when the pressurizing belt 43 is being moved by the belt roll 41 and the tension roll 42 , the pressurizing belt 43 is in contact with the upper corrugating roll 44 (the solid line state in fig. 7 ). at this time, the tension roll 42 is at a predetermined position, and the tension of the pressurizing belt 43 is adjusted to a desired value. then, when the operation of the single facer 15 is stopped and the corrugating roll unit 40 is replaced, the hydraulic cylinder 161 is operated to move the tension roll 42 from a retracted position shown by a two-dot chain line in fig. 14 to a support position shown by a solid line so as to separate the tension roll 42 from the belt roll 41 . here, the existing corrugating roll unit 40 is lowered as shown by the solid line in fig. 14 , and then moved in the removal direction x 2 and removed. subsequently, another corrugating roll unit 40 is moved in the mounting direction x 1 to the space where the existing corrugating roll unit 40 has been removed, and then lifted. at this time, since the distance between the belt roll 41 and the tension roll 42 becomes long, the pressurizing belt 43 does not hang down. for this reason, even if the corrugating roll unit 40 is moved in the removal direction x 2 or the mounting direction x 1 at the time of the replacement of the corrugating roll unit 40 , the corrugating roll unit 40 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 is prevented. here, a method of replacing a corrugating roll unit by the apparatus for replacing a corrugating roll unit 100 of the first embodiment configured in this manner will be described. figs. 16 to 18 are plan views showing the method of replacing a corrugating roll unit of the first embodiment. the method of replacing a corrugating roll unit by the apparatus for replacing a corrugating roll unit 100 of the first embodiment includes a step of mounting the corrugating roll unit 40 on the second accommodation part n 2 with the first accommodation part n 1 of the mounting base 111 empty, a step of moving the mounting base 111 to a first replacement position where the first accommodation part n 1 faces the existing corrugating roll unit 40 , a step of moving the existing corrugating roll unit 40 to the first accommodation part n 1 at the first replacement position, a step of moving the mounting base 111 to a second replacement position where the second accommodation part n 2 faces the space where the existing corrugating roll unit 40 has been removed, a step of moving the corrugating roll unit 40 of the second accommodation part n 2 to the space at the second replacement position, and a step of retracting the mounting base 111 from the second replacement position. the method of replacing a corrugating roll unit by the apparatus for replacing a corrugating roll unit 100 will be specifically described. as shown in figs. 4 and 15 , the corrugating roll unit 40 to be newly mounted is mounted on the second accommodation part n 2 with the first accommodation part n 1 of the mounting base 111 empty, and a worker operates the operating panel 135 to operate the first traveling device 125 , thereby moving the mounting base 111 in the mounting direction x 1 . then, as shown in figs. 4, 15, and 16 , the front end portion of the mounting base 111 comes into contact with the stopper 142 , so that the mounting base 111 stops, and the worker operates the operating panel 135 to stop the operation of the first traveling device 125 . then, the worker operates the operating panel 135 to operate the lifting device 127 , thereby lowering the wheels 132 a and 132 b . then, the wheels 132 a are fitted to the guide rail 145 , and the mounting base 111 is positioned with the minute distance s interposed between itself and the stopper 142 . then, the worker operates the operating panel 135 to operates the second traveling device 126 , thereby moving the mounting base 111 along the second horizontal direction y, and thus the mounting base 111 is moved to the first replacement position where the first accommodation part n 1 of the mounting base 111 faces the existing corrugating roll unit 40 , and stopped. the stop of the mounting base 111 may be manually performed by the operation of the operating panel 135 by the worker, or may be automatically performed by detecting the mounting base 111 by a detection sensor provided at an appropriate position. if the mounting base 111 stops at the first replacement position, as shown in fig. 16 , here, the existing corrugating roll unit 40 is moved to the first accommodation part n 1 by the unit replacement mechanism 103 . although not described in detail, the unit replacement mechanism 103 is provided on the single facer 15 side and moves the corrugating roll unit 40 between the frame 141 of the single facer 15 and the corrugating roll unit replacement carriage 101 . further, immediately before the existing corrugating roll unit 40 is moved by the unit replacement mechanism 103 , the lowering of the pressurizing belt 43 is blocked by the support device 102 of the pressurizing belt for the corrugating roll unit. if the existing corrugating roll unit 40 is accommodated in the first accommodation part n 1 of the mounting base 111 , as shown in figs. 16 and 17 , the worker operates the operating panel 135 to operate the second traveling device 126 , thereby moving the mounting base 111 along the second horizontal direction y, and the mounting base 111 is moved to the second replacement position where the second accommodation part n 2 of the mounting base 111 faces the space n 3 where the existing corrugating roll unit 40 has been removed, and stopped. the stop of the mounting base 111 may be manually performed by the operation of the operating panel 135 by the worker, or may be automatically performed by detecting the mounting base 111 by a detection sensor provided at an appropriate position. if the mounting base 111 stops at the second replacement position, the corrugating roll unit 40 of the second accommodation part n 2 is moved to the space n 3 by the unit replacement mechanism 103 . if the corrugating roll unit 40 of the second accommodation part n 2 is moved to the space n 3 , the support of the pressurizing belt 43 by the support device 102 of the pressurizing belt for the corrugating roll unit is stopped. then, as shown in figs. 4, 17, and 18 , the worker operates the operating panel 135 to operate the lifting device 127 , thereby lifting the wheels 132 a and 132 b . then, the wheels 132 a are separated from the floor surface g, and the front wheels 128 a and the rear wheels 128 b of the first traveling device 125 are grounded to the floor surface g. then, the worker operates the operating panel 135 to operates the first traveling device 125 , thereby moving the mounting base 111 along the removal direction x 2 , and the mounting base 111 is retracted from the second replacement position, whereby the replacement work is finished. in this manner, the corrugating roll unit replacement carriage of the first embodiment includes the mounting base 111 having the first accommodation part n 1 for accommodating the corrugating roll unit 40 to be removed and the second accommodation part n 2 for accommodating the corrugating roll unit 40 to be mounted, and the movement device 112 which moves the mounting base 111 to the first replacement position where the first accommodation part n 1 faces the existing corrugating roll unit 40 , the second replacement position where the second accommodation part n 2 faces the space n 3 where the existing corrugating roll unit 40 has been removed, and the retracted position separated from the first replacement position and the second replacement position. therefore, first, if the mounting base 111 is moved from the retracted position to the first replacement position by the movement device 112 , the first accommodation part n 1 faces the existing corrugating roll unit 40 . here, the existing corrugating roll unit 40 is moved to the first accommodation part n 1 . next, the mounting base 111 is moved from the first replacement position to the second replacement position where the second accommodation part n 2 faces the space n 3 where the existing corrugating roll unit 40 has been removed, by the movement device 112 . here, the corrugating roll unit 40 in the second accommodation part n 2 is moved to the space n 3 where the existing corrugating roll unit 40 has been removed. then, the mounting base 111 is moved from the second replacement position to the retracted position by the movement device 112 , whereby the replacement work is completed. as a result, it is possible to perform the replacement work of the corrugating roll unit 40 with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit 40 without disturbing various types of work by the worker. in the corrugating roll unit replacement carriage of the first embodiment, as the movement device 112 , the first traveling device 125 which allows the mounting base 111 to travel along the first horizontal direction x which is the mounting direction x 1 and the removal direction x 2 of the corrugating roll unit 40 , the second traveling device 126 which allows the mounting base 111 to travel along the second horizontal direction y orthogonal to the first horizontal direction x, and the lifting device 127 as a switching device which performs switching so as to be able to selectively use the first traveling device 125 and the second traveling device 126 are provided. therefore, if the first traveling device 125 is selected and operated, it is possible to allow the mounting base 111 to travel along the first horizontal direction x, and if the second traveling device 126 is selected and operated, it is possible to allow the mounting base 111 to travel along the second horizontal direction y. for this reason, the mounting base 111 can be smoothly moved to the first replacement position and the second replacement position. in the corrugating roll unit replacement carriage of the first embodiment, the wheels 132 a and 132 b of the second traveling device 126 can be lifted and lowered by the lifting device 127 . therefore, the use of the first traveling device 125 and the second traveling device 126 can be easily switched, and thus it is possible to smoothly move the mounting base 111 in a predetermined direction and to simplify a structure. in the corrugating roll unit replacement carriage of the first embodiment, the guide rails 121 and 122 which move the corrugating roll unit 40 along the mounting direction x 1 and the removal direction x 2 are provided in the first accommodation part n 1 and the second accommodation part n 2 of the mounting base 111 . therefore, the corrugating roll unit 40 can be moved in the removal direction x 2 by the guide rails 121 and 122 and easily accommodated in the first accommodation part n 1 , and the corrugating roll unit 40 in the second accommodation part n 2 can be moved in the mounting direction x 1 by the guide rails 121 and 122 and easily mounted at a predetermined position. further, the apparatus for replacing a corrugating roll unit of the first embodiment includes the corrugating roll unit replacement carriage 101 , and the unit replacement mechanism 103 which performs removal and mounting of the corrugating roll unit 40 between the single facer 15 and the corrugating roll unit replacement carriage 101 . therefore, since the replacement work of the corrugating roll unit 40 is performed between the single facer 15 and the corrugating roll unit replacement carriage 101 by the unit replacement mechanism 103 , it is possible to perform the replacement work of the corrugating roll unit 40 with the movement of one corrugating roll unit replacement carriage 101 , and thus it is possible to improve the workability of the replacement work of the corrugating roll unit 40 without disturbing various types of work by the worker. the apparatus for replacing a corrugating roll unit of the first embodiment includes the belt support mechanism which blocks the lowering of the pressurizing belt 43 at the time of the replacement of the corrugating roll unit 40 composed of the upper and lower corrugating rolls 44 and 45 . therefore, at the time of the replacement of the corrugating roll unit 40 , the upper corrugating roll 44 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 can be prevented. as a result, it is possible to improve the workability of the replacement work of the corrugating roll unit 40 . the belt support mechanism operates at the time of the replacement of the corrugating roll unit 40 to block the lowering of the pressurizing belt 43 . however, there is no limitation to such an operation. it is preferable to operate the belt support mechanism before the existing corrugating roll unit 40 is moved in the removal direction x 2 and accommodated in the first accommodation part n 1 of the mounting base 111 . however, when the existing corrugating roll unit 40 is removed, the existing corrugating roll unit 40 is lowered and then moved in the removal direction x 2 , and therefore, the belt support mechanism may be operated after the existing corrugating roll unit 40 is moved in the removal direction x 2 and accommodated in the first accommodation part n 1 and before the corrugating roll unit 40 in the second accommodation part n 2 of the mounting base 111 is moved in the mounting direction x 1 to move to the space n 3 . in the apparatus for replacing a corrugating roll unit of the first embodiment, as the belt support mechanism, the support member for supporting the pressurizing belt 43 wound around the belt roll 41 and the tension roll 42 is provided. therefore, since the pressurizing belt 43 is supported by the support member at the time of the replacement of the corrugating roll unit 40 , it is possible to easily prevent the contact between the upper corrugating roll 44 and the pressurizing belt 43 with a simple configuration. in the apparatus for replacing a corrugating roll unit of the first embodiment, the belt support mechanism includes the support member moving device which moves the support member to a retracted position where the support member is separated from the pressurizing belt 43 by a predetermined distance, and a support position where the support member supports the pressurizing belt 43 . therefore, the support member is normally located at the retracted position where the support member is separated from the pressurizing belt 43 , so that the operation of the single facer 15 is not hindered. then, at the time of the replacement of the corrugating roll unit 40 , the support member is moved to the support position where the support member supports the pressurizing belt 43 , by the support member moving device, and therefore, the support member easily supports the pressurizing belt 43 with a simple configuration, whereby it is possible to prevent the contact between the upper corrugating roll 44 and the pressurizing belt 43 . in the apparatus for replacing a corrugating roll unit of the first embodiment, as the support member, the support rod 152 a , 152 b , 154 , 157 , or 160 for supporting the pressurizing belt 43 from below in the vertical direction is provided to be movable. therefore, at the time of the replacement of the corrugating roll unit 40 , the support rod 152 a , 152 b , 154 , 157 , or 160 is moved to the support position and supports the pressurizing belt 43 from below, and therefore, it is possible to prevent the contact between the upper corrugating roll 44 and the pressurizing belt 43 by easily supporting the pressurizing belt 43 with a simple configuration. in the apparatus for replacing a corrugating roll unit of the first embodiment, as the support member, the suction member 151 which suctions the pressurizing belt 43 from above in the vertical direction is provided to be movable up and down. therefore, at the time of the replacement of the corrugating roll unit 40 , the pressurizing belt 43 is suctioned from above by the suction member 151 , and therefore, it is possible to prevent the contact between the upper corrugating roll 44 and the pressurizing belt 43 by easily supporting the pressurizing belt 43 with a simple configuration. in the apparatus for replacing a corrugating roll unit of the first embodiment, as the belt support mechanism, an adjustment device (the hydraulic cylinder 161 ) for adjusting the distance between the belt roll 41 and the tension roll 42 is provided. therefore, it is possible to prevent the contact between the upper corrugating roll 44 and the pressurizing belt 43 by easily supporting the pressurizing belt 43 with the existing device. the apparatus for replacing a corrugating roll unit of the first embodiment includes the corrugating roll unit replacement carriage 101 , the stopper 142 which blocks the movement of the mounting base 111 when the mounting base 111 is moved along the mounting direction x 1 of the corrugating roll unit 40 by the first traveling device 125 , and the unit replacement mechanism 103 which performs removal and mounting of the corrugating roll unit 40 between the single facer 15 and the corrugating roll unit replacement carriage 101 . therefore, first, if the first traveling device 125 is operated to allow the mounting base 111 to travel along the first horizontal direction x 1 , the mounting base 111 comes into contact with the stopper 142 , whereby the movement thereof is blocked, and next, the second traveling device 126 is operated to allow the mounting base 111 to travel along the second horizontal direction y, thereby moving the mounting base 111 to the first replacement position or the second replacement position. then, at the first replacement position, the existing corrugating roll unit 40 is moved to the first accommodation part n 1 by the unit replacement mechanism 103 . further, at the second replacement position, the corrugating roll unit 40 in the second accommodation part n 2 is moved to the space n 3 by the unit replacement mechanism 103 . then, the mounting base 111 is moved from the second replacement position to the retracted position by the movement device 112 , whereby the replacement work is completed. as a result, it is possible to perform the replacement work of the corrugating roll unit 40 with the movement of one corrugating roll unit replacement carriage 101 , and thus it is possible to improve the workability of the replacement work of the corrugating roll unit 40 without disturbing various types of work by the worker. in the apparatus for replacing a corrugating roll unit of the first embodiment, the minute movement mechanism 143 is provided which moves the mounting base 111 in the removal direction x 2 opposite to the mounting direction x 1 of the corrugating roll unit 40 by the minute distance s set in advance, from the contact position with the stopper 142 . therefore, when the mounting base 111 has come into contact with the stopper 142 , the mounting base 111 is moved in the removal direction x 2 by the minute distance s from the contact position by the minute movement mechanism 143 , and therefore, it is possible to allow the mounting base 111 to travel in the second horizontal direction y in a state of being separated from the stopper 142 , and thus it is possible to allow the mounting base 111 to smoothly travel. in the apparatus for replacing a corrugating roll unit of the first embodiment, as the minute movement mechanism 143 , the first inclined surfaces 144 a and 144 b having a convex shape are formed on each of the wheels 132 a of the second traveling device 126 and the second inclined surfaces 146 a and 146 b having a concave shape are formed on the guide rail 145 of the floor surface g. therefore, when the mounting base 111 has come into contact with the stopper 142 , if the lifting device 127 lowers the wheels 132 a and 132 b , the wheels 132 a and 132 b are grounded to the floor surface g, and at this time, since the first inclined surfaces 144 a and 144 b and the second inclined surfaces 146 a and 146 b come into contact with each other and the mounting base 111 is moved in the removal direction x 2 by the minute distance s from the contact position with the stopper 142 , it is possible to allow the mounting base 111 to travel in the second horizontal direction y in a state of being separated from the stopper 142 , and thus it is possible to allow the mounting base 111 to smoothly travel. in the apparatus for replacing a corrugating roll unit of the first embodiment, the support device 102 , 102 a, 102 b, 102 c, 102 d, or 102 e of the pressurizing belt for the corrugating roll unit is provided. therefore, at the time of the replacement of the upper and lower corrugating roll units 40 , lowering of the pressurizing belt 43 is blocked by the belt support mechanism, and therefore, the upper corrugating roll 44 does not come into contact with the pressurizing belt 43 , and thus damage to the pressurizing belt 43 can be prevented. as a result, it is possible to improve the workability of the replacement work of the corrugating roll unit 40 . further, the method of replacing a corrugating roll unit of the first embodiment includes a step of mounting the corrugating roll unit 40 on the second accommodation part n 2 with the first accommodation part n 1 of the mounting base 111 empty, a step of moving the mounting base 111 to the first replacement position where the first accommodation part n 1 faces the existing corrugating roll unit 40 , a step of moving the existing corrugating roll unit 40 to the first accommodation part n 1 at the first replacement position, a step of moving the mounting base 111 to the second replacement position where the second accommodation part n 2 faces the space where the existing corrugating roll unit 40 has been removed, a step of moving the corrugating roll unit 40 of the second accommodation part n 2 to the space at the second replacement position, and a step of retracting the mounting base 111 from the second replacement position. therefore, it is possible to perform the replacement work of the corrugating roll unit 40 with the movement of one corrugating roll unit replacement carriage 101 , and thus it is possible to improve the workability of the replacement work of the corrugating roll unit 40 without disturbing various types of work by the worker. second embodiment fig. 19 is a plan view showing an apparatus for replacing a corrugating roll unit of a second embodiment, and fig. 20 is a front view showing the apparatus for replacing a corrugating roll unit. the members having the same functions as those in the embodiment described above are denoted by the same reference numerals, and detailed description thereof is omitted. in the second embodiment, as shown in figs. 19 and 20 , an apparatus for replacing a corrugating roll unit 200 includes a corrugating roll unit conveyance apparatus 201 , the support device 102 of the pressurizing belt for the corrugating roll unit, and the unit replacement mechanism 103 (all refer to fig. 15 ). here, the support device 102 of the pressurizing belt for the corrugating roll unit and the unit replacement mechanism 103 are the same as those in the first embodiment, and thus description thereof is omitted. the corrugating roll unit conveyance apparatus 201 includes a mounting base 211 and a movement device 212 . the mounting base 211 has a rectangular plate shape and has the first accommodation part n 1 for accommodating the corrugating roll unit 40 to be removed from the single facer 15 and the second accommodation part n 2 for accommodating the corrugating roll unit 40 to be mounted to the single facer 15 . then, in the mounting base 111 , guide rails (guide members) 221 and 222 which support the corrugating roll unit 40 so as to be able to move the corrugating roll unit 40 along the first horizontal direction x in the first accommodation part n 1 and the second accommodation part n 2 , respectively, are provided at an upper surface portion thereof. further, the mounting base 211 is provided with contact parts 223 and 224 at the upper surface portion on one end portion side in the longitudinal direction in the guide rails 221 and 222 . when the corrugating roll unit 40 is moved in the removal direction x 2 by the guide rails 221 and 222 of the mounting base 211 , the corrugating roll unit 40 is positioned by coming into contact with the contact parts 223 and 224 . the movement device 212 is composed of a first movement device 225 and a second movement device 226 . the first movement device 225 is for lifting and lowering the mounting base 211 along a vertical direction z, and the second movement device 226 is for traveling the mounting base 211 along the second horizontal direction y. that is, a stand 231 is installed adjacent to the single facer 15 , and a pair of guide rails 232 is fixed onto the stand 231 along the second horizontal direction y 2 . a conveyance stand 233 has a rectangular plate shape and is supported to be movable on the guide rails 232 by a plurality of traveling wheels 234 . then, the conveyance stand 233 can be moved along the second horizontal direction y by driving and rotating the traveling wheels 234 with a drive device (not shown). the conveyance stand 233 has lifting mechanisms 235 provided on four sides, and a screw shaft 236 is suspended from each of the lifting mechanisms 235 , and each screw shaft 236 is screwed to each support portion 237 of the mounting base 211 . the first movement device 225 can lift and lower the mounting base 211 by rotating each of the screw shafts 236 by each of the lifting mechanisms 235 . the second movement device 226 can move the mounting base 211 along the second horizontal direction y through the conveyance stand 233 by driving and rotating the traveling wheels 234 by the drive device. here, a method of replacing a corrugating roll unit by the apparatus for replacing a corrugating roll unit 200 of the second embodiment configured in this manner will be described. figs. 21 to 23 are plan views showing the method of replacing a corrugating roll unit of the second embodiment. the method of replacing a corrugating roll unit by the apparatus for replacing a corrugating roll unit 200 of the second embodiment includes a step of mounting the corrugating roll unit 40 on the second accommodation part n 2 with the first accommodation part n 1 of the mounting base 211 empty, a step of moving the mounting base 211 to the first replacement position where the first accommodation part n 1 faces the existing corrugating roll unit 40 , a step of moving the existing corrugating roll unit 40 to the first accommodation part n 1 at the first replacement position, a step of moving the mounting base 211 to the second replacement position where the second accommodation part n 2 faces the space where the existing corrugating roll unit 40 has been removed, a step of moving the corrugating roll unit 40 of the second accommodation part n 2 to the space at the second replacement position, and a step of retracting the mounting base 211 from the second replacement position. as shown in figs. 20 and 21 , the corrugating roll unit to be newly mounted is mounted on the second accommodation part n 2 with the first accommodation part n 1 of the mounting base 211 empty, and the first movement device 225 is operated to move the mounting base 211 on the stand 231 , which is the retracted position, downward in the vertical direction z. then, the mounting base 211 is stopped at a predetermined height position. subsequently, the second movement device 226 is operated to move the mounting base 211 along the second horizontal direction y, and the mounting base 211 is moved to the first replacement position where the first accommodation part n 1 of the mounting base 211 faces the existing corrugating roll unit 40 , and stopped. the stop of the mounting base 111 may be performed manually by the worker or may be automatically performed by a detection sensor detecting the mounting base 211 . if the mounting base 211 stops at the first replacement position, here, the existing corrugating roll unit 40 is moved to the first accommodation part n 1 by the unit replacement mechanism 103 . further, immediately before the existing corrugating roll unit 40 is moved by the unit replacement mechanism 103 , lowering of the pressurizing belt 43 is blocked by the support device 102 of the pressurizing belt for the corrugating roll unit. if the existing corrugating roll unit 40 is accommodated in the first accommodation part n 1 of the mounting base 111 , as shown in figs. 21 and 22 , the worker operates the second movement device 226 to move the mounting base 211 along the second horizontal direction y, and thus the mounting base 211 is moved to the second replacement position where the second accommodation part n 2 of the mounting base 211 faces the space where the existing corrugating roll unit 40 has been removed, and stopped. the stop of the mounting base 211 may be performed manually by the worker or may be automatically performed by a detection sensor detecting the mounting base 211 . if the mounting base 211 stops at the second replacement position, here, the corrugating roll unit 40 of the second accommodation part n 2 is moved to the space by the unit replacement mechanism 103 . if the corrugating roll unit 40 of the second accommodation part n 2 moves to the space, the support of the pressurizing belt 43 by the support device 102 of the pressurizing roller for the corrugating roll unit is stopped. then, as shown in fig. 23 , the worker operates the first movement device 225 to move the mounting base 211 upward in the vertical direction z and retract the mounting base 211 from the second replacement position to the upper side which is a retracted position of the stand 231 , whereby the replacement work is finished. in this manner, the corrugating roll unit replacement carriage of the second embodiment includes the mounting base 211 having the first accommodation part n 1 for accommodating the corrugating roll unit 40 to be removed and the second accommodation part n 2 for accommodating the corrugating roll unit 40 to be mounted, and the movement device 212 which moves the mounting base 211 to the first replacement position where the first accommodation part n 1 faces the existing corrugating roll unit 40 , the second replacement position where the second accommodation part n 2 faces the space where the existing corrugating roll unit 40 has been removed, and the retracted position separated from the first replacement position and the second replacement position. therefore, it is possible to perform the replacement work of the corrugating roll unit 40 with the movement of one carriage, and thus it is possible to improve the workability of the replacement work of the corrugating roll unit 40 without disturbing various types of work by the worker. in the corrugating roll unit replacement carriage of the second embodiment, as the movement device 212 , the first movement device 225 for lifting and lowering the mounting base 211 and the second movement device 226 for moving the mounting base 211 along the second horizontal direction y are provided. therefore, if the first movement device 225 is operated, it is possible to lift and lower the mounting base 211 , and if the second movement device 226 is operated, it is possible to allow the mounting base 211 to travel along the second horizontal direction y. for this reason, it is possible to smoothly move the mounting base 211 to the first replacement position and the second replacement position.
|
083-456-625-104-843
|
KR
|
[
"EP",
"KR",
"WO",
"US"
] |
D06F31/00,D06F29/00,D06F33/02,D06F58/28,D06F39/08,D06F58/26,D06F73/00,D06F87/00,D06F37/00
| 2006-06-23T00:00:00 |
2006
|
[
"D06"
] |
total laundry treating system
|
a multiple laundry treating system is provided to reduce size of the system and to reduce water consumption by supplying steam to a plurality of laundry treating devices. a multiple laundry treating system comprises a plurality of laundry treating devices(20,30,40), a control unit(21), a steam generating unit(10), and a steam supply line(60). the laundry treating devices have the control unit. the steam generating unit is installed in one of laundry treating devices. the steam generating unit which is under control of the control unit, generates steam and supplies the steam into the laundry treating devices. the steam supply line supplies the steam from the steam generating unit to another laundry treating devices.
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[1] a total laundry treating system comprising: a plurality of laundry treating apparatuses in which at least one controller is provided to treat laundry; a steam generator provided a predetermined one of the laundry treating apparatuses, wherein the steam generator generates steam based on a control of the controller and the steam generator supplies the steam to the laundry treating apparatuses; a steam supply line through which the steam generated by the steam generator is supplied to the other laundry treating apparatuses having no steam generators. [2] the total laundry treating system as claimed in claim 1, wherein the plurality of the laundry treating apparatuses comprise a washer for washing laundry and a washer having a drying function for washing and drying laundry. [3] the total laundry treating system as claimed in claim 1, wherein the plurality of laundry treating apparatuses comprise a dryer for drying laundry. [4] the total laundry treating system as claimed in claim 3, wherein the plurality of laundry treating apparatuses further comprise a refresher for refreshing laundry. [5] the total laundry treating system as claimed in claim 4, wherein the controller is provided in each of the laundry treating apparatuses. [6] the total laundry treating system as claimed in claim 5, wherein the data transmitting part is a wire cable connected between the controllers or a wireless communication device provided at each of the controllers to send and receive the data among the controllers wirelessly. [7] the total laundry treating system as claimed in claim 6, wherein the data transmitting part is a wire cable connected between the controllers or a wireless communication device provided at each of the controllers to send and receive the data among the controllers wirelessly. [8] the total laundry treating system as claimed in claim 1, wherein the plurality of laundry treating apparatuses further comprise a steam iron. [9] the total laundry treating system as claimed in claim 1, wherein the predetermined laundry treating apparatus including the steam generator is a washer. [10] the total laundry treating system as claimed in claim 1, wherein the predetermined laundry treating apparatus having the steam generator is a dryer for drying laundry or a washer having a drying function for washing and drying r. laundry. [11] the total laundry treating system as claimed in claim iq wherein the dryer or the washer having a drying function comprises a hot air generator that generates hot air based on a control of the controller. [12] the total laundry treating system as claimed in claim 11, fiirther comprising a hot air supply line through which the hot air generated by the hot air generator is supplied to the other laundry treating apparatuses having no hot air generator. [13] the total laundry treating system as claimed in claim 12, further comprising; a hot air collect line through which hot air exhausted from the other laundry treating apparatuses is collected. a condenser that the hot air collected through the hot air collect line is condensed. [14] the total laundry treating system as claimed in claim 1, wherein the steam generator is a capacity adjustable type steam generator that adjusts a steam amount supplied to the laundry treating apparatuses. [15] the total laundry treating system as claimed in claim 1, wherein at least one of the laundry treating apparatuses has a different laundry treating module.
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scoro copy description total laundry treating system technical field [1] the present invention relates to a total laundry treating system. more specifically, the present invention relates to a total laundry treating system composed of laundry treating devices as a set. background art [2] laundry treating apparatuses are all kinds of appliances that are used in houses, laundromats or dry cleaners' to treat clothes, cloth items, bedding and the like (hereinafter, laundry) sich as washing, drying, removing wrinkles. [3] for example, laundry treating apparatuses include washers, dryers, laundry devices having washing and drying functions, refreshers, irons for removing or producing wrinkles of laundry and steamers for removing unnecessary wrinkles. [4] more specifically, the refreshers are appliances that performs drying, supplying aroma to laundry, prevents static electricity of laundry or removing winkles of laundry. these kinds of refreshers are consumed a lot in north america. [5] the steamers are appliances that supplies steam to laundry to remove wrinkles of laundry. the steamer may not allow a hot plate to contact with the laundry, different from the iron. as a result, the steamers are consumed a lot in here in korea via home shopping channels. [6] recently, washers having steam generators, especially, drum type washers have come into wide use. the products have become popular in recent years which supplies steam to laundry during washing or before/after washing, to maximize washing efficiency by using functions of sterilization, laundry soaking time reduction and detergent activation. disclosure of invention technical problem [7] as mentioned above, it is common that these kinds of laundry treating apparatuses are separately placed in places where laundry is treated. [8] that is, such laundry treating apparatuses happen to be scattered in space. even though such laundry treating apparatuses are placed in one space, the laundry treating apparatuses have no interrelation with each other and a user has to spend quite a time in treating laundry. [9] it may not be preferred as a matter of space utility or laundry treating time efficiency and production cost that the steam used in laundry treating is generated in each of the laundry treating apparatuses. [10] in addition, if each of the laundry treating apparatuses has a water supply source for generating the steam, a user can feel inconvenient. technical solution [11] to solve the problems, an object of the present invention is to provide a total laundry treating system composed of laundry treating devices as a set. [12] to achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, a total laundry treating system includes a plurality of laundry treating apparatuses in which at least one controller is provided to treat laundry; a steam generator provided a predetermined one of the laundry treating apparatuses, wherein the steam generator generates steam based on a control of the controller and the steam generator supplies the steam to the laundry treating apparatuses; a steam supply line through which the steam generated by the steam generator is supplied to the other laundry treating apparatuses having no steam generators. [13] here, the plurality of the laundry treating apparatuses may include a washer for washing laundry, a washer having a drying function for washing and drying laundry and a dryer for drying laundry, also, the plurality of the laundry treating apparatuses may include a refresher or iron. [14] on the other hand, the plurality of the laundry treating apparatuses may be various kinds of laundry treating apparatuses having separate laundry treating modules. that is, in one total laundry treating system, there are provided a plurality of washers, a dryer and a refresher, or a plurality of dryers, a washer and a refresher. [15] commonly, such laundry treating apparatuses in houses may be configured to be different kinds of laundry treating apparatuses performing separate laundry treating modules. here, the laundry treating module is modules for washing, drying and refreshing. [16] the controller may be provided in a predetermined one of the plurality of the laundry treating apparatuses. in this case, the controller controls an operation of each laundry treating apparatus and an operation of the steam generation. the controller may be connected to each of the laundry treating apparatuses via only a control wire. [17] the controller may be provided in each of the laundry treating apparatuses. in this case, each controller separately controls the corresponding laundry treating apparatus. [18] here, the total laundry treating system may further include a data transmitting part • <vf a,&» l u. d l , uv v i < that transmits data between the controller provided in the predetermined laundry treating apparatus including the steam generator and the controllers provided in the other laundry treating apparatuses. [19] the data transmitting part may be a wire cable connected between the controllers or a wireless communication device provided at each of the controllers to send and receive the data among the controllers wirelessly. [20] the plurality of laundry treating apparatuses may further include a steam iron. [21] by the way, the total laundry treating system may include a predetermined one laundry treating apparatus having the steam generator and the other laundry treating apparatuses receiving steam from the steam generator. [22] here, the capacity of the steam generator may be adjustable according to a case that steam is requested by all of the laundry treating apparatuses and a case that steam is requested by one of the laundry treating apparatuses. this is because user inconvenience and energy saving caused by insufficient steam supply or time delay of steam supply may be accomplished. [23] on the other hand, the total laundry treating system may further include a hot air generator that generates hot air based on a control of the controller; a data transmitting part for transmitting data between a controller of the hot air generator and the controller of the laundry treating apparatuses; and an hot air supply line through which the hot air generated by the hot air generator is supplied to the other laundry treating apparatuses having no hot air generator. [24] the total laundry treating system may fiirther include a hot air collect line through which hot air exhausted from the other laundry treating apparatuses is collected. the hot air generator may include a condenser that the hot air collected through the hot air collect line is condensed. [25] that is, it is possible to embody an air condensation type drying function in that hot air is not exhausted outside but circulated and to embody an air exhaustion type drying function in that hot air is exhausted by each of the laundry treating apparatuses separately. [26] in the total laundry treating system including the hot air generator, the steam generator and the hot air generator are controlled by one controller, which is efficient as a matter of production cost. in addition, there is an effect of a simple structure, because an auxiliary data transmitting part for sharing the hot air generator does not have to be provided other than the data transmitting part for sharing the steam generator. ^ mvfδufe 1 i,. [β il . £!/(//. [27] at least one of the laundry treating apparatuses has a different laundry treating module. advantageous effects [28] the present invention has following advantageous effects. [29] each of the laundry treating apparatuses is inter-relative and thus a convenient total laundry treating system may be provided. that is, the total laundry treating system according to the present invention is efficient and convenient in a view of space or a laundry treating time. [30] furthermore, according to the present invention there are provided the plurality of the laundry treating apparatuses that uses steam, respectively, and the steam the total laundry treating system having the steam generator for supplying steam to each of the laundry treating apparatuses. as a result, the present invention has an advantageous effect that a series of laundry treating processes may be performed conveniently. [31] a still farther, the steam generator able to adjust the amount of steam supply is provided in the total laundry treating system according to the present invention. as a result, efficient steam supply is possible and energy saving is possible. [32] a still farther, according to the present invention, steam is supplied to the plurality of the laundry treating apparatuses through the single steam generator. as a result, a user may easily secure a water source for steam generation. [33] a still farther, the hot air generator for supply air, especially, hot air as well as the steam generator is provided in each of the laundry treating apparatuses. as a result, the laundry treating process may be performed convenient. [34] lastly, the total laundry treating system may be embodied by using conventional washers having the steam generators or dryers having the hot air generators. brief description of the drawings [35] the accompanying drawings, which are included to provide farther understanding of the disclosure and are incorporated in and constitute a part of this application, illustrate embodiments of the disclosure and together with the description serve to explain the principle of the disclosure. [36] in the drawings: [37] fig. 1 is a block view illustrating a first embodiment of the present invention; [38] fig. 2 is a block view illustrating a second embodiment of the present invention; [39] fig. 3 is a block view illustrating a third embodiment of the present invention; [40] fig. 4 is a block view illustrating a fourth embodiment of the present invention; and [41] fig. 5 is a diagram schematically illustrating a steam generator provided in the present invention. best mode for carrying out the invention [42] reference will now be made in detail to the specific embodiments of the present invention, examples of which are illustrated in the accompanying drawings. wherever possible, the same reference numbers will be used thrαghout the drawings to refer to the same or like parts. [43] in reference to figs. 1 to 5, preferred embodiments of the present invention will explained. [44] fig. 1 is a block view illustrating a first embodiment of the present invention. next, the first embodiment will be explained. [45] a total laundry treating system 100 according to the first embodiment may include a steam generator 10 and a plurality of laundry treating apparatuses 2q 30 and 40. here, the laundry treating apparatuses may be appliances that have the same laundry treating module, or may be appliances that have different laundry treating modules, respectively. [46] the steam generator 10 may be provided in a predetermined one of the laundry treating apparatuses. fig. 1 presents that the steam generator 10 is provided in a washer 20. [47] such washers having steam generators have been used a lot and demands of such washers have been increasing in market because of high washing efficiency. [48] fig. 1 illustrates a washer 2q a dryer 30 and a refresher 40 as laundry treating apparatuses. of course, these laundry treating apparatuses may be different kinds of laundry treating apparatuses and may include more laundry treating apparatuses. [49] meanwhile, the present specification may not explain junctions and structures of individual laundry treating apparatuses in detail, because the functions and the structures are well-known knowledge to those skilled in the art and the present invention is not limited to the detailed functions or structures. accordingly, the technical subject matter of the present invention may pertain to any kinds of laundry treating apparatuses applied to the present invention. [50] next, as shown in fig. 1, a total laundry treating system including the washer 2q the dryer 30 and the refresher 40 as the plurality of the laundry treating apparatuses will be explained. [51] steam may be supplied to the washer 2q the dryer 30 and the refresher 40 to 6 wjm, i l u f . έwi. improve washing efficiency, remove wrinkles, prevent static electricity, perform sterilization or remove bad smell of laundry. [52] here, the steam supplied to the washer 2q the dryer 30 and the refresher 40 is generated by a steam generator that is provided in a predetermined one of the laundry treating apparatuses. [53] fig. 1 illustrates that a controller 21 and the steam generator 10 are provided in the washer 20. [54] as shown in fig. 1, the controller 21 provided in the washer 10 controls operations of dryer 30 and the refresher 40 as well as the washer 20. that is, only driving parts operated by the control of the controller 21 are provided in the dryer 30 and the refresher 40. as a result, only a control wire 50 is connected among the controller 21, the dryer 30 and the refresher 40 to allow a control signal transmitted, such that the total laundry treating system is embodied. [55] the controller 21 operates the steam generator 10 if necessary to generate steam and it controls the steam to be supplied to the washer 2q the dryer 30 and the refresher 40. [56] in case the washer 20 having the steam generator 10 is applied to the total laundry treating system, a steam supply line (d should be additionally provided and the steam is supplied from the steam generator 10 outside the washer 20 through the steam supply line (d. [57] if the controller 21 performs all the control of the total laundry treating system, the dryer 30 or the refresher 40 do not have to include controllers. as a result, a user uses the total laundry treating system via the controller 21 provided in the washer 20. [58] next, in reference to fig. 2, a second embodiment of the present invention will be explained. [59] the embodiment shown in fig. 2 substantially has the same structure of the above embodiment, except that an additional controller is provided in each of the laundry treating apparatuses without the steam generator 10. specifically, if the steam generator 10 is provided in the washer iq a dryer controller 31 is provided in the dryer 31 and a refresher controller 41 is provided in the refresher 40. [(d] here, each controller 21, 31 and 41 controls an operation of each laundry treating apparatus. [61] a washer controller 21 is provided in the washer 20 and a dryer controller 31 is provided in the dryer 30 and a refresher 41 is provided in the refresher 4q separately. as a result, the laundry treating apparatuses perform separate laundry treating modules u by using separate controllers 21, 31 and 41. [62] for example, if the dryer 30 needs steam, the controller 31 of the dryer 30 requests steam supply to the controller 21 of the washer 20 via a data transmitting part 50. the controller 21 of the washer 20 controls an operation of the steam generator iq corresponding to the request, to supply the requested steam to the dryer 30. at this time, the steam is supplied through the steam supply line (d. [63] in this embodiment, the steam is supplied to each of the laundry treating apparatuses by the steam generator 10 provided in a predetermined one of the laundry treating apparatuses, for example, the washer 20. [64] such control logic may be applied to the case that the steam generator 10 is provided in the dryer 20 or the refresher 40. [65] by the way, the data transmitting part 50 may be a cable. while, the data transmitting part 50 may include a wireless communication device (not shown) provided in the controller 21 of the washer 20 and wireless communication devices (not shown) provided the other controllers 31 and 41 of the other laundry treating apparatuses. at this time, data may be sent and received wirelessly. [66] the wire/wireless data transmitting is well-known knowledge to those skilled in the art and easy for them to expect. therefore, the detailed explanation thereof will be omitted. [67] the present invention includes the steam supply line (d through which the steam generated by the steam generator 10 is supplied to the laundry treating apparatuses. the steam supply line (d may be formed between the steam generator 10 and each of the laundry treating apparatuses. [68] as shown in fig. 2, the steam supply line (d may include a header 61 and branched steam pipes 62 and 63. the header 61 is connected to an outlet (not shown) of the steam generator 10 for branching a steam flow. the branched steam pipes 62 and 63 are branched from the header 6 such that each branched steam pipe is branched to each of the laundry treating apparatuses. the branched steam pipes 62 and 63 are connected to an inlet (not shown) of each laundry treating apparatus and steam is supplied to the laundry treating apparatuses thrαgh the branched steam pipes 62 and 63. [©] although not shown in fig. 2, a valve may be provided at the header 61, the branched steam pipes 62 and 63, the outlet of the steam generator 10 or the inlets of the laundry treating apparatuses to be selectively opened and closed. controlling the valve enables the steam to be supplied to the laundry treating apparatus that needs the steam. [70] next, in reference to fig. 3, a third embodiment will be explained. fig. 3 is a block view illustrating the third embodiment. [71] a total laundry treating system according to this embodiment further includes a hot air generator 80. specifically, according to this embodiment the laundry treating apparatuses share the hot air generator 80 as well as the steam generator iq while according to above embodiments the laundry treating apparatuses share only the steam generator 10. [72] dryers or washers having a drying function typically include means for forcibly supply hot air to the laundry to dry the laundry and one of the examples is a hot air generator. the hot air generator 80 includes a fan (not shown) that forcibly circulates air and a heater (not shown) that heats the air. as a result, the hot air is supplied into a dryer to dry the laundry. here, the damp air inside the dryer may be exhausted outside right away, or may be re-circulated after passing a condenser to remove its moisture. the former is called an exhaustion type drying and the latter is called a condensation type drying. [73] a heating source of the heater may be a gas burner or an electric heater, which is not limited thereto. [74] the subject matter of the present invention may not pertain to such specific dryer and thus the detailed description thereof will be omitted. [75] as shown in fig. 3, this embodiment has the same configuration of the above embodiment shown in fig. 2, except that the hot air generator 80 is provided in a predetermined one of the laundry treating apparatuses. [76] fig. 3 shows that the hot air generator 80 is provided in a dryer 30 and the dryer 30 may be a washer having a drying function that can perform a drying and washing function. as a result, according to this embodiment, the plurality of the laundry treating apparatuses may share the hot air generator 80 as well as the steam generator 10. [77] as mentioned above, generally the dryer 30 includes the hot generator 80. as a result, the total laundry treating system according to this embodiment can be embodied without any additional hot generator and thus the detailed description thereof will be omitted. [78] here, hot air may not mean only literally hot air, which may include normal temperature air. [79] such normal and high temperature air is forcibly supplied to the dryer to dry or 9 aw ι «. «ι. -mm ( . refresh the laundry. [80] in this case, it is preferable that a hot air supply line 70 is provided to supply hot air to each of the laundry treating apparatuses 20 and 40 from the hot air generator 80. that is, the hot air supply line 70 is a separate component from the steam supply line ©. [81] next, in reference to fig. 4, a fourth embodiment will be explained. [82] as shown in fig. 4, this embodiment has the same configiration as that of the third embodiment, except that the steam generator 10 and the hot air generator 80 are provided in a predetermined one of the laundry treating apparatuses and that they are shared by the other laundry treating apparatuses. [83] specifically, the steam generator 10 and the hot air generator 80 may be provided in the dryer 30 or the washer 20. for example, if the steam generator 10 and the hot air generator 80 are provided in the washer 2q the washer 20 is a washer having a steam washing and drying function. [84] each of the laundry treating apparatuses 2q 30 and 40 performs a separate laundry treating module via each of the controllers 21, 31 and 41 and the controller 21 controls operations of the steam generator 10 and the hot air generator 8q when each of the laundry treating apparatuses 2q 30 and 40 needs hot air or steam. hence, steam or hot air is supplied to the laundry treating apparatus that needs the steam or hot air. [85] pipes or control logic for such supply of the steam or hot air has been explained in above embodiments and thus the explanation thereof will be omitted. [86] according to this embodiment, there is an effect that a total laundry treating system can be embodied via a conventional dryer or conventional dryer having a washing function that includes the steam generator 10 and the hot air generator 80. [87] it is easy to make a control program, because the steam generator 10 and the hot air generator 80 are controlled via one controller 21. [88] the steam supply line (d and the hot air supply line 70 have been explained in the above first embodiment and the specific descriptions thereof will be omitted. of course, the control method of opening/closing those lines ® and 70 has been explained in the above first embodiment, and the description thereof will be also omitted. [89] in the above embodiments, a hot air circulation method by the hot air generator provided in a predetermined laundry treating apparatus may be an air exhaustion type or air condensation type. [90] specifically, in case of the air exhaustion type, the air supplied to each of the laundry treating apparatuses throtgh the hot supply line 70 is not circulated into the ^ q «wj aa«r i b. \j 1 , l$ \l\h . hot air generator 8q but exhausted outside. that is, the air is exhausted to an outside or an inside through an air outlet of each laundry treating apparatus, which is identical to an air passage of the air exhaustion type. [91] in case of the air condensation type, the air supplied to each of the laundry treating apparatuses through the hot air supply line 70 is re-circulated to the hot air generator 80. for that, an auxiliary hot air collect line (not shown) may be provided. [92] that is, when the air is supplied to each of the laundry treating apparatuses through the hot air supply line 7q the air gets to contain moisture in the laundry treating apparatuses and the damp air is collected through the hot air collect line (not shown). here, the moisture of the air may be removed before the collected air is re-supplied to each of the laundry treating apparatuses. [93] as a result, in case of the condensation type, a condenser (not shown) may be fiirther provided to condense the moisture of the air. the moisture of the air is condensed in the condenser and the air having its moisture removed is supplied to each of the laundry treating apparatuses thrαgh the hot air supply line 70. [94] the structure of such condensation type is applicable to a case in that an air outlet is difficult to form at laundry devices in houses or dry cleaners'. that is, it is easy to install the air exhaustion type in a room near an external wall of a building and it is easy to install the air condensation type in a room near a center area of a building, because complicated air outlet pipes are difficult to install in the room near the center area of the building. [95] next, in reference to fig. 5, a steam generator applicable to the present invention will be explained. fig. 5 is a diagram schematically illustrating the steam generator. [96] the total laundry treating system according to the present invention may include one steam generator 500. the steam generator 500 may be provided in a predetermined one of plural laundry treating apparatuses. [97] bbwever, the amount of steam supply supplied to the steam generator may be variable, because each of the laundry treating apparatuses requires steam simultaneously or one of them requires steam. [98] as a result, the amount of steam generation or steam supply may be variable based on demands of steam. that is preferable for energy saving or for time reduction of steam supply. [99] fig. 5 illustrates an embodiment of the steam generator that is such a capacity variable type. [100] as shown in fig. 5, the steam generator 500 is configured to be a plurality of 11 λϋ/λft l «5. u /. -iwf- chambers 52q 521 and 522 the chambers may have separate volumes and the heaters 53q 531 and 532 are mounted in the chambers 52q 521 and 522, respectively. of course, these heaters 53q 531 and 532 may have separate capacities. [101] fig. 5 illustrates a chamber 520 having a relatively large volume and a heater 530 having a relatively large volume, and chambers 521 and 522 having relatively small volumes and heaters 531 and 532 having relatively small capacities. [102] for example, if the amount of requested steam is most, all the heaters are operated to generate steam. if the amount of requested is least, one of the heaters having the small capacity is operated to generate steam. as a result, the amount of steam generation and supply may be adjustable based on the amount of requested steam. [103] the operation of the heaters 53q 531 and 532 is controlled by a controller of the laundry treating apparatus having the steam generator 500 therein. the controller receives data for the amount of requested steam from the controllers of the laundry treating apparatuses. [104] on the other hand, a steam outlet (not shown) is formed at each of the chambers 52q 521 and 522. steam discharged through the steam outlets is supplied to each of the laundry treating apparatuses through the steam supply line 56). [105] such method of steam amount adjustment may be embodied in a different way. for example, the amount of water supplied to the steam generator may be controlled by the controller based on the amount of requested steam. hence, the heating amount of the heater may be controlled or the number of the operated heaters may be controlled. [106] specifically, if the steam amount is most in the steam generator having one chamber and the plurality of the heaters are provided therein, the largest mount of water may be supplied to the steam generator and all of the heaters may be operated. if the steam amount is least, the least amount of water may be supplied to the steam generator and only a predetermined heater may be operated. [107] if only one heater is provided, the heating amount of the heater is controlled based on the amount of requested steam to adjust the steam amount to adjust the steam amount. [108] water should be supplied to the steam generator according to the present invention. a source of such water supply may be a common water pipe or a user may directly supply water to the steam generator. [109] a water pipe as a water source is not provided in every house and is commonly, for example, only in a kitchen or bathroom. in addition even such places as a kitchen or bathroom have limited water taps and washers that use a lot of water are connected to 12 ku/m l z. uy. jju ( h, the water taps. [110] as a result, lack of water source can be prevented because only one steam generator may be used according to the present invention. [ill] in the meantime, if there is no such water source, a user may directly supply water to the steam generator by using a water basket. in this case, even when water is supplied to only one steam generator provided in the predetermined one of the laundry treating apparatuses, the water may be supplied to the other laundry treating apparatuses and thus there is an effect of minimized fatigue to the user. [112] if the steam generator is provided in the washer, the steam generator may uses a water tap for supplying water to the washer and thus an auxiliary water source may not be provided. [113] next, in reference to fig. 2, an operation of the total laundry treating system according to the present invention will be explained. an operation according to other embodiment can be easily understood through the following explanation and thus the description thereof will be omitted. [114] firstly, each of the laundry treating apparatuses may be operated separately. that is, the water performs washing, the dryer performs drying and the refresher performs refreshing. when steam is requested during an operation of each laundry treating apparatus, each of the controllers transmits a signal for steam request to the controller of the predetermined laundry treating apparatus having the steam generator. [115] hence, the controller of the predetermined laundry treating apparatus controls the steam generator to be operated and to generate steam based on the steam request. here, the controller may controls the water amount for steam generation, the heating capacity of the heater or the number of the operated heaters. that is, the steam generation and steam supply amount may be adjustable based on the amount of requested steam. [116] the steam is supplied to each of the laundry treating apparatus. [117] therefore, according to the present invention, the steam generator does not have to be provided in each of the laundry treating apparatuses and the present invention is advantageous as a matter of cost. in addition, it is limited that the efficient steam generator is mounted in each of the laundry treating apparatus. such problematic limitation may be solved by the present invention in which the steam generator is provided in the predetermined laundry treating apparatuses. [118] it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. industrial applicability [119] the present invention has an industrial applicability. [120] each of the laundry treating apparatuses is inter-relative and thus a convenient total laundry treating system may be provided. that is, the total laundry treating system according to the present invention is efficient and convenient in a view of space or a laundry treating time. [121] furthermore, according to the present invention there are provided the plurality of the laundry treating apparatuses that uses steam, respectively, and the steam the total laundry treating system having the steam generator for supplying steam to each of the laundry treating apparatuses. as a result, the present invention has an industrial applicability that a series of laundry treating processes may be performed conveniently. [122] a still further, the steam generator able to adjust the amount of steam supply is provided in the total laundry treating system according to the present invention. as a result, efficient steam supply is possible and energy saving is possible. [123] a still further, according to the present invention, steam is supplied to the plurality of the laundry treating apparatuses through the single steam generator. as a result, a user may easily secure a water source for steam generation. [124] a still further, the hot air generator for supply air, especially, hot air as well as the steam generator is provided in each of the laundry treating apparatuses. as a result, the laundry treating process may be performed convenient. [125] lastly, the total laundry treating system may be embodied by using conventional washers having the steam generators or dryers having the hot air generators.
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087-861-108-843-861
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JP
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[
"US"
] |
C23C2/06,C23C2/08,C23C2/26,C23C2/28,C23C28/00
| 1986-11-21T00:00:00 |
1986
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[
"C23"
] |
colored zinc coating
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this invention permits, in a colored galvanized coating using ti-zn, mn-zn, ti-mn-zn, (ti, mn)-(cu, ni, cr)-zn, etc., to clearly and stably develop yellow, purple, green, blue or other color by controlling the composition of a galvanizing bath and oxidizing conditions. further, a gold, dark red, olive gray and iridescence color which have not yet obtained can be developed. the color development effected by this invention is clearer than conventional. instead of galvanizing, the spraying process may be adopted. the surface painting on the colored zinc coating is effective.
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1. a method of forming a colorized zinc coating on an iron or steel surface characterized in that using a galvanizing zinc alloy comprising 0.15 to less than 0.3 wt. % ti, said iron or steel surface coated on a hot dipping bath of said alloy at a temperature of 470.degree. to less than 550.degree. c. and the coated surface obtained is heated to a temperature of 450.degree. to 520.degree. c. followed by cooling whereby a coating having a purple color is formed. 2. a method as recited in claim 1 wherein the zinc alloy contains 0.15 to 0.25 wt. % titanium. 3. a method as recited in claim 1 wherein the temperature of the hot dipping bath is maintained within the range to 480.degree. to 530.degree. c. 4. a method as recited in claim 1 wherein, after being dipped, the coated surface is heated to a temperature of 470.degree.-510.degree. c. 5. a method as recited in claim 4 wherein the zinc alloy contains 0.15 to 0.25 wt % titanium, and wherein the temperature of the dipping bath is maintained within the range of 480.degree. to 530.degree. c. 6. a method as recited in claim 5 wherein, after being dipped, the coated surface is heated to a temperature of 500.degree. c., wherein the zinc alloy contains 0.2 wt % titanium, and wherein the dipping bath is maintained at a temperature of 480.degree. c. 7. a method of forming a colored zinc coating on an iron or steel surface characterized in that it is employs a galvanizing zinc alloy comprising 0.2 to 0.7 wt. titanium, said iron or steel surface being coated in a hot dipping bath of said zinc alloy maintained at a temperature of greater than 530.degree.-570.degree. c. and the coated surface obtained is immediately cooled or is cooled after being heated to a temperature of 450.degree. to 550.degree. c. whereby a coating having a yellow color is formed. 8. a method as recited in claim 7 wherein the zinc alloy contains 0.2-0.5 wt. % titanium. 9. a method as recited in claim 7 wherein the temperature of the hot dipping bath is maintained within the range of 540.degree. to 560.degree. c. 10. a method as recited in claim 9 wherein, after being dipped, the coated surface is heated to a temperature of 470.degree. to 510.degree. c. 11. a method as recited in claim 10 wherein the zinc alloy contains 0.2 to 0.5 wt % titanium, and wherein the temperature of the hot dipping bath is maintained within the range of 540.degree.-560.degree. c. 12. a method as recited in claim 11 wherein, after being dipped, the coated surface is heated to a temperature of 500.degree. c., wherein the zinc alloy contains 0.25 wt % of titanium, and wherein the hot dipping bath is maintained at a temperature of 550.degree. c. 13. a method of forming a colored zinc coating on a substrate comprising the steps of: a. preparing a coloring zinc alloy containing 0.1 to 2.0 wt. % titanium; b. heating said zinc alloy to a temperature at which the alloy is in the form of a melt; c. thermally spraying said zinc alloy in the form of a melt onto the surface of a metal substrate; and d. heating said thermally sprayed surface to a temperature of 380.degree. to 450.degree. c., whereby a clear colored surface is formed. 14. a method as recited in claim 13 wherein said zinc alloy further comprises 0.01 to 4.0 wt. % of at least one of the components selected from the group consisting of mn, cu, cr, and ni. 15. a method as recited in claim 13 wherein, by manipulating the heating temperature and time of step (d), the colored surface can take a gold, purple or blue hue. 16. a method as recited in claim 1 wherein the colored zinc coating is coated with a paint. 17. a method as recited in claim 16 wherein the paint is selected from the group consisting of synthetic resin paints. 18. a method as recited in claim 17 wherein said synthetic resin paint is selected from the group consisting of polyurethane resin, acrylic resin, epoxy resin and chlorinated rubber paints. 19. a method as recited in claim 7 wherein the colored zinc coating is coated with a paint. 20. a method as recited in claim 19 wherein the paint is selected from the group consisting of synthetic resin paints. 21. a method as recited in claim 20 wherein said synthetic resin paint is selected from the group consisting of polyurethane resin, acrylic resin, epoxy resin and chlorinated rubber paints. 22. a method as recited in claim 13 wherein the colored zinc coating is coated with a paint. 23. a method as recited in claim 22 wherein the paint is selected from the group consisting of synthetic resin paints. 24. a method as recited in claim 23 wherein said synthetic resin paint is selected from the group consisting of polyurethane resin, acrylic resin, epoxy resin and chlorinated rubber paints.
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field of the invention this invention relates to a colored zinc coating technique applied onto the surface of an iron or steel material, and particularly to a colored zinc coating method with the use of ti-zn, mn-zn, ti-mn-zn, mn-cu-zn or ti-cu-zn system or other zinc alloys by which the development of new colors not obtained by conventional techniques and clearer color developments compared to conventional ones are permitted. according to this invention, the developments of gold, dark red, olive gray and iridescent colors which could not have yet obtained are permitted and simultaneously yellow color, green color, blue color, purple color, young grass color, etc. may be more clearly developed. thus, this invention provides colored zinc coated materials which are applicable to wider variety of fields and have coloring more suitable to the environment where they are placed. background of the invention hot-dip galvanized iron and steel materials, coated by dipping in molten zinc, are used for corrosion protection purposes in a wide range of applications, forming parts and facilities in the fields: of building and construction, civil engineering, agriculture, fisheries, chemical plants, electric power supply and communications, and so forth. for pylons and other towers, lighting poles, guard rails, temporary stands and frames for various operations and displays, shells and planks, and the like, there has been growing demand in recent years for colored hot-dip galvanized materials that present attractive appearances matching the environments involved, in preference to the classic hot-dip galvanized steels with metallic luster. with the spread of the aesthetic sense the colored hot-dip galvanized articles show promise, with extensive potential demand in architecture, civil engineering, industrial plants, electric power supply and communications, transportation, agriculture, marine products and other industries. coloration of hot-dip galvanized steels has usually been by the application of paints. the method has the disadvantage of the paint film eventually coming off the coated surface. this results from the activity of zn in the coating of the hot-dip galvanized steel that causes gradual alkali decomposition of the fatty acid constituting the oily matter in the paint, leading to the formation of zinc soap that hampers the adhesion of the paint film to the underlying surface. in an effort to eliminate the disadvantage, a complex procedure has had to be followed. an iron or steel article is first galvanized by dipping it into a molten zinc bath. the coated article is exposed to the air for one to three weeks so that corrosion products such as zn(oh).sub.2, zno, znco.sub.3, zncl.sub.2 and the like deposit on the coated steel surface. the surface is then cleaned and colored. aside from the coating method described above, another approach that depends on the color-developing action of the oxide film in the hot-dip galvanizing is known in the art. for example, japanese patent application publication no. 42007/1971 discloses a coloring treatment that uses a coating bath prepared by adding at lest one element selected from the group consisting of titanium, manganese, vanadium and the like to a hot-dip galvanizing bath. however, the hot-dip galvanized coatings obtained by the disclosed technique have been found to be generally very thin and light, with tendencies of rapid color fading and film separation with time. the desired color development is difficult to control precisely, often bringing out dim, indefinite hues. for such reasons, even though many years have lapsed since its development, hot-dip galvanized coloring technique has not been put into practical use on a commercial scale. under such circumstances, there is a steady demand in the art for many improvements such as: (a) the development of new colorings which have not yet obtained in the past; (b) the development of colors which are more beautiful and clearer than ones previously obtained; (c) the enhanced stability of color development; (d) the development of a coloring system wherein the inherent corrosion resistance of galvanized zinc coating is not sacrificed; (e) the development of a coloring system wherein there is a lesser degree of color change with the lapse of time; and (f) the development of a coloring system which has an easy and stable operation. object of the invention the object of this invention is to establish colored zinc coating technique by which the above-mentioned improvements may be attained using zinc alloys such as ti-zn, ti-mn-zn, mn-zn, ti-cu-zn, mn-cu-zn or others. other objects, embodiments, advantages, features and deficits of this invention will become apparent to those skilled in the art from the following summary, detailed description, examples and appended claims. summary of the invention toward the above object, we have made many efforts. in the colored hot-dip galvanizing, the composition of the plating bath and the conditions of producing an oxidized film delicately combine to present coloring effects by light interference. by ingeniously controlling these factors, this invention succeeded in selectively developing yellow, purple, green or blue color in a clearer manner when compared to colors obtained heretofore in ti-zn, ti-cu-zn, ti-ni-zn and ti-cr-zn systems. this invention also succeeds in more clearly developing various kinds of colorings in ti-mn-zn and mn-cu-zn systems. further, in ti-zn alloys, we successfully attained the development of a golden color which had been thought that such was beyond the range of possibilities. moreover, we have also succeeded in developing dark-red color which has been strongly desired. in addition, it became possible to attain the development of clearer yellow, purple, green or other colors compared to ones previously obtained. further, in ti-mn-zn alloys, we were successful in developing a strongly needed dark-red color, and in obtaining yellow, green and blue color clearer than previous ones. this invention is unique in the point that an olive-gray color strongly demanded may be developed using mn-zn and mn-cu-zn alloys. in mn-zn and mn-cu alloys, an iridescent color, the development of which had never thought was successfully obtained. by using a mn-ti alloy with the impurity pb content controlled, selective color development of purple and blue colors markedly clearer than one obtained heretofore, was successfully attained. surprisingly, even golden color, which had never thought possible, could also be successfully developed by practicing the present invention. this invention also found that a colored zinc coating may be applied by a spraying method. the change of the colored zinc coating with the lapse of time may be suppressed by painting thereon. detailed explanation of the invention zinc alloy hot dipping is carried out by melting a zinc alloy in a coating bath and immersing a member to be coated therein. a) selective color development of clear yellow-purple-blue-green using ti and/or mn-zn alloy or ti and/or mn-(cu,ni,cr)-zn alloy using a galvanizing zinc alloy containing 0.3 to 0.7 wt % ti or 0.1 to 0.5 wt % mn or the both, yellow, purple, blue or green color may be clearly developed, depending upon the extent of oxidation, by hot dipping an iron or steel material in a bath at temperature of 480.degree. to 530.degree. c. followed by cooling under a specified condition selected from air cooling, water cooling etc. or by cooling after the hot dipped material was heated to a temperature atmosphere at 450.degree. to 550.degree. c. the metallic zinc bullion to be used in forming the zinc alloy for hot dipping is typically one of the grades conforming to jis h2107, for example, distilled zinc 1st grade (at least 98.5% pure), purest zinc (at least 99.99% pure), and special zinc grades. the impurities inevitably contained in these zinc materials are, for example in the distilled zinc 1st grade, all up to 1.2 wt pb, 0.1 wt % cd, and 0.020 wt % fe. for the purposes of the invention a metallic zinc with a total impurity content of less than 1.5 wt % is desirable. in this embodiment, the hot dipping is carried out with the use of a molten zinc bath composed of the above-mentioned zinc bullion (chiefly, distilled zinc bullion is employed) with the addition of 0.3 to 0.7 wt % j ti and/or 0.1 to 0.5 wt % mn. further, a molten zinc bath, further including at least one of 0.1 to 0.5 wt % cu, 0.01 to 0.05 wt % cr and 0.01 to 0.05 wt % ni other than ti and mn, may be advantageously used. in order to carry out galvanizing with the use of above-mentioned molten zinc bath, an iron or steel material is dipped in the bath of said zinc alloy at a bath temperature of 480.degree. to 530.degree. c. for 1 to 2 minutes and the coated material is drawn up from the bath and cooled in air followed by cooling with water. alternatively, after similarly dipping the iron or steel material into the bath and withdrawing it from the bath, it may be heated in an atmosphere at a temperature of 450.degree.-550.degree. c. for a short time period and then cooled in air followed by cooling with water. when the coated material is allowed to cool in air, the oxidation time period is shortened to lessen the production of oxidized film. on the other hand, when the coating step is followed by heating, the oxidation time period is extended to make the resulting oxidized film heavier. thus, the extent of oxidation in the resulting oxide film can be controlled by cooling and/or heating under varied conditions following the galvanizing procedure. when an iron or steel material is dipped into a zinc alloy bath and then is allowed to stand in air, the material is formed at its surface with a plated layer or coating while forming oxidized film(s) thereon. in the case where the oxide film is allowed to stand for cooling for 5 to 10 seconds and then water cooled, the oxide film exhibits a yellow color hue. in the case where the material is dipped into the zinc alloy bath, then heated and is followed air cooling and water cooling, the oxide film presents purple, blue or green color hue depending upon time period and temperature the material is subjected to during heating. for example, when the iron or steel material is, after galvanizing, heated at an atmosphere at 450.degree. c. for 50 to 60 seconds and then is air cooled and water cooled, a purple color is developed. on the other hand, when it is heated for two minutes and then air cooled and water cooled, a blue color is developed. thus, when the heating step is employed after the galvanizing step, a desired color such as purple, blue, green (young grass) or other colors may be selectively developed. in addition, when ti and mn contents, as well as amounts of cu, cr and ni, are added and/or varied within specified ranges as described before, the color hue and tone of the oxide film formed may be adjusted. explanations will now be provided as to how the contents of these metals in a zinc alloy used for galvanizing influence the formation of the oxide film and its color hue: (a) titanium (ti) when the ti content in said galvanizing bath is less than 0.3 wt %, the formation of the oxide film on the galvanized layer becomes too slow. therefore, even if the heating temperature and the time period are set at their upper limits, the color hue and tone of the oxide film become too light, resulting in a product having a low commercial value as a colored zinc coated product. on the other hand, when the ti content is higher than 0.7 wt %, the formation rate of the oxide film become too fast. therefore, the change of the color hue of the oxide film produced is quick, thus making its color adjustment more difficult. in addition, the amount of oxides produced in the bath having this level of ti is too great and the wetability of the oxide film to the galvanized material decreases. (b) manganese (mn) when the mn content in said galvanizing bath is less than 0.1 wt %, the formation of the oxide film becomes too slow; thus resulting in a light-tone oxide film. on the other hand, when the mn content is higher than 0.5 wt %, the adjustment of color hue becomes increasingly difficult and the wetability of the oxide film to the galvanized material becomes poor. (c) copper (cu) as described above, when ti and mn contents in the galvanizing bath are increased near to their upper limits the formation rate of the oxide film increases which makes it more difficult to hold the color hue constant. however, when the galvanizing bath contains cu in the range of 0.1 to 0.5 wt %, the formation rate of the oxide film is suppressed. accordingly the result the adjustment of the color hue and the wetability of the oxide film is improved. when the cu concentration is outside of the above specified range, such effects cannot be expected. (d) chromium (cr) and nickel (ni) in a ti-containing galvanizing bath (ti-zn alloy bath) and a mn-containing bath (mn-zn alloy bath), ti and mn tend to distribute at a top layer of the bath. for this reason, the amount of oxides produced in the bath increases results in decreasing which the wetability of the oxide film to the galvanized material, in addition to lowering the yield of the bath. however, when cr or ni is present in a concentration range of 0.01 to 0.05 wt %, the ti and mn uniformly distributed throughout the bath. therefore, the wetability of the oxide film to the galvanized material and the yield of the bath are improved. outside the specified ranges of cr and ni, such effects are not obtainable. in addition, when cu, cr or ni is contained in the galvanizing bath of a molten zinc alloy, beside the aforementioned effects, interference colors inherent to these metals may be generated. this leads to an advantage that enhances clearness and brightness of the color hue of the oxide film produced. (b-1) the development of golden color with ti-zn alloy it is possible to form a colored coating with a golden hue on an iron or steel surface by plating the base metal using a bath of a zinc alloy for hot dipping of a composition comprising 0.1-0.5 wt % ti--and the balance zn at a bath temperature of 450.degree.-470.degree. c., allowing the plated work to stand in air for 5-20 seconds, and thereafter cooling it with cold or warm water. with regard to the zinc used, the explanation in a) also applies here. particularly, distilled zinc is preferred because it permits to effect plating with the use of ordinary flux and color strength produced becomes higher. in this embodiment, the plating is carried out using a molten zinc alloy bath containing 0.1-0.5 wt % ti--with the balance being zn. this is obtained by adding 0.1-0.5 wt % ti to the above-mentioned zinc. a bath of a molten zinc alloy containing 0.3 wt % ti is particularly desirable. in order to produce the golden colored coating from the hot-dip zinc alloy bath having the above composition, a base metal of iron or steel is immersed in the plating bath at 450.degree.-470.degree. c. for at least one minute, the base metal is pulled out of the bath and allowed to cool in air for about 5-20 seconds. the partially cooled material is then immediately quenched with cold or warm water to form thereon an oxide film with a golden hue. thus, in producing a golden colored coating, it is essential to immerse the iron or steel base metal in the bath of molten zinc alloy having the composition of 0.1-0.5 wt % ti with the balance being zn, while the bath is at a temperature of 450.degree.-470.degree. c. the material is then removed from the bath and allowed to cool in air for a very short period of about 5-20 seconds, preferably for 10-20 seconds. if the conditions are outside the ranges specified above, the desired golden hue will not result. for example, if the heating temperature is above 470.degree. c., and if the period of time for which the plated materials are allowed to cool in air exceeds 20 seconds, the hue of the coating will turn purple. as stated above, a colored coating with a uniform, stable golden hue can be formed on a base metal of iron or steel by plating it under specific conditions using a molten zinc alloy of the specific composition. it thus provides a corrosion-resistant material for the components and facilities for uses where they are required to be golden in color from an aesthetic viewpoint. the iron or steel products with colored coatings of the invention are highly corrosion-resistant and are of value in a wide range of commercial uses. (b-2) the development of clear purple color with ti-zn alloy it is possible to form a colored coating with a purple hue on an iron or steel surface by plating the base metal using a bath of a zinc alloy for hot dipping having a composition comprising 0.1-0.5 wt % ti with the balance being zn, while the bath is at a temperature of 500.degree.-550.degree. c. the purple color can be obtained by either (a) allowing the plated work to cool in air for 10-50 seconds or (b) by heating the plated work in an atmosphere at 500.degree.-520.degree. c. for 10-20 seconds, and thereafter cooling it with cold or warm water. with regard to a zinc bullion, the same explanation as in a) also applies here. the plating is carried out using a molten zinc alloy bath of the composition comprising 0.1-0.5 wt % ti with the balance being zn. this alloy bath is obtained by adding 0.1-0.5 wt %, preferably 0.3 wt %, ti to the abovementioned zinc. in order to produce the purple colored coating from the hot-dip zinc alloy bath having the above composition, a base metal of iron or steel is immersed in the plating bath maintained at a temperature of 500.degree.-550.degree. c., preferably 500.degree.-520.degree. c., for at least one minute. the base metal is then removed from the bath and allowed to cool in air for about 10-50 seconds, preferably for 40-50 seconds. thereafter, the partially cooled material is immediately quenched with cold or warm water to form thereon an oxide film with a purple hue. alternatively, the work taken out of the bath can be heated in an atmosphere at a temperature of 500.degree.-520.degree. c. for 10-20 seconds and then cooled with cold or warm water to form a purple-colored oxide film thereon. thus, in producing a purple colored coating, it is essential to immerse the iron or steel base metal in the bath of molten zinc alloy having a composition comprising 0.1-0.5 wt % ti with the balance being zn, while the bath is at a temperature of 500.degree.-550.degree. c., preferably of 500.degree.-520.degree. c. thereafter, the plated work is removed from the bath and is either (a) allowed to cool in air for a very short period of 10-50 seconds, preferably of 40-50 seconds or (b) heated in an atmosphere at a temperature of 500.degree.-520.degree. c. for 10-20 seconds, and then cooled with cold or warm water. if the conditions are outside the ranges specified above, the desired purple hue will not result. as stated above, a colored coating with a uniform, stable purple hue can be formed on a base metal of iron or steel by plating it under specific conditions using a molten zinc alloy of the specific composition. it thus provides a corrosion resistant material for the components and facilities for uses where they are required to be purple in color from an aesthetic viewpoint. the iron or steel products with colored coatings of the invention are highly corrosion-resistant and are of value in a wide range of commercial uses. (b-2a) the development of clear purple color with ti-zn alloy it has also been discovered that another possible method of forming a colored coating with a purple hue on an iron or steel surface comprises the steps of plating the base metal by hot-dipping it in a bath of a zinc alloy. the zinc alloy bath comprises 0.15 to less than 0.3 wt % ti, with the balance being zinc. the alloy bath is maintained at a temperature of 470.degree. to less than 550.degree. c. after the base metal is dipped into the zinc alloy bath, it is withdrawn and heated to a temperature of 450.degree. to 520.degree. c. this is followed by a cooling step. when practicing the above procedure, the color of the coating on the base metal is that of a purple hue. with regard to the zinc bullion, the same explanation as in a) also applies here. the plating is carried out by using a molten zinc alloy bath having the composition of 0.15 to less than 0.3 wt % ti with the balance being zinc. this is obtained by adding 0.15 to less than 0.3 wt %, preferably 0.15-0.25 wt %, ti to the above-mentioned zinc. in order to produce the purple color coating in accordance with this embodiment from the hot-dip zinc alloy bath of the above composition, a base metal of iron or steel is immersed in the plating bath at a temperature of 470.degree. to less than 550.degree. c., preferably at a temperature of 480.degree.-530.degree. c., for at least one minute. the base metal is then pulled out of the bath and heated in an atmosphere at a temperature of 450.degree.-520.degree. c., preferably 470.degree.-510.degree. c., for at least one minute, preferably between 1-2 minutes. thereafter, the heated, coated material is cooled with cold or warm water to form a purple colored oxide film thereon. as stated above, a colored coating with a uniform, stable purple hue can be formed on a base metal of iron or steel by plating it under specific conditions using a molten zinc alloy of a specific composition. if the conditions are outside of the aforementioned ranges, the desired purple color will not result. this embodiment of the invention provides a corrosion-resisted material for the components and facilities for uses where they are required to be purple in color from an aesthetic viewpoint. the iron or steel products colored by this process are highly corrosion-resistant and are of value in a wide range of commercial uses. (b-3) selective development of yellow, dark red, green color with ti-zn alloy this invention also provides a zinc alloy for colored hot-dip galvanizing capable of developing yellow, dark red, and green colors selectively as desired. in order to achieve these colors, a bath of a zinc alloy for hot-dipping is employed wherein the bath is composed of 0.2-0.7 wt % ti and the balance zinc and inevitable impurities. it has further been found that the following alloys, made by adding the ingredients as follows to the above ti-zn alloy, are useful in uniform coloring in yellow, dark red, and green: (a) a zinc alloy for colored hot-dip galvanizing capable of developing yellow, dark red, and green colors selectively as desired, composed of 0.2-0.7 wt % ti, 1.3-5.9 wt % pb, and the balance zinc and inevitable impurities. (b) a zinc alloy for colored hot-dip galvanizing capable of developing yellow, dark red, and green colors selectively as desired, composed of 0.2-0.7 wt % ti, 1.2-1.3 wt % pb, 0.1-0.2 wt % cd, and the balance zinc and inevitable impurities. (c) a zinc alloy for colored hot-dip galvanizing capable of developing yellow, dark red, and green colors and desired, composed of 0.2-0.7 wt % ti, 1.0-1.2 wt % pb, 0.05-0.2 wt % cd, 0.01-0.05 wt % of at least one element selected from the group consisting of cu, sn, bi, sb, and in, and the balance zinc and inevitable impurities. a base material of iron or steel is galvanized by immersion into a molten zinc bath of such an alloy. the coated metal is withdrawn from the bath and (a) allowed to cool in the air or (b) heated at a specific temperature. through proper control of the conditions, it is possible to bring out yellow, dark red, and green colors selectively at will. even with an alloy based on a purest metallic zinc (at least 99.995% pure) or special zinc (at least 99.99% pure), galvanizing with good wetability and uniformity in hue can be achieved. zinc alloy hot dipping is carried out by melting a zinc alloy in a coating bath and immersing a work to be galvanized in the bath. the zinc alloy is prepared by adding a specific alloying additive to a metallic zinc. in the practice of the invention, a metallic zinc bullion with a high purity of at least 99.9%, typified by a purest zinc (99.995% pure) and special zinc (at least 99.99% pure) as defined in jis h2107, is used. this prevents any adverse effects resulting from the variable introduction of impurities (pb, cd, fe, etc.) such as decreasing the controllability of color development. nevertheless, the use of such a high purity zinc brings shortcomings while it eliminates variations in the coating conditions due to the presence of impurities. for example, when an iron or steel material is galvanized by immersion in a coating bath (fe saturated) containing predetermined amounts of ti and mn, the formation of an oxide film on the bath surface is rapid and large in amount. these and other factors tend to produce color shading, such as partial two-color mixing of the colored oxide film of the coating layer. under the circumstances the present inventors have found that the addition of 0.2-0.7 wt % ti is effective in giving a yellow, dark red, or green color clearly and brightly without partial lackness of plating or unevenness in color. if the ti content in the coating bath is less than 0.2 wt %, the formation of a colored oxide film in the coating layer of the galvanized metal is inadequate, and the hue is low and nonuniform. this phenomena reduces the marketable value of the colored galvanized product. on the other hand, if the ti content is above 0.7 wt %, the oxide film forms too rapidly. therefore, the change in hue of the colored oxide film becomes too fast to control. moreover, too much oxide formation on the coating bath reduces t wetability of the bath with respect to the base metal to be galvanized. for the further improvement in the coating wetability, various alloys, prepared by adding pb, cd, sn, bi, sb, in, and/or the like to the ti-zn alloy, were investigated. as a result, the zinc alloys (a), (b), and (c) referred to above have now been found particularly useful. these three alloys will be described below. (a) alloy containing 1.3-5.9 wt % pb in addition to ti if the pb content is less than 1.3% the wetability-improving effect is limited. in colored coating at a bath temperature of 470.degree.-500.degree. c. partial uncoating will result. especially in the bath temperature range of 470.degree.-490.degree. c. deposition on the coating film will frequently occur. in the 500.degree.-600.degree. c. range, color shading in the colored oxide film will result. the pb addition proves increasingly effective up to the limit of its solubility. since the pb solubility in molten zinc at a bath temperature of 600.degree. c. is 5.9 wt %, this value is taken as the upper concentration limit. (b) alloy containing 1.2-1.3 wt % pb and 0.1-0.2 wt % cd in addition to ti where pb and cd are used together, small additions can prove effective. if the pb content is less than 1.2 wt %, partial uncoating occurs in the colored coating at a bath temperature of 470.degree.-600.degree. c., even in the presence of cd. in the temperature range of 470.degree.-490.degree. c. the possibility of dross deposition on the coating film will be greater. even when the pb content is within the specified range, similar troubles will take place if the cd content is less than 0.1 wt %. if the pb content exceeds 1.3 wt % or the cd content is more than 0.2 wt %, the oxide formation on the coating bath becomes so much that the rate of uncoating rises. (c) alloy containing, besides ti, 1.0-1.2 wt % pb, 0.05-0.2 wt % cd, and 0.01-0.05 wt % of at least one element selected from cu, sn, bi, sb, and in the addition of at least one element selected from the group consisting of cu, sn, bi, sb, and in promotes the wetability-improving effect of pb and cd. if the pb content is less than 1.0 wt %, and if the cd content is below 0.05 wt %, partial uncoating results from colored galvanizing at a bath temperature of 470.degree.-600.degree. c. especially in the bath temperature range of 470.degree.-490.degree. c., the dross deposit on the coating film will increase. on the other hand, if the pb content is more than 1.2 wt %, and if the cd exceeds 0.2 wt %, a large degree of oxide formation on the coating bath surface is observed. the addition of 0.01-0.05 wt % of at least one of cu, sn, bi, sb, and in (a) retards the rate of oxide film formation on the bath surface and (b) improves the wetability for the work to be galvanized. the addition elements set out above prevent uncoating, color shading, dross deposition, and other troubles, thus rendering it easy to control the hue of the colored oxide film, and increasing the color depth or strength. in the hot dip galvanizing process with such a zinc alloy, the work to be galvanized is degreased, for example, by the use of an alkaline bath, descaled by pickling or the like, and then treated with a flux to be ready for galvanizing. the flux treatment is effected, for example, by a dip for a short time in a zncl.sub.2 --kf solution, zncl.sub.2 --nh.sub.4 cl solution, or other known flux solution. after the pretreatment, the material to be galvanized is immersed into a coating bath at a specific controlled temperature for 1 to 3 minutes. the coated metal is pulled out of the bath and, through proper control of the degree of oxidation, a yellow, dark red, or green color is selectively obtained. for instance, after the coated work has been pulled out of the bath, it is cooled under control by (a) natural cooling in the air, (b) cooling with cold or warm water, (c) slow cooling in an oven, or (d) by any other coating means known to those skilled in the art. alternatively, the coated metal from the bath can be held in an atmosphere at a temperature of 450.degree.-550.degree. c. for a predetermined period of time, so that the degree of its oxidation can be controlled. the holding temperature, holding time, and subsequent cooling method are chosen as desired. as the degree of oxidation is increased, yellow, dark red, and green colors are developed successively in the order of mention. an example of the oxidation degree control is as follows: yellow: after the work has been pulled out of the coating bath at a bath temperature of 590.degree. c., it is held in atmosphere at 500.degree. c. for 15-20 seconds and then is cooled with hot water. dark red: the bath temperature is increased by 5.degree.-10.degree. c., and either the atmosphere temperature is raised or the holding time is increased by 5-10 seconds. green: the bath temperature is made even higher by 5.degree.-10.degree. c., and either the atmosphere temperature is further increased or the holding time is extended by a further period of 5-10 seconds. with the alloys of the invention, i.e., (a) the ti--1.3-5.9 wt % pb--bal. zn alloy, (b) ti--1.2-1.3 wt % pb--0.1-0.2 wt % cd--bal. zn alloy, and (c) ti--1.0-1.2 wt % pb--0.05-0.2 wt % cd--0.01-0.05 wt % (cu, sn, bi, sb, and/or in)--bal. zn alloy, the color development is controllable in the order of golden, purple, and blue hues. in the order of increasing degrees of oxidation, gold, purple, blue, yellow, dark red, and green colors are brought out. (b-4) the development of a yellow color with ti-zn alloy it is possible to form a colored coating with a yellow hue on an iron or steel surface by plating the base metal using a zinc alloy for hot-dipping having a composition comprising 0.2-0.7 wt % ti with the balance being zn, while the bath is at a temperature of more than 530.degree.-570.degree. c. the yellow color can be obtained by either (a) allowing the plated work to cool in air for 10-50 seconds or (b) by heating the plated work in an atmosphere of 450.degree.-550.degree. c. and thereafter cooling it with cold or warm water. with regard to the zinc bullion, the same explanation as in a) also applies here. the plating is carried out by using a molten zinc alloy bath of the composition comprising 0.2-0.7 wt % ti with the balance being zn. this alloy bath is obtained by adding 0.2-0.7 wt %, preferably 0.2-0.5 wt %, ti to the above-mentioned zinc. in order to produce the yellow color coating from the hot-dip zinc alloy bath having the above composition, a base metal of iron or steel is immersed in the plating bath maintained at a temperature of more than 530.degree.-570.degree. c., preferably 540.degree.-560.degree. c. for at least one minute. the base metal is then removed from the bath and allowed to cool in air for about 10-50 seconds, preferably for 40-50 seconds. thereafter, the partially cooled material is immediately quenched with cold or warm water to form thereon an oxide film with a yellow hue. alternatively, the work taken out of the bath can be heated in an atmosphere at a temperature of 450.degree.-550.degree. c., preferably 470.degree.-510.degree. c., for at least one minute, preferably 1-2 minutes; and then cooled to form a yellow-colored oxide film thereon. thus, in order to produce a colored coating with a uniform, stable yellow hue on a base metal of iron or steel in accordance with the above process, it is essential to have the base metal plated under the specific conditions using a molten zinc alloy of a specific composition. if the conditions are outside the aforementioned ranges, the desired yellow hue will not result. this embodiment of the invention provides a corrosion-resistant material for the components and facilities for uses where they are required to be yellow in color from an aesthetic viewpoint. the iron or steel products colored by this process are highly corrosion-resistant and are of value in a wide range of commercial uses. (c-1) the development of dark-red color with ti-mn-zn alloy it is possible to form a colored coating with a dark red hue on a base metal of iron or steel by plating the base metal using a bath of a molten zinc alloy of a composition comprising 0.2-0.5 wt % ti, 0.05-0.15 wt % mn, and the balance zn at a bath temperature of 580.degree.-600.degree. c., by heating the plated work in an atmosphere at a temperature of 500.degree.-520.degree. c. for 30-70 seconds, after it is withdrawn from the bath and thereafter cooling it with cold or hot water. the metallic zinc to be used in forming the zinc alloy for hot dipping is typically one of the grades conforming to jis h2107, for example, distilled zinc 1st grade (at least 98.5% pure), purest zinc (at least 99.99% pure), and special zinc grades. the impurities inevitably contained in these zinc materials are, for example, in the distilled zinc 1st grade, all up 1.2 wt % pb, 0.1 wt % cd, and 0.020 wt % fe. for the purposes of the invention a metallic zinc with a total impurity content of less than 1.5 wt % is desirable. among these zinc varieties, distilled zinc is preferred practically because it can be plated with ordinary flux and the concentration is high. under this embodiment the plating is carried out using a bath of molten zinc alloy made by adding 0.2-0.5 wt %, preferably 0.3 wt %, ti and 0.05-0.15 wt %, preferably 0.1 wt %, mn to the above-mentioned zinc. in order to produce the dark red colored coating from the hot-dip zinc alloy bath of the above composition, a base metal of iron or steel is immersed in the plating bath at a temperature of 580.degree.-600.degree. c. for at least one minute. the base metal is pulled out of the bath and held in an atmosphere at a temperature of 500.degree.-520.degree. c. (for example in an oven) for 30-70 seconds. then the coated material is immediately quenched with cold or warm water to form thereon an oxide film with a dark red hue. thus, in producing a colored coating with a specific dark red hue, it is important to (a) plate the iron or steel base metal using the bath of the molten zinc alloy of the specific composition at the specific bath temperature, (b) heat it under specific temperature conditions, and then (c) quench it with cold or hot water. if the conditions are outside the ranges specified above, no coating with the desired dark red hue be obtained. (c-2) the development of green color with ti-mn-zn alloy using a zinc alloy for hot dipping to form on a base surface a green colored coating containing 0.2-0.5 wt % ti and 0.05-0.15 wt % mn, it is possible to produce a green colored coating on an iron or steel surface by (a) coating the base metal with the zinc alloy useful for hot dipping which is maintained at a bath temperature of 600.degree.-620.degree. c., (b) removing the coated material from the bath and heating it in an atmosphere at a temperature of 500.degree.-520.degree. c. for 50-60 seconds, and (o) quenching it with cold or hot water or with a coolant gas. the zinc to be used is in accordance with c-1). the coating is carried out using a molten zinc alloy bath of the above-mentioned zinc with the addition of 0.2-0.5 wt % ti and 0.05-0.15 wt % mn. the use of a hot-dip bath of a zinc alloy containing 0.3 wt % ti and 0.1 wt % mn is particularly desirable for forming a green colored coating. in order to produce the green colored coating from the hot-dip bath of the zinc alloy containing the above-specified percentages of ti and mn, a base metal of iron or steel is (a) immersed in the molten zinc alloy bath at 600.degree.-620.degree. c. for at least one minute, (b) pulled out of the bath and heated in an atmosphere (for example, in an oven) at a temperature of 500.degree.-520.degree. c. for 50-60 seconds and (c) quenched with cold or warm water or with coolant gas. as described above, a colored coating with a uniform, stable green hue can be obtained by conducting the plating by the use of a hot-dip bath of molten zinc alloy containing 0.2-0.5 wt % ti and 0.05-0.15 wt % mn under the specified condition. if the ti and mn contents in the zinc alloy are outside the ranges specified, the green hue of the resulting colored coating will be uneven and the oxide film will show poor wetability with respect to the coated based metal. also if the bath temperature and subsequent heating temperature and time are not within the specific ranges, other hues can mix in, rendering it impossible to produce a coating having a uniform green hue. thus, when producing a green colored coating uniform in hue, important roles are played by the ti and mn contents in the molten zinc alloy for the hot-dip bath, the hot-dip conditions, and the subsequent heating conditions. it is only by the combination of such specific conditions that the objective green colored coating is obtained. the colored coating formed resists corrosive attacks with the so-called corrosion weight loss by far the less than that of coatings using ordinary molten zinc alloys. (c-3) the development of yellow color with ti-mn-zn alloy it is possible to form a colored coating with a yellow hue on an iron or steel surface by (a) plating the base metal with a zinc alloy for hot dipping containing 0.2-0.5 wt % ti and 0.05-0.15 wt % mn at a bath temperature of 580.degree.-600.degree. c., (b) heating the plated work in an atmosphere at a temperature 500.degree.-520.degree. c. for 20-30 seconds, and (c) quenching it with cold or warm water with coolant gas. the zinc to be used is according to (c-1). the plating is carried out using a molten zinc alloy bath of the above-mentioned zinc with the addition of 0.2-0.5 wt % ti and 0.05-0.15 wt % mn. a bath of a molten zinc alloy containing 0.3 wt % ti and 0.1 wt % mn is particularly desirable. in order to produce the yellow colored coating from the hot-dip bath of the zinc alloy containing the above-specified amounts of ti and mn, a base metal of iron or steel is immersed in the plating bath at 580.degree.-600.degree. c. for at least one minute. the base metal is then pulled out of the bath and heated in an atmosphere (for example, in an oven) at a temperature of 500.degree.-520.degree. c. for 20-30 seconds. after the heating, the work is water-cooled for about 10 seconds to form thereon a colored coating of an oxide with a yellow hue. thus, in producing a yellow colored coating, it is especially important to perform the plating by the use of the bath of molten zinc alloy of the specific composition under the specific conditions and then heat the plated work in an atmosphere at a temperature of 500.degree.-520.degree. c. for 20-30 seconds. if the heating, after the plating process, is done under conditions outside the ranges specified above, no uniform yellow hue will be attained. for example, if the heating time exceeds 30 seconds the yellow color hue will be mixed with green, and the desired yellow colored coating will no longer be obtained. the colored coating obtained is excellent in its corrosion resistance. (c-4) the development of blue color with ti-mn-zn alloy it is possible to form a colored coating with a blue hue on an iron or steel surface by (a) plating the base metal using a bath of a zinc alloy for hot dipping of a composition comprising 0.1-0.5 wt % ti, 0.05-0.15 wt % mn, and the balance being zn at a bath temperature of 530.degree.-550.degree. c., (b) withdrawing the plated material from the bath and allowing it to cool in air for 15-25 seconds, and (c) quenching it with cold or warm water. the zinc to be used is in accordance with (c-1). the plating is carried out using a bath of molten zinc alloy made by adding 0.1-0.5 wt %, preferably 0.3 wt %, ti and 0.05-0.15 wt %, preferably 0.1 wt %, mn to the above-mentioned zinc. in order to produce the blue colored coating from the hot-dip zinc alloy bath of the above composition, a base metal of iron or steel is immersed in the plating bath at a temperature of 530.degree.-550.degree. c., for at least one minute. the base metal is pulled out of the bath and allowed to cool in air for about 15-25 seconds. the partially cooled material is then immediately quenched with cold or warm water to form thereon an oxide film with a blue hue. thus, in producing a blue colored coating, it is essential to plate the iron or steel base metal using the bath of molten zinc alloy of the composition comprising 0.1-0.5 wt % ti, 0.05-0.15 wt % mn, and the balance being zn at a bath temperature of 530.degree.-550.degree. c., and then allow it to cool in air for a short period of 15-25 seconds. if the conditions are outside the ranges specified above, no coating with the desired blue hue will result. the colored coating obtained in excellent is its corrosion resistance. (d-1) the development of olive gray color with mn-zn alloy using a zinc alloy for hot dipping having a composition composed of 0.2-0.8 wt % mn with the balance being zn, it is possible to form an olive gray colored coating on a base metal of iron or steel by (a) plating the base metal using a bath of the above zinc alloy at a bath temperature of 490.degree.-530.degree. c., (b) removing the coated material from the bath and heating it in an atmosphere at a temperature of 500.degree.-520.degree. c. for 50-150 seconds, and (c) either cooling the heated coated material with warm water or first forcibly air-cooling and then cooling it with warm water. the plating is carried out using a bath of molten zinc alloy made by adding 0.2-0.8 wt % mn to a purest metallic zinc bullion (at least 99.995% pure) or special zinc bullion (at least 99.99% pure) conforming to jis h2107 and used primarily as molten zinc alloy. the metallic zinc bullion for use in making the molten zinc alloy is desired to have a pb content of 0.005 wt % or less. in order to produce the olive gray colored coating from the hot-dip zinc alloy bath of the above composition, an iron or steel material is immersed in the plating bath at a temperature of 490.degree.-530.degree. c. for at least one minute. the base metal is pulled out of the bath and heated in an atmosphere at a temperature of 500.degree.-520.degree. c. for 50-150 seconds. finally, the heated, coated material and then is either (a) cooled with hot water or (b) first air-cooled forcibly in air and then cooled with warm water. thus, in producing a colored coating with an olive gray hue by the use of the molten zinc alloy bath of a composition comprising 0.2-0.8 wt % mn with the balance being zn, it is important to heat the plated metal in an atmosphere at a temperature of 500.degree.-520.degree. c. if the composition of the molten zinc alloy bath or the plating conditions deviate from the ranges specified above, the resulting colored coating can become uneven in hue or lose its hue, or the colored oxide film formed by the plating can tend to come off, rendering it impossible to obtain the desired olive gray colored coating. as stated hereinbefore, a colored coating with a uniform olive gray hue can be formed on an iron or steel material by (a) plating it under the specific conditions using the molten zinc alloy bath of the specific composition, (b) heating the plated metal, and (c) cooling the heated, plated material. this process provides a corrosion-resistant material for the components and facilities for uses where they are required to be olive gray in color from an aesthetic viewpoint. since the color-coated metal thus obtained is highly corrosion-resistant, the iron and steel products with such colored coatings according to the invention can be effectively used in a wide range of commercial applications. (d-2) the development of olive gray color with mn-cu-zn alloy using a zinc alloy for hot dipping to form on a base surface an olive gray colored coating of a composition comprising 0.2-0.8 wt % mn, 0.05-1.10 wt % cu, and with the balance being zn, it is possible to form a colored coating with an olive gray hue on a base metal of iron or steel by (a) plating the base metal using a bath of a the above zinc alloy for hot dipping at a bath temperature of 490.degree.-530.degree. c., (b) heating the plated work in an atmosphere at a temperature of 500.degree.-520.degree. c. for 50-150 seconds, and (c) either cooling the heated, plated material with warm water or first forcibly subjecting it to air-cooling followed by cooling it with warm water. the zinc to be used in making the molten zinc alloy is according to (d-1). in order to produce the olive gray colored coating on an iron or steel material, the base metal is immersed in the plating bath of the molten zinc alloy of the above zinc containing 0.2-0.8 wt % mn and 0.05-1.0 wt % cu at a temperature of 490.degree.-530.degree. c. for at least one minute. the metal is pulled out of the bath and heated in an atmosphere at a temperature of 500.degree.-520.degree. c. for 50-150 seconds. the heated, plated material is then either (a) cooled with warm water or (b) first air-cooled forcibly in air and then cooled with warm water. in this way an olive gray colored coating of oxide film is formed on the iron or steel surface. thus, in producing a colored coating with an olive gray hue it is important to use the molten zinc alloy bath of the specific composition, and carry out the plating, heating, and other after treatments under the specific conditions set out above. if the composition and the plating conditions deviate from the ranges specified above, the resulting colored coating can mix with some other hue or lose its hue, or the colored oxide film can tend to come off, rendering it impossible to obtain the desired olive gray hue. the colored zinc coated steel obtained is excellent in its corrosion. (d-3) the development of iridescent color with mn-zn or mn-cu-zn alloy iridescent, multicolored coating which exhibits a blend of golden, purple, blue, and green colors was found in an epochal way of color development that is not mere coloration of the ordinary metallic-colored hot-dip galvanized articles, but which is a breakthrough in the traditional concept of hues with ordinarily colored galvanized products. this is achieved by using a zinc alloy comprising either 0.1-0.8 wt % mn alone or 0.1-0.8 wt % mn and 0.05-1.0 wt % cu and the balance zn and inevitable impurities. this process comprises hot-dipping a base metal of iron or steel into a bath at a temperature of 450.degree.-550.degree. c., and then cooling the galvanized metal with warm water. the zinc alloy is made by adding a specific alloying additive or additives to metallic zinc bullion. the metallic zinc bullion to be used in making the molten zinc alloy under the invention is typically one of the grade conforming to jis h2107, for example, distilled zinc 1st grade (at least 98.5% pure), purest zinc (at least 99.99% pure), and special zinc grades. the impurities inevitably contained in these zinc materials are, for example in the distilled zinc 1st grade, all up to 1.2 wt % pb, 0.1 wt % cd, and 0.020 wt % fe. for the present invention a metallic zinc with a total impurity content below 1.5 wt % is desirable. according to this invention, a molten zinc alloy bath of the above metallic zinc containing (1) 0.1-0.8 wt %, preferably 0.2-0.8 wt %, mn or (2) 0.1-0.8 wt %, preferably 0.2-0.8 wt %, mn and 0.05-1.0 wt % cu is employed. if the mn content in the coating bath is less than 0.1 wt %, the oxide film formation is too slow and the resulting hues are thin. on the other hand, if there is more than 0.8 wt % mn present, this renders the hue adjustment difficult and reduces the wetability relative to the material being cooled. moreover, an mn content in excess of 0.2 wt % promotes the color development with a stable, blended multicolored effect. the addition of 0.05-1.0 wt % cu makes it possible for the coating solution to uniformly and smoothly flow off to produce a coated film having a uniform thickness and is helpful in preventing the separation of the oxide film. hot dipping is effected by the use if the above molten zinc alloy bath is at a temperature of 45.degree.-550.degree. c. the immersion, time is about 1 to 3 minutes. after the immersion the coated work is cooled with warm water. the cooling is done by dipping the work in warm water at 40.degree.-60.degree. c. for 3-30 seconds. if the bath composition and treating conditions are outside the specified ranges, the desired iridescent color development will not be attained. experiments revealed that too thin sheets sometimes cannot be colored in blended iridescent hues, presumably due to high cooling rates. the workpieces to be galvanized are desired to be 1.6 mm or more in thickness. before being galvanized, the work is pretreated in the usual way. it is degreased, for example by the use of an alkaline bath, descaled by pickling or other treatment, and then fluxed by a quick dip in a flux solution such as zncl.sub.2 --kf solution or zncl.sub.2 --nh.sub.4 cl solution. the simple procedure described above yields an iridescent multicolored coating which exhibits a blend of golden, purple, blue and green colors. the articles galvanized in this way are resistant to corrosive attacks and are capable of extensive use in the fields where both beautiful appearance and corrosion resistance are required. (d-4) the development of gold-purple-blue color with mn-ti-zn alloy it has been discovered that, by maintaining a relative high mn level and low ti level with the restriction of the impurity lead level in mn-ti-containing zinc alloy, it is possible to develop colors in the series of golden-purple-blue hues with a substantial reduction of the holding time in the heating atmosphere following the galvanizing. namely, these colors can be developed by using a hot-dip galvanizing zinc alloy containing 0.2-0.8 wt % mn and 0.01-0.1 wt % ti, with impurity pb limited to 0.005 wt % or less. the galvanized surface is outstandingly smooth to the beauty of the appearance. moreover, the bath temperature may be lower than usual. the metallic zinc bullion to be used in making the zinc alloy of this embodiment must be such that its impurity pb content is limited to 0.005 wt % or less. for this reason the use of the purest zinc bullion (at least 99.995% pure) defined in jis h2107 is desirable. special zinc bullion (at least 99.99 wt % pure) may also be used provided its pb content is confined within the limited 0.005 wt % or below. if more than 0.005 wt % lead is present in the coating bath, the colors of the golden-purple-red series will not develop within short periods of time. in accordance with the invention, 0.2-0.8 wt % mn and 0.01-0.1 wt % ti are added to the metallic zinc of high purity. these ranges of additions are based on the fact that a relatively small amount of ti and a relatively large amount of mn in the zinc alloy have been found helpful in shortening the period of time for which the galvanized work is held in the heating atmosphere. thus, the upper limit of ti is fixed to be 0.1 wt %. if the ti content is less than 0.01 wt %, there is no beneficial effect of the ti addition and coloring in desired hues becomes impossible. a large mn content of 0.2 wt % or above is necessary to obtain desired hues rapidly, but if the content exceeds 0.8 wt % the adjustment of hues becomes difficult and the work is not adequately wetted with the bath. in the hot-dip galvanizing with the zinc alloy, the work to be galvanized is degreased, for example by the use of an alkaline bath, descaled by pickling or the like, and then treated with a flux to be ready for galvanizing. the flux treatment is effected, for example, by a dip for a short time in a zncl.sub.2 --kf solution, zncl.sub.2 --nh.sub.4 cl solution, or other known flux solution. after the pretreatment, the work is immersed in a coating bath at a specific controlled temperature for 1 to 3 minutes. the coated metal is pulled out of the bath and, through proper control of the degree of oxidation of the coating film, a golden, purple, or blue color is selectively obtained. as the degree of oxidation increases, golden, purple, and blue colors are brought out successively in the order of mention. the galvanizing bath temperature is generally at a temperature of 480.degree.-550.degree. c., preferably 490.degree.-520.degree. c., or lower than the usual bath temperatures. this means a substantial reduction of energy cost in the case of mass treatment. after the coated work has been taken out of the bath, its degree of oxidation is changed through control of the cooling rate by cooling the work in a variety of ways, including natural cooling in the air, cooling with cold or warm water, forcible cooling, and slow cooling in an oven. a desirable practice consists in holding the galvanized metal in an atmosphere at a temperature of 450.degree.-550.degree. c. for a predetermined period of time and changing the rate of subsequent cooling so as to control the degree of oxidation. if the alloy layer comes up to the surface no color will develop. therefore, it is important to thicken the oxide film in preference to the growth of the alloy layer. the holding temperature, holding time, or cooling rate is so chosen as to cause appropriate color development. under the invention the heating time can be shortened. thus, within shorter periods of time than in the past, colors of the golden-purple-blue series are brought out. the rapid color development combines with great smoothness of the coated surface to give a fine-looking colored hot-dip galvanized material. this embodiment produces the following effect: 1. because of the short heating time in the heating atmosphere, the process involving the zinc alloy of the invention is adapted for continuous hot-dip galvanizing lines. 2. the lower bath temperature and shorter heating time than heretofore permit reduction of energy cost and provide favorable conditions for quantity production. 3. the zinc alloy gives very smooth, fine-looking galvanized surfaces with bright hues in the golden-purple-blue series. it was found to be effective to further include ce in the alloys used in said a) to d). (e) after-treatment the colored oxide film formed on the colored, hot-dip galvanized material tends to discolor or fade with time, with changes in hue due to the progress of deterioration, depending on the environmental conditions including the sunlight, temperature, and humidity. although the deterioration of the colored oxide film, of course, does not adversely affect the corrosion resistance of the hot-dip galvanized steel itself, the original beautiful appearance is unavoidably marred. as a simple measure for protecting the colored oxide film on the colored hot-dip galvanized material to suppress the discoloring or fading with time. surprisingly, painting has been found appropriate for realizing this object. as noted already, painting of the coated surface of ordinary (uncolored) hot-dip galvanized steel poses the problems of inadequate adhesion or separation of the paint film on short-period exposure. partly responsible for these are the deposits on the galvanized steel surface of oxides (zinc white rust) and flux such as ammonium chloride used for the galvanizing. presumably responsible too is the basic zinc dissolution product formed between zinc and the water that has permeated through the paint film. it is presumed that this product acts to decompose the resinous content (oily fatty acid) of an oily paint or long oil resin paint, causing the decomposition product to react with the zinc to produce zinc soap along the interface between the zinc surface and the paint film, thereby substantially reducing the adhesion of the paint. a common belief has been that the colored oxide film layer formed on the surface of the colored hot-dip galvanized steel does not provide an adequate barrier between the zinc surface and the surrounding air. the pessimistic view that painting over the oxide film would, after all, be the same as direct paint application to the galvanized surface has been predominant. contrary to these predictions, it has now been found that the colored oxide film has good affinity for and adhesion to paints, allowing the applied paint to permeate through the film to show high separation resistance, and is sufficiently capable of preventing water permeation to inhibit the reaction of the zinc layer with water and therefore the formation of zinc soap. in accordance with the invention, the hot-dip galvanized materials thus colored may be coated with a paint having excellent adhesion, weather resistance, durability, and environmental barrier properties. for the painting of ordinary hot-dip galvanized steels, pretreatment is essential and the types of paints that may be limited. with colored, hot-dip galvanized steels, by contrast, there is no need of pretreatment and various paints may be used. since the heating for oxidation that follows the galvanized step produces a film of oxide such as tio.sub.2 or mno on the galvanized surface, the coating on the galvanized steel is so clean that there is no necessity of treating the surface before painting. the paint to be used may be any type which does not unfavorably affect, but protect, the colored oxide film layer to be painted. typically a synthetic resin paint is used. among synthetic resin paints, those superior in protective effects are polyurethane resin, acrylic resin, epoxy resin, and chlorinated rubber paints. the paint is properly chosen in consideration of the price, environments to be encountered, ease of application, and other factors. where the color of the colored oxide film is to be shown as it is, a clear paint is the best choice; and where the color tone is to be modified, an aqueous paint is the easiest to handle. in any case, the paint can be applied by brushing, spraying, or dipping. in certain situations multicoating is not impractical. for instance, where the environments are very severe or adverse, multiple painting may be taken into account. an example is the application of an aqueous paint as the base coat and a clear paint as the intermediate and top coats. alternatively, an epoxy resin paint, durable against the alkali attacks that result from zinc elution, may form the undercoat, and a chlorinated rubber or polyurethane paint, which is resistant to water, chemicals, and weather, may form the intermediate and surface coats. even if the paint degrades with time, leading to chipping or flaking of the coat, the beautiful appearance of the galvanized steel will remain unaffected thanks to the colored oxide film on the steel surface. under the invention, such chipping or flaking seldom takes place because the paint permeated through and binds solidly with the colored oxide film. the paint that had permeated the oxide film keeps off water and the like by its water-repelling action and thereby protects the film. (f) spraying for the colored hot-dip galvanizing, it is prerequisite that the work to be coated must be dipped in a molten zinc alloy bath. in practice, this sometimes meets with the following limitations: (1) the dipping process is difficult to apply to shapes too large to be dipped in the bath. (2) the coating of assembly parts and structures is sometimes difficult. (3) localized coloring is cumbersome. although masking and other techniques may be resorted to, they involve much complexities and difficulties. the techniques are difficult to cope with the trend toward more frequent situations requiring pattern drawing for decorative purposes. (4) for repairs of installations and the like the process is difficult to practice at sites. (5) there are tendencies that the larger the content of such an alloying element as ti and mn, the worse the wetability of the bath and the more the number of holidays and other coating defects. although an increase in the content of the additive element improves the durability of the resulting coating accordingly, such addition is sometimes difficult from the standpoint of the coating technology. (6) the process sometimes brings failure of coating and other coating defects. it has been discovered, however, that the colored zinc alloy coating can be applied by spraying. specifically, the colored zinc coating by metal spraying basically involves spraying a zinc alloy, which is otherwise used for a coating bath, in the form of wire, rod, or powder, over the object. surprisingly, the oxidation reaction of the additional element had been found to proceed more favorably than expected during the spraying process, achieving at least as satisfactory effects as the colored hot-dip galvanizing. thus, in the present invention, a colored zinc coating may be attained by spraying a coloring, oxidizing zinc alloy over a base surface by a metal spraying process, whereby a colored oxide film is formed on the base surface. after the spraying, the color development of the colored oxide film may be controlled by cooling and/or heating. metal spraying comprises heating a sprayable material to a half-molten state and spraying it over a base surface to form a coating tightly bonded to the surface. the sprayable material takes the form of a wire, rod, or powder, any of which may be employed under the invention. the sprayable material may be any of the zinc alloys in common use for colored hot-dip galvanizing. it may, for example, be a ti-zn, mn-zn, or ti-mn-zn alloy with or without the further addition of cu, ni and/or cr. in the case of hot dipping, a work high in ti, mn or the like is not readily wetted when dipped in the bath, leaving flaws on the surface. the possibility of uncoating puts limitations to the amounts of the additive ingredients. metal spraying is free from the wetability problem, and larger proportions of the additional elements can be used. accordingly, the range of color development is wider and the hues have longer life. an example of desirable sprayable material is a zinc alloy containing 0.1-2.0 wt % ti and optionally 0.01-4.0 wt % of at least one element selected from the group consisting of mn, cu, cr, and ni. with good workability the zinc alloy can be easily made into a wire or rod or powdered by crushing or melt dropping. the sprayer that may usually be used is of the type known as a gas flame spray gun. an arc type spray gun may be employed as well. the sprayable material is melted by the sprayer and sprayed over the base surface to be coated. the corners and intricate portions of the work difficult to coat by hot dipping can be completely coated by aiming the spray gun to those portions. localized coatability permits figures and other patterns to be made easily. another major advantage of metal spraying is the ability of coating iron and steel structures or the like at the sites. after the spraying, the degree of surface oxidation is controlled so as to develop a desired color. a variety of colors, e.g., yellow, dark red, green, golden, purple, and blue colors, can be selectively developed as desired, depending on the degree of oxidation. for the oxidation control, the cooling rate of the sprayed coat can be adjusted by the use of natural cooling in the air or forced cooling with water or air. also, the spray coat may be heated for a variable period with flame, infrared lamp, oven (where usable) or the like, and the subsequent cooling may be controlled. proper combination of the sprayable material composition and surface oxidation conditions renders it possible to bring out a desired hue. in this way a zinc sprayed coating with both corrosion resistance and colorability is produced. the painting described above may be applied onto the sprayed coating. the functional effects of the spraying are summarized as follows: 1. applicable to large components that cannot be hot-dipped. 2. capable of easily coating the portions of assembly parts and structures difficult to hot-dip. 3. permits localized color development and display of a desired figure or other pattern thus enhancing the decorative value of the coating. 4. possibility of coating at the site. 5. ability to use high-melting alloys. 6. ease of forming a thick coat suited for providing long-term corrosion protection. 7. a high ti content in the alloy enhances the corrosion resistance and enriches the color hue. 8. the coating film, with a rough and porous surface, is suited as a base to be painted, and painting with a clear paint or various colored dyes can improve the durability of the colored oxide film of the coating. other than spraying process, vapor deposition process, sputtering process, ion plating process or other surface coating process may be applied in this invention. in addition to the aforementioned features pertaining to obtaining colored galvanized coatings via a spraying process, it has been discovered that clearer colorings are obtained when the thermal spraying step is followed by a heating step. a specific example of this process will be set out later in this application. the examples will be described below: the examples a to f correspond to the items a to f described in the detailed explanation. example a test pieces of steel sheet, ss41, 50 mm wide, 100 mm long, and 3.2 mm thick, were degreased by immersion in an alkaline bath at 80.degree. c. for 30 minutes. they were washed with hot water, and then derusted by immersion in a 10% hydrochloric acid bath at ordinary temperature for 30 minutes. next, the steel sheets were washed with warm water and fluxed by a dip in a solution containing zncl.sub.2 -nh.sub.4 cl for 30 seconds. the fluxing treatment is for removing the oxides on the surface of the steel sheet to promote the active surface of the sheet to a melt. the steel sheets thus pretreated were plated by immersion in plating baths of the various compositions as shown in table 1 at a temperature of 480.degree.-500.degree. c. for one to two minutes. they were pulled out of the bath at the rate of 3/m/min. each set of steel sheets pulled out of the bath was subjected to the following cooling conditions to form oxide films thereon: i) after the steel sheet were pulled out of the bath, it was allowed to cool in air followed by water cooling. ii) after the steel sheet was pulled out of the bath, it was heated in an atmosphere at a temperature 500.degree. c. for 10 to 30 seconds followed by air cooling and water cooling. iii) after the steel sheet was pulled out of the bath, it was heated in an atmosphere at a temperature of 500.degree. c. for 1.5 to 2.0 minutes followed by air cooling and water cooling. iv) after the steel sheet was pulled out of the bath, it was heated in an atmosphere at a temperature 500.degree. c. for 2.0 to 3.0 minutes followed by air cooling and water cooling. as shown in table 1, in the case where the steel sheets were dipped into the plating baths having various compositions and pulled out of the baths followed by being allowed to cool in air and water, oxide films having yellow hues were produced. on the other hand, when after the plating, heating step is adopted before air cooling and water cooling, purple, blue or young grass (light green) oxide films were produced according to the heating conditions. as seen in no. 6 of table 1, when mn and cu contents in the plating bath are near to their upper limits, it is known that bright color tones are developed. table 1 ______________________________________ no. plating bath plating condition ______________________________________ 1 0.5% shg: virgin 500.degree. c. - 2 min - 3 m/min ti--zn shg: fe saturate 500.degree. c. - 2 min - 3 m/min pw: fe saturate 480.degree. c. - 1 min - 3 m/min 2 0.5% ti - pw: fe saturate 480.degree. c. - 1.5 min - 0.5% 3 m/min cu--zn 3 0.5% ti - pw: fe saturate 500.degree. c. - 1 min - 3 m/min 0.5% ni--zn 4 0.5% ti - pw: fe saturate 480.degree. c. - 1.5 min - 0.01% 3 m/min cr--zn 5 0.5% ti - pw: fe saturate 500.degree. c. - 1 min - 3 m/min 0.0% mn--zn 6 0.5% mn - pw: fe saturate 480.degree. c. - 1 min - 3 m/min 0.5% cu--zn ______________________________________ formation of oxide no. film (color development) color ______________________________________ 1 1) allowed to cool in air for 10 sec - water yellow cooling 2) 450.degree. c. - 60 sec heating - air cooling - purple water cooling 3) 450.degree. c. - 2 min heating - air cooling - blue water cooling 1) the same as above the same 2) as above 3) 1) allowed to cool in air for 5 sec - water the same cooling as above 2) 450.degree. c. - 50 sec heating - air cooling - water cooling 3) 450.degree. c. - 2 min heating - air cooling - water cooling 2 1) allowed to cool in air for 10 sec - water the same cooling as above 2) 500.degree. c. - 1 min heating - air cooling - water cooling 3) 500.degree. c. - 2 min heating - air cooling - water cooling 3 1) allowed to cool in air for 5 sec - water the same cooling as above 2) 500.degree. c. - 70 sec heating - air cooling - water cooling 3) 500.degree. c. - 110 sec heating - air cooling - water cooling 4 1) allowed to cool in air for 5 sec - the same water cooling as above 2) 500.degree. c. - 1 min heating - air cooling - water cooling 3) 500.degree. c. - 2 min heating - air cooling - water cooling 5 1) allowed to cool in air for 10 sec - dark blue water cooling 2) 500.degree. c. - 30 sec heating - air cooling - blue water cooling 3) 500.degree. c. - 1.5 min heating - air cooling - young grass water cooling 4) 500.degree. c. - 2 min heating - air cooling - wall color water cooling 6 1) allowed to repidly cool in air - yellow water cooling 2) 500.degree. c. - 10 sec heating - air cooling - red purple water cooling 3) 500.degree. c. - 20 sec heating - air cooling - dark green water cooling 4) 500.degree. c. - 30 sec heating - air cooling - light green water cooling ______________________________________ note) "shg: virgin" indicates a plating bath based on 99.99% purity highest zinc. "shg: fe saturate" indicates a fesaturated plating bath based on 99.99% purity highest zinc. "pw: fe saturate" indicates a fesaturated plating bath based on not less than 98.5% purity distilled zinc. example b-1 development of golden color with ti-zn alloy a test piece of steel sheet, ss41, 50 mm wide, 100 mm long, and 3.2 mm thick, was degreased by immersion in an alkaline bath at 80.degree. c. for 30 minutes. it was washed with hot water, and then derusted by immersion in a 10% hydrochloric acid bath at ordinary temperature for 30 minutes. next, the steel sheet was washed with hot water and was fluxed by a dip in a solution containing 35% zncl.sub.2 -nh.sub.4 cl at 60.degree. c. for 30 seconds. the steel sheet thus pretreated was plated by immersion in a plating bath of the composition comprising 0.3 wt % ti, with the balance being zn, when at a temperature of 450.degree.-470.degree. c. for one minute. it was pulled out of the bath, allowed to cool in air for 10-20 seconds, and immediately cooled with water at ordinary temperature. the steel surface so obtained had a coating of oxide with a lustrous, uniform golden hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss was 72 g/m.sup.2. by way of comparison, ordinary plated steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120-150 g/m.sup.2. example b-2 development of purple color with ti-zn alloy the steel sheet, pretreated in the same manner as the previous example, was plated by immersion in a plating bath of the composition comprising 0.3 wt % ti, with the balance being zn, when at a temperature of 500.degree.-520.degree. c. for one minute. it was pulled out of the bath, allowed to cool in air for 40-50 seconds, and immediately cooled with water at ordinary temperature. the steel surface so obtained had a coating of oxide with a uniform purple hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss ws 63 g/m.sup.2. by way of comparison, ordinary plated steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120-150 g/m.sup.2. example b-2a development of purple color the steel sheet, pre-treated in the same manner as the previous example was plated by immersion in a plating bath for 90 seconds. the plating bath had a composition comprising 0.2 wt. % ti, with the balance being zinc. the bath was maintained when at a temperature of 480.degree. c. the coated material was pulled out of the bath and conveyed to a heating furnace in 17 seconds. there, the coated sheet was heated in air at a temperature of 500.degree. for 90 seconds. when the coated sheet was withdrawn from the furnace, a uniform purple color had been developed. the heated, colored material was let to cool. example b-3 development of yellow - dark red - green color and additional development of gold - purple - blue color the individual pieces pretreated as described previously were immersed in coating baths of the compositions given in table 2 for one minute and then were pulled out at a rate of about 6 meters per minute. the steel pieces thus taken out of the baths were heated in an atmosphere at a temperature of 500.degree. c. for given periods of time, and cooled with hot water to form the following colored oxide films. the treating conditions were as follows: ______________________________________ yellow: bath temperature 590.degree. c. .dwnarw. holding at 500.degree. c. for 15-20 seconds dark red: bath temperature 600.degree. c. .dwnarw. holding at 500.degree. c. for 25-30 seconds green: bath temperature 610.degree. c. .dwnarw. holding at 500.degree. c. for 35-40 seconds ______________________________________ table 2 __________________________________________________________________________ zinc alloy ingredient (wt %) color dross alloy no. ti pb cd cu, sn, bi, sb, in holiday shading deposition rating __________________________________________________________________________ this 1 0.25 -- -- -- .smallcircle. .smallcircle. .smallcircle. acceptable invention 2 0.25 1.5 -- -- .smallcircle. .smallcircle. .smallcircle. good 3 0.50 1.2 0.1 -- .smallcircle. .smallcircle. .smallcircle. good 4 0.30 1.2 0.1 cu 0.01 .smallcircle. .smallcircle. .smallcircle. very good 5 0.45 1.1 0.1 cu 0.02 .smallcircle. .smallcircle. .smallcircle. very good in 0.05 sn 0.04 comparative 6 0.17 1.3 .smallcircle. x .smallcircle. unaccept- example able 7 0.35 1.1 0.05 x x x unaccept- able __________________________________________________________________________ .smallcircle. no x yes using alloys nos. 2 to 5 of this example, golden, purple, and blue colors were successfully developed under the following conditions: ______________________________________ golden: bath temperature 490.degree. c. (1 min) .dwnarw. holding at 500.degree. c. for 1-2 seconds purple: bath temperature 500.degree. c. (1 min) .dwnarw. holding at 500.degree. c. for 10-15 seconds blue: bath temperature 520.degree. c. (1 min) .dwnarw. holding at 500.degree. c. for 15-20 seconds ______________________________________ thus, in the same manner as in the earlier examples, the oxidation conditions were gradually intensified to provide a wide variety of colors, as many as six, i.e., golden - purple - blue - yellow - dark red - green, in succession in a controllable manner. no flaws or color shading were observed. example b-4 development of yellow color with ti-zn alloy four steel grating members, each having a weight of 20 kg, were pre-treated in the same manner as the previous example. these grating members were plated by immersing them in a hot dipping bath of a zinc alloy for 90 seconds. this dipping bath contained 0.25 wt. % ti, with the balance being zinc and was maintained at a temperature of 550.degree. c. the coated members were then withdrawn from the bath and conveyed to a heating furnace in 17 seconds. there, the coated members were heated at a temperature of 500.degree. c. for 90 seconds. upon withdrawing the heated members from the heating furnace, they all had a uniform yellow colored coating. these members were then conveyed to a water tank in 16 seconds and cooled with water until their temperature fell below 100.degree. c. example c-1 development of dark red color with ti-mn-zn alloy a test piece of steel sheet, ss41, 50 mm wide, 100 mm long, and 3.2 mm thick, was degreased by immersion in an alkaline bath at a temperature of 80.degree. c. for 30 minutes. it was washed with hot water, and then derusted by immersion in a 10% hydrochloric acid bath at ordinary temperature for 30 minutes. next, the steel sheet was washed with hot water and was fluxed by a dip in a solution containing 35% zncl.sub.2 -nh.sub.4 cl at a temperature of 60.degree. c. for 30 seconds. the steel sheet thus pretreated was plated by immersion in a plating bath of the composition comprising 0.3 wt % ti, 0.1 wt % mn, and with the balance being zn while at a temperature of 580.degree.-600.degree. c. for one minute. it was pulled out of the bath, held in an oven at a temperature 500.degree.-520.degree. c. for 30-70 seconds, taken out of the oven, and was immediately cooled with warm water at a temperature of 40.degree.-60.degree. c. the steel surface so obtained had a coating of oxide film with a dark red hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss was 60 g/m.sup.2. by way of comparison, ordinary plated steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120.degree.-150 g/m.sup.2. example c-2 development of green color with ti-mn-zn alloy the steel sheet thus pretreated as described was plated by immersion in a plating bath of the composition given below at a temperature of 600.degree.-620.degree. c. for one minute. it was pulled out of the bath, held in an oven at a temperature of 500.degree.-520.degree. c. for 50-60 seconds, taken out of the oven, and cooled with warm water by a dip in the bath for 10 seconds. composition of the bath was as follows: 0.3 wt % ti, 0.1 wt % mn, and the balance zn. the zinc used was distilled zinc 1st grade. the sequential steps of plating, heating, and cooling with warm water gave a uniformly colored coating layer with a bright green hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss ws 61 g/m.sup.2. by way of comparison, ordinary steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120-150 g/m.sup.2. example c-3 development of yellow color with ti-mn-zn alloy the steel sheet pretreated as previously described was plated by immersion in a plating bath of the composition comprising 0.3 wt % ti, 0.1 wt % mn, and the balance being zn, while at a temperature of 580.degree.-600.degree. c. for one minute. it was pulled out of the bath, held in an oven at a temperature of 500.degree.-520.degree. c. for 20-30 seconds, taken out of the oven, and immediately cooled by dipping in warm water at a temperature of 40.degree.-60.degree. c. for 10 seconds. the steel surface so obtained had a coating of oxide with a bright yellow hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss ws 48 g/m.sup.2. by way of comparison, ordinary steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120-150 g/m.sup.2. example c-4 development of blue color with ti-mn-zn alloy the steel sheet pretreated as previously described was plated by immersion in a plating bath of the composition comprising 0.3 wt % ti, 0.1 wt % mn, and with the balance being zinc, while at a temperature of 530.degree.-550.degree. c. for one minute. it was pulled out of the bath, allowed to cool in air for 15-25 seconds, and immediately cooled with water at ordinary temperature. the steel surface so obtained had a coating of oxide film with a uniform blue hue. the test piece of steel sheet with color coating thus obtained was subjected to a salt spray corrosion test for 240 hours. the corrosion weight loss ws 70 g/m.sup.2. by way of comparison, ordinary plated steel sheets hot-dip galvanized with distilled zinc were likewise tested. the corrosion weight loss amounted to as much as 120-150 g/m.sup.2. example d-1 development of olive-gray color with mn-zn alloy a test piece of steel sheet, ss41, 50 mm wide, 100 mm long, and 3.2 mm thick, was degreased by immersion in an alkaline bath at a temperature of 80.degree. c. for 30 minutes. it was washed with hot water, and then descaled by immersion in a 10% hydrochloric acid bath at ordinary temperature for 30 minutes. next, the steel sheet was washed with hot water and was fluxed by a dip in solution containing 35% zncl.sub.2 -nh.sub.4 cl at a temperature of 60.degree. c. for one minute. the steel sheet thus pretreated was plated by the use of a plating bath of the following composition under the following conditions: ______________________________________ plating bath composition element (wt. %) ______________________________________ mn 0.3-0.5 zn (pb content = 50 ppm or less) bal. ______________________________________ plating conditions bath temp. heating temp. heating time (.degree.c.) (.degree.c.) (sec) ______________________________________ 500 500 150 ______________________________________ the plated steel sheet surface had a colored coating with a uniform olive gray hue. example d-2 development of olive gray color with mn-cu-zn alloy the steel sheet pretreated as previously described was plated by immersion in a plating bath of the following composition at a temperature of 490.degree.-530.degree. c. for one minute. the sheet was then pulled out of the bath and held in an oven at a temperature 500.degree.-520.degree. c. for 50-150 seconds. the plated sheet taken out of the oven was either cooled with warm water or forcibly air-cooled in air and then cooled with warm water. ______________________________________ plating bath composition element (wt. %) ______________________________________ mn 0.3-0.5 cu 0.1 zn (pb content = 50 ppm or less) bal. ______________________________________ plating conditions bath temp. heating temp. heating time (.degree.c.) (.degree.c.) (sec) ______________________________________ 520 500 100 500 500 150 ______________________________________ the plated steel sheet surface had a colored coating with a uniform olive gray hue. example d-3 development of iridescent color with mn-zn or mn-cu-zn alloy test pieces of steel sheets, grade ss41, measuring 50 mm wide, 100 mm long, and 1.6-6.0 mm thick, were degreased by immersion in an alkaline bath at a temperature of 80.degree. c. for 30 minutes. they were washed with hot water, and then were descaled by immersion in a 10% hydrochloric acid solution at ordinary temperature for 30 minutes. next, the steel pieces were washed with hot water fluxed by immersion in a 35% zncl.sub.2 -nh.sub.4 cl solution at a temperature of 60.degree. c. for one minute. the steel pieces so pretreated were galvanized by immersion in the baths of compositions shown in table 3 at a temperature of 450.degree.-550.degree. c. for one minute, and then cooled with warm water. the cooling was done by a dip in a bath of warm water at a temperature of 40.degree. c. for 5 seconds. the results are shown in table 3. table 3 ______________________________________ galvanizing oxide zinc condition film drip- alloy bath dip cool- separ- less (wt %) temp. time ing hue ation.sup.1 ness.sup.2 ______________________________________ 0.2% 460.degree. c. 1 min warm irides- .smallcircle. x mn--zn water cent cooling colored 0.35% 450 " warm irides- .smallcircle. x mn--zn water cent cooling colored 0.5% 555 " warm irides- x .smallcircle. mn--zn water cent cooling colored 0.6% mn-- 0.08% 480 " warm irides- .smallcircle. .smallcircle. cu--zn water cent cooling colored 0.5% mn-- 0.2% 500 " warm irides- .smallcircle. .smallcircle. cu--zn water cent cooling colored ______________________________________ .sup.1 oxide film separation: .smallcircle. no x yes .sup.2 driplessness: .smallcircle. good x poor example d-4 development of gold - purple - blue with mn-ti-zn alloy the steel pieces treated as described in d-1 were immersed in a bath of molten zinc alloy containing 0.5 wt % mn and 0.08 wt % ti, with the pb content restricted to 0.004 wt %, at a temperature of 500.degree. c. for one minute. they were then held in a heating atmosphere at a temperature of 500.degree. c. and cooled. the relations between the treating conditions and coloring are shown in the following table 4. golden and purple colors came out very rapidly and even blue color developed in 30 seconds. the galvanized surfaces were quite smooth and beautiful in appearance. table 4 ______________________________________ color bath heating heating cooling smoothness develop- temp. temp. time time and beauti- ment (.degree.c.) (.degree.c.) (sec) (sec) fulness ______________________________________ golden 500 500 2 6 good purple 500 500 7 10 " blue 500 500 30 50 " (allowed to cool) ______________________________________ example e after treatment test pieces of steel sheet, measuring 50 mm wide, 100 mm long, and 3.2 mm thick, were either conventionally hot-dip galvanized or colored, hot-dip galvanized (with a zn-ti alloy). the galvanized pieces were coated with a clear polyurethane resin (resin : hardener=5:1) or a colored, aqueous acrylic resin paint by brushing or dipping. the coated pieces, together with uncoated ones, were subjected to outdoor weathering tests. the tests were conducted within a plant under the possession of the present applicant. the degrees of degradation after test periods of three months, six months, and one year were visually inspected. the results are tabulated below in table 5. conventionally hot-dip galvanized pieces became defective in only three months after the painting. among the colored, hot-dip galvanized pieces, the golden-colored piece had a thinner oxide film than the rest because of the incomplete oxidation. without a paint coat, therefore, the golden-colored piece degraded in three months and the blue-colored in one year. painting could retard the degradation. needless to say, an increase in the thickness of the paint coat, multicoating, or other similar step would prove effective in further retarding the degradation. with regard to ti-mn-zn system, mn-zn system etc., good effects with the painting were confirmed. table 5 ______________________________________ outdoor weathering test test piece condition 3 months 6 months 1 year ______________________________________ aqueous hot-dip x x x acrylic galvanized resin colored blue .smallcircle. .smallcircle. .smallcircle. galvanized yellow .smallcircle. .smallcircle. .smallcircle. green .smallcircle. .smallcircle. .smallcircle. clear colored golden .smallcircle. .delta. x poly- galvanized blue .smallcircle. .smallcircle. .smallcircle. urethane yellow .smallcircle. .smallcircle. .smallcircle. resin green .smallcircle. .smallcircle. .smallcircle. olive .smallcircle. .smallcircle. .smallcircle. not colored golden x x x painted galvanized blue .smallcircle. .smallcircle. .delta. yellow .smallcircle. .smallcircle. .smallcircle. green .smallcircle. .smallcircle. .smallcircle. olive .smallcircle. .smallcircle. .smallcircle. ______________________________________ .smallcircle.: good .delta.: rather poor x: poor example f-1 spraying a rod of zinc alloy containing 1.9 wt % ti and 0.3 wt % mn was used as a sprayable material. it was sprayed over a steel material by means of an oxy-acetylene gas flame type spray gun. the sprayed surface was allowed to cool, heated to a temperature of 500.degree. c. for 30 seconds, and again allowed to cool in the air. a green colored coating was obtained. example f-2 spraying under the same conditions as in example f-1 but by the use of a zinc alloy rod containing 1.0 wt % ti, spraying and after heat treatment were carried out. a blue colored coating resulted. example f-3 spraying a rod of zinc alloy containing 0.3 wt % mn was used as a sprayable material. it was sprayed over a steel material by means of an oxy-acetylene gas flame type spray gun. the sprayed surface was allowed to cool, heated to a temperature of 500.degree. c. for 30 seconds, and again allowed to cool in the air. a olive gray colored coating was obtained. example f-4 spraying a zinc alloy containing 0.2 wt. % ti, with the balance being zinc was formed into rods having a diameter of 1.6 mm. these rods were to be used for thermal spraying in accordance with the present invention. the thermal spraying was carried out using a spray gun with nitrogen gas as the carrier gas. the spraying rods were heated to a high temperature to form melts within the gun. the melts were entrained by the nitrogen carrier gas towards the metal substrate and deposited thereon. an iron plate, an aluminum plate and a refractory member were employed as the substrates. after spraying it was observed that the color of the thermally sprayed surface was not adequately clear and uniform. thereafter, the thermally sprayed surfaces were heated to 425.degree. c. and 450.degree. c. for varied time periods. as the result, gold, purple and blue colors were obtained. the specific color obtained depended upon the heating time periods, such as is listed in the following table: table ______________________________________ heated temperature color heated time period developed ______________________________________ 425.degree. c. 10 min gold 13 min. purple 15 min. blue 450.degree. c. 8 min. gold 12 min. purple 14 min. blue ______________________________________ it is evident from the foregoing that various modifications can be made to the embodiments of this invention without departing from the spirit and scope thereof which will be apparent to those skilled in the art. having thus described the invention, it is claimed as follows:
|
088-571-729-209-821
|
US
|
[
"US"
] |
C12N9/64,G06F19/00,G16B15/20,G16B20/30
| 2001-10-19T00:00:00 |
2001
|
[
"C12",
"G06",
"G16"
] |
crystal structure of a mutant of cathepsin s enzyme
|
the invention relates to the x-ray crystal structure of a cathepsin s mutant. the invention further relates to an apparatus programmed with one or more of the structure coordinates of the cathepsin s binding pockets, wherein said apparatus is capable of displaying a three-dimensional representation of that binding pocket.
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1 . a crystalline cathepsin s polypeptide, free of any irreversible inhibitor bound thereto. 2 . a crystalline cathepsin s polypeptide comprising the amino acid sequence of any of of seq id nos: 1-8, free of any inhibitor irreversibly bound thereto. 3 . a substantially pure crystalline cathepsin s polypeptide comprising the amino acid sequence of any one of seq id nos: 1-8. 4 . a substantially pure crystalline cathepsin s polypeptide comprising a variant of any one of seq id nos: 1-8, which variant does not possess the activity of cathepsin b, h, k or l. 5 . a cathepsin s polypeptide comprising a variant of the amino acid sequence of any one of seq id nos: 1, 2, 5 and 6, wherein the cys25 residue is replaced with a ser residue. 6 . the cathepsin s polypeptide according to claim 4 or 5 , wherein said variant comprises all or part of the cathepsin s active site. 7 . the cathepsin s polypeptide according to claim 5 , which comprises the amino acid sequence of any one of seq id nos: 3, 4, 7 and 8. 8 . a crystalizable composition comprising a cathepsin s polypeptide which is free of any irreversible inhibitor bound thereto. 9 . the crystalizable composition according to claim 8 , wherein the cathepsin s polypeptide comprises a variant of the amino acid sequence of any one of seq id no: 1, 2, 5 and 6, wherein the cys25 residue is replaced with a ser residue. 10 . the crystalizable composition according to claim 8 , wherein the cathepsin s polypeptide comprises the amino acid sequence of any one of seq id no: 3, 4, 7 and 8. 11 . the crystalizable composition according to claim 8 , wherein the cathepsin s polypeptide is a variant of any one of seq id no:1-8, which comprises all or part of the cathepsin s active site. 12 . the crystalizable composition of claim 11 , wherein said active site comprises binding pockets s ₁ , s ₂ , s ₃ , and s ₁ . 13 . the crystalizable composition of claim 11 , wherein said variant is a fragment. 14 . the crystalizable composition of claim 13 , wherein said fragment comprises at least one member of the group consisting of binding pockets s ₁ , s ₂ , s ₃ , and s ₁ . 15 . the crystalizable composition of claim 12 or 14 , wherein said s ₁ binding pocket comprises gln19. 16 . the crystalizable composition of claim 12 or 14 , wherein said s ₂ binding pocket comprises met71, gly137, val138, val162, asn163, gly165 and phe211. 17 . the crystalizable composition of claim 12 or 14 , wherein said s ₃ binding pocket comprises gly62, asn63, lys64, asn67, gly68 and gly69. 18 . the crystalizable composition of claim 12 or 14 , wherein said s ₁ binding pocket comprises trp186. 19 . the composition of claim 13 , wherein said fragment is fused to another polypeptide. 20 . an apparatus for producing a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , wherein said apparatus comprises: i) an input for accessing data that includes the structure coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3; ii) a processor for processing said data into said three-dimensional representation; and iii) a display for displaying said three-dimensional representation generated by said processor. 21 . the apparatus according to claim 20 , wherein said apparatus produces a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , wherein said data includes the structure coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3. 22 . an apparatus for producing a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , said apparatus comprising: i) an input for accessing data that includes the structure coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; ii) a processor for processing said data into said three-dimensional representation; and iii) a display for displaying said three-dimensional representation generated by said processor. 23 . the apparatus according to claim 22 , wherein said apparatus produces a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , wherein said data includes the structure coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3. 24 . an apparatus for producing a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids gln19, gly23 and cys25 according to table 3; or c) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , said apparatus comprising: i) an input for accessing data that includes the structure coordinates of cathepsin s amino gln19, gly23 and cys2 according to table 3; ii) a processor for processing said data into said three-dimensional representation; and iii) a display for displaying said three-dimensional representation generated by said processor. 25 . the apparatus according to claim 24 , wherein said apparatus produces a three-dimensional representation of: a) a molecule or molecular complex, wherein said molecule or molecular complex comprises a binding pocket defined by structure coordinates of cathepsin s amino acids gln19, gly23 and cys2 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , wherein said data includes the structure coordinates of cathepsin s amino acids gln19, gly23 and cys2 according to table 3. 26 . an apparatus for determining at least a portion of the structure coordinates corresponding to x-ray diffraction data obtained from a molecule or molecular complex, wherein said apparatus comprises an input for accessing first data that includes at least a portion of the structural coordinates of cathepsin s according to table 3 and; a) second data that includes x-ray diffraction data obtained from said molecule or molecular complex; b) a processor for performing a fourier transform of said first data and said second data for processing said first data and said second data into structure coordinates; and c) a display for displaying said structure coordinates of said molecule or molecular complex. 27 . the apparatus according to claim 26 , wherein said molecule or molecular complex comprises a polypeptide having cathepsin s activity. 28 . a method for evaluating the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , comprising the steps of: i) employing computational means to perform a fitting operation between the chemical entity and a binding pocket defined by structure coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.54 , and ii) analyzing the results of said fitting operation to quantify the association between the chemical entity and the binding pocket. 29 . the method according to claim 28 , wherein said method evaluates the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids gly68, gly69, phe70, gly62, asn63 and lys64 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 30 . a method for evaluating the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , comprising the steps of: i) employing computational means to perform a fitting operation between the chemical entity and a binding pocket defined by structure coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , and ii) analyzing the results of said fitting operation to quantify the association between the chemical entity and the binding pocket. 31 . the method according to claim 30 , wherein said method evaluates the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 . 32 . a method for evaluating the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids met71, gly137, val138, val162, gly165 and phe211 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , comprising the steps of: i) employing computational means to perform a fitting operation between the chemical entity and a binding pocket defined by structure coordinates of cathepsin s amino acids gln19, gly23 and cys25 according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , and ii) analyzing the results of said fitting operation to quantify the association between the chemical entity and the binding pocket. 33 . the method according to claim 30 , wherein said method evaluates the potential of a chemical entity to associate with: a) a molecule or molecular complex comprising a binding pocket defined by the coordinates of cathepsin s amino acids gln19, gly23 and cys25 according to table 3; or b) a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 . 34 . the method according to any one of claims 28 , 30 and 32 , wherein said method evaluates the potential of a chemical entity to associate with a molecule or molecular complex: a) defined by structure coordinates of all of the cathepsin s amino acids, as set forth in table 3, or b) a homologue of said molecule or molecular complex having a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 35 . a method for identifying a potential cats inhibitor molecule comprising a cathepsin s s3-like binding pocket comprising the steps of: a) using the atomic coordinates of gly68, gly69, phe70, gly62, asn63 and lys64, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensional structure of molecule comprising a cathepsin s s3-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor; and d) contacting said inhibitor with said molecule to determine the ability of said potential agonist or antagonist to interact with said molecule. 36 . a method for identifying a potential cats inhibitor molecule comprising a cathepsin s s2-like binding pocket comprising the steps of: a) using the atomic coordinates of acids met71, gly137, val138, val162, gly165 and phe211, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensional structure of molecule comprising a cathepsin s s2-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor; and d) contacting said inhibitor with said molecule to determine the ability of said potential inhibitor to interact with said molecule. 37 . a method for identifying a potential cats inhibitor molecule comprising a cathepsin s s1-like binding pocket comprising the steps of: a) using the atomic coordinates of acids gln19, gly23 and cys25, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensional structure of molecule comprising a cathepsin s s1-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor; and d) contacting said inhibitor with said molecule to determine the ability of said potential inhibitor to interact with said molecule. 38 . the method according to any one of claims 35 - 37 , wherein in step (a), the atomic coordinates of all the amino acids of cathepsin s according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 are used. 39 . a method for making a cats inhibitor molecule comprising a cathepsin s s2-like binding pocket comprising the steps of: a) using the atomic coordinates of acids met71, gly137, val138, val162, gly165 and phe211, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensionsal structure of molecule comprising a cathepsin s s2-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor. 40 . the method according to claim 39 , wherein in step (a), the atomic coordinates of all the amino acids of cathepsin s according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 are used. 41 . a method for producing a potential cats inhibitor molecule comprising a cathepsin s s3-like binding pocket comprising the steps of: a) using the atomic coordinates of gly68, gly69, phe70, gly62, asn63 and lys64, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensional structure of molecule comprising a cathepsin s s3-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor. 42 . the method according to claim 41 , wherein in step (a), the atomic coordinates of all the amino acids of cathepsin s according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 are used. 43 . a method for producing a potential cats inhibitor molecule comprising a cathepsin s s1-like binding pocket comprising the steps of: a) using the atomic coordinates of gln19, gly23 and cys25, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 , to generate a three-dimensional structure of molecule comprising a cathepsin s s1-like binding pocket; b) employing said three-dimensional structure to design or select said potential inhibitor; c) synthesizing said inhibitor. 44 . the method according to claim 43 , wherein in step (a), the atomic coordinates of all the amino acids of cathepsin s according to table 3, plus or minus a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 are used.
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technical field of invention the present invention relates to crystals of a mutant cathepsin s (cats) enzyme and more particularly to the high resolution structure of a mutant cats obtained by x-ray diffraction. this invention also relates to other mutants of cats. in addition, this invention relates to methods of using the structure coordinates of a mutant cats and other mutant cats to screen and design compounds that bind to the active site and accessory binding site of cats. background art cathepsin s is a single-chain cysteinyl proteinase of the papain superfamily, highly stable at neutral or slightly acidic ph, which was first isolated from bovine lymph nodes and spleen (kirschke et al., 1986; turnsek et al., 1975). subsequent investigations have shown that expression of cathepsin s is almost exclusively restricted to cells of lymphoid origin (kirschke et al., 1989; qian et al., 1991; shi et al., 1994). interest has recently focused on cathepsin s and its role in immune system regulation. extracellular protein antigens are transported into antigen presenting cells via endocytosis or phagocytosis. these protein antigens must be digested to small peptides which are then loaded onto the binding groove of major histocompatibility complex (mhc) class ii and presented for recognition by cd4 t lymphocytes (germain & margulies, 1993). invariant chain (ii) is removed from mhc class ii dimers by gradual regulated cleavage of ii by lysosomal proteinases (cresswell, 1996; newcomb & cresswell, 1993; roche & cresswell, 1991) including cathepsin s (riese et al., 1998; riese et al., 1996). indeed, mouse gene knockout experiments have demonstrated that cathepsin s deficiency results in a block in the processing of mhc class ii-associated invariant chain ii leading to markedly delayed mhc class ii peptide loading in b lymphocytes and dendritic cells (nakagawa et al., 1999; shi et al., 1999). moreover, administration of the selective irreversible cathepsin s inhibitor lhvs to mice results in accumulation of a ii breakdown product, attenuation of mhc class ii peptide complex formation and inhibition of antigen presentation (riese et al., 1998). for this reason, cathepsin s is considered a target for autoimmune disease therapy. however, inhibition of the closely related family members cathepsin l and k could lead to changes in skin and hair and bone remodeling (gowen et al., 1999; hofbauer & heufelder, 1999; nakagawa et al., 1998; saftig et al., 1998), highlighting the need for inhibitor selectivity. a homology model for cathepsin s was published in 1997 (sumpter et al., 1997), but provides little guidance for the modeling of inhibitors which are potent against cathepsin s without also inhibiting other members of the papain superfamily. a 2.5 crystal structure of cathepsin s liganded to and distorted by a potent irreversible vinyl sulfone inhibitor, apc 2848 has been published (mcgrath et al., 1998). as is apparent from mcgrath, however, this structure was based on a single crystal of questionable quality and a significant amount of the structure has been inferred from homologies with cathepsin k. accordingly this publication is not suitable for accurate modeling of selective cathepsin s inhibitors. it will thus be apparent that the prior art has been unable to prepare cathepsin s crystals unliganded or liganded with reversible inhibitors which would allow the detailed structure of the active site to be elucidated. thus, x-ray crystallographic analysis of such proteins has not been possible, thereby hampering development of effective drugs. summary of the invention the present invention solves this problem by providing, for the first time, a crystalizable mutant of the cats enzyme. it is an object of the invention to provide a crystalline cats polypeptide, or a variant thereof, free of any irreversible inhibitor bound thereto, for solving the three-dimensional structure of the cats enzyme and to determine its structure coordinates. it is an object of the invention to provide a crystalizable composition comprising a cathepsin s polypeptide, free of any irreversible inhibitor bound thereto, for solving the three-dimensional structure of the cats enzyme and to determine its structure coordinates. it is a further object of the invention to provide cats mutants characterized by one or more different properties as compared with wild-type cats. these properties include altered surface charge, altered substrate specificity or altered specific activity, including tendency to autodigestion. cats mutants are useful for producing high concentrations of cathepsin s for crystallography and other assays and for identifying those amino acids that are most important for the enzymatic activity of cats. this information, in turn, allows the design of cats inhibitors. it is also an object of the invention to provide a method that uses the structure coordinates and atomic details of cats, or its mutants or homologues or co-complexes, to design, evaluate computationally, synthesize and use inhibitors of cats that avoid the undesirable physical and pharmacologic properties of the current proteinase inhibitors. it is also an object of the invention to provide a computer for producing a three-dimensional representation of a molecule or molecular complex, which molecule or molecular complex comprises at least one of the binding pockets of cathepsin s. the computer comprises a computer-readable data storage material encoded with computer-readable data (which comprises the structure coordinates of cathepsin s binding pocket amino acids), a working memory for storing instructions for processing the computer-readable data, a central-processing unit coupled to the working memory and to the computer-readable data storage medium for processing the computer-machine readable data into said three-dimensional representation and a display coupled to the central-processing unit for displaying said three-dimensional representation. it is also an object of the invention to provide a computer for determining at least a portion of the structure coordinates corresponding to x-ray diffraction data obtained from a molecule of molecular complex of cathepsin s. the computer comprises a computer-readable data storage medium, a computer-readable data storage medium, a working memory for storing instructions for processing the computer-readable data, a central processing unit coupled to the working memory and to the computer-readable data storage medium for performing a fourier transform of the machine readable data and for processing the computer-readable data into structure coordinates and a display coupled to the central-processing unit for displaying the structure coordinates of the cathepsin s molecule or molecular complex. it is a also object of the invention to provide a method for evaluating the potential of a chemical entity to associate with a cathepsin s molecule, molecular complex, homologue or homologue complex that comprises the steps of employing computational means to perform a fitting operation between the chemical entity and at least one cathepsin s binding pocket and analyzing the results to quantify the association between the chemical entity and the binding pocket. it is also an object of the invention to provide a method for producing an inhibitor of a molecule comprising a cathepsin s-like binding pocket comprising the steps of using the atomic coordinates of the cathepsin s binding pockets to generate a three-dimensional structure of the molecule comprising a cathepsin s-like binding pocket, using the three-dimensional structure to design or select the potential agonist or antagonist and synthesizing the agonist or antagonist. the invention allows the modeling and provision of cathepsin s inhibitors which do not substantially inhibit other members of the papain superfamily. the use of the invention will thus lead to methods for the treatment of autoimmune disease by administration to a patient in need thereof an effective amount of an inhibitor of cathepsin s. it is also an object of the invention to provide a method for identifying a potential inhibitor of a molecule comprising a cathepsin s-like binding pocket comprising the steps of using the atomic coordinates of the cathepsin s binding pockets to generate a three-dimensional structure of the molecule comprising a cathepsin s-like binding pocket, using the three-dimensional structure to design or select the potential inhibitor and synthesizing the inhibitor and contacting the inhibitor with an active cathepsin s enzyme or fragment thereof to determine the ability of the inhibitor to interact with cathepsin s. brief description of the drawings fig. 1 represents the c trace of papain (9pap.pdb-purple) and cathepsin l (1cs8.pdb-green), k (1mem.pdb-red), h (8pch.pdb-yellow) and s (blue). fig. 2 stereo picture of c-c trace of cathepsin s. the figure was produced using sybyl 6.6 (tripos). fig. 3 represents a ribbon model of cathepsin s with the catalytic triad cys25ser, his164 and asn184 shown as ball and sticks color coded by atom type. fig. 4 represents the hydrogen bonding network in the active site. the catalytic triad (with the ser25 mutation) is shown on the right, with three water molecules in the center and gln19 and trp186 to the left. hydrogen bonds are shown as dashed lines. the observed network may provide a mechanism for correct catalytic residue side chain orientation prior to substrate hydrolysis. fig. 5 represents the final maximum likelihood-weighted electron density map (2f ₒ -f _{c} ) contoured at 1 above the mean. the catalytic residues for cathepsin k and mutant cathepsin s are represented by ball and stick models with atom-specific colors: oxygen-red, nitrogen-blue, carbon-gray. this figure shows that the constellation of the active site residues is essentially unchanged in the mutant. fig. 6 represents a view of the substrate-binding cleft of cathepsin s showing the proposed substrate-binding sites s3 to s1. the enzyme is shown with a surface colored by electrostatic potential (gasteiger charges). fig. 7 is a 2d representation of the residues present in the non-prime side of the cathepsin s substrate binding site. for substrate specificity comparisons, the equivalent residues in cathepsin k (1mem.pdb) and cathepsin l (1cs8.pdb) are shown in blue and red, respectively. fig. 8 is a block diagram of an exemplary computer system for implementing 3-dimensional modeling of a molecule or molecular complex according to principles of the present invention. fig. 9 shows a cross section of a magnetic storage medium. fig. 10 shows a cross section of an optically-readable data storage medium. table 1 lists the data collection and refinement statistics, and the model statistics. table 2 lists the crystallographic coordinate transformation data. table 3 lists the atomic structure coordinates for cats as derived by x-ray diffraction from a crystal of the mutant cats. the following abbreviations are used in table 3: refers to the atom serial number. atom type refers to the element whose coordinates are measured. the first letter in the column defines the element. res denotes the amino acid residues' name using the three letter code. the abbreviations used are listed below. chn i.d. is the chain identifier. res provides the residue sequence number. x coord., y coord. and z coord. represent the values for the s, y and z coordinates and crystallographic ally define the atomic position of the element measured. occ is an occupancy factor that refers to the fraction of the molecules in which each atom occupies the position specified by the coordinates. a value of 1 indicates that each atom has the same conformation, i.e., the same position, in all molecules of the crystal. temp fact is a thermal factor that measures movement of the atom around its atomic center. atomic provides the correct atomic number. structure coordinates for cats according to table 3 may be modified from this original set by mathematical manipulation. such manipulations include, but are not limited to, crystallographic permutations of the raw structure coordinates, fractionalization of the raw structure coordinates, integer additions or subtractions to sets of the raw structure coordinates, inversion of the raw structure coordinates, and any combination of the above. abbreviations and definitions abbreviations amino acids aalaalanine vvalvaline lleuleucine iileisoleucine pproproline fphephenylalanine wtrptryptophan mmetmethionine gglyglycine sserserine tthrthreonine ccyscysteine ytyrtyrosine nasnasparagine qglnglutamine daspaspartic acid egluglutamic acid klyslysine rargarginine hhishistidine definitions the term naturally occurring amino acids means the l-isomers of the naturally occurring amino acids. the naturally occurring amino acids are glycine, alanine, valine, leucine, isoleucine, serine, methionine, threonine, phenylalanine, tyrosine, tryptophan, cysteine, proline, histidine, aspartic acid, asparagine, glutamic acid, glutamine,, arginine, and lysine. unless specifically indicated, all amino acids referred to in this application are in the l-form. the term unnatural amino acids means amino acids that are not naturally found in proteins. examples of unnatural amino acids include racemic mixtures of selenocysteine and selenomethionine. in addition, unnatural amino acids include the d or l forms of nor-leucine, -carboxyglutamic acid, ornithine, para-nitrophenylalanine, homophenylalanine, para-fluorophenylalanine, 3-amino-2-benzylpropionic acid, homoarginine, and d-phenylalanine. the term positively charged amino acid includes any naturally occurring or unnatural amino acid having a positively charged side chain under normal physiological conditions. examples of positively charged naturally occurring amino acids are arginine, lysine and histidine, with ornithine representing a non-natural amino acid the term negatively charged amino acid includes any naturally occurring or unnatural amino acid having a negatively charged side chain under normal physiological conditions. examples of negatively charged naturally occurring amino acids are aspartic acid and glutamic acid. the term hydrophobic amino acid means any amino acid having an uncharged, nonpolar side chain that is relatively insoluble in water. examples of naturally occurring hydrophobic amino acids are alanine, leucine, isoleucine, valine, proline, phenylalanine, tryptophan and methionine. the term hydrophilic amino acid means any amino acid having an uncharged, polar side chain that is relatively soluble in water. examples of naturally occurring hydrophilic amino acids are serine, threonine, tyrosine, asparagine, glutamine, and cysteine. the term mutant refers to a nucleic acid that encodes a cats polypeptide, but whose sequence differs from the wild-type cats nucleic acid. such a mutant may be prepared, for example, by expression of cats cdna previously altered in its coding sequence by oligonucleotide-directed mutagenesis. the mutant would preferably contain 80%, 85%, 90% or 95% sequence identity with the wild-type cats nucleic acid. more preferably, the mutant would contain 96%, 97%, 98%, 99% or 99.5% identity with the wild-type cats nucleic acid sequence. the term variant refers to a cats polypeptide, i.e characterized by the replacement of at least one amino acid from the wild-type, human cats sequence according to shi et al. (1994) j biol chem 269:11530-6 (seq id no: 1). such a variant may be prepared, for example, by expression of cats cdna previously altered in its coding sequence by oligonucleotide-directed mutagenesis. this polypeptide may or may not display the biological activity of wild-type, human cats, but would contain all or part of the cats active site. the variant would not possess substantial amounts of the catalytic activity of cathepsin b, h, k or l. a variant containing substituted amino acids retains the overall spatial juxtaposition of the binding pockets and their associated key functional residues. cats mutants may also be generated by site-specific incorporation of unnatural amino acids into cats proteins using the general biosynthetic method of noren et al. (1989) science, 244: 182-188. in this method, the codon encoding the amino acid of interest in wild-type cats is replaced by a blank nonsense codon, tag, using oligonucleotide-directed mutagenesis (described in detail, infra). a suppressor trna directed against this codon is then chemically aminoacylated in vitro with the desired unnatural amino acid. the aminoacylated trna is then added to an in vitro translation system to yield a mutant cats enzyme with the site-specific incorporated unnatural amino acid. selenocysteine or selenomethionine may be incorporated into wild-type or mutant cats by expression of cats-encoding cdnas in auxotrophic e. coli strains (hendrickson et al. (1990) embo j. 9(5): 1665-1672). in this method, the wild-type or mutagenized cats cdna may be expressed in a host organism on a growth medium depleted of either natural cysteine or methionine (or both) but enriched in selenocysteine or selenomethionine (or both). the term altered surface charge means a change in one or more of the charge units of a mutant polypeptide, at physiological ph, as compared to wild-type cats. this is preferably achieved by mutation of at least one amino acid of wild-type cats to an amino acid comprising a side chain with a different charge at physiological ph than the original wild-type side chain. the change in surface charge is determined by measuring the isoelectric point (pi) of the polypeptide molecule containing the substituted amino acid and comparing it to the isoelectric point of the wild-type cats molecule. the pi of wild-type human cats is between 8.3 and 8.6 (bromme et al. (1993) j biol chem 268:4832-8). the term altered substrate specificity refers to a change in the ability of a mutant cats to cleave a substrate as compared to wild-type cats. substrate specificity may be measured using the method described by bromme et al. (1993) j biol chem 268:4832-8. the kinetic form of cats refers to the condition of the enzyme in its free or unbound form or bound to a chemical entity at either its active site or accessory binding site. a competitive inhibitor is one that inhibits cats activity by binding to the same kinetic form of cats as its substrate binds, thus directly competing with the substrate for the active site of cats. competitive inhibition can be reversed completely by increasing the substrate concentration. an uncompetitive inhibitor is one that inhibits cats by binding to a different kinetic form of the enzyme than does the substrate. such inhibitors bind to cats already bound with the substrate and not to the free enzyme. uncompetitive inhibition cannot be reversed completely by increasing the substrate concentration. a non-competitive inhibitor is one that can bind to either the free or substrate bound form of cats. those of skill in the art may identify inhibitors as competitive, uncompetitive or non-competitive, by computer fitting enzyme kinetic data using standard equations according to segel, enzyme kinetics, j. wiley & sons, (1975). it should also be understood that uncompetitive or non-competitive inhibitors according to this invention may bind to the accessory binding site. the term homologue means a protein having at least 30% amino acid sequence identity with cats or any functional domain of cats. the term co-complex means cats or a mutant or homologue of cats in covalent or non-covalent association with a chemical entity or compound. the term associating with refers to a condition of proximity between a chemical entity or compound, or portions thereof, and a cats molecule or portions thereof. the association may be non-covalent, wherein the juxtaposition is energetically favored by hydrogen bonding or van der waals or electrostatic interactions or it may be covalent. the term -sheet refers to the conformation of a polypeptide chain stretched into an extended zig-zig conformation. portions of polypeptide chains that run parallel all run in the same direction. polypeptide chains that are antiparallel run in the opposite direction from the parallel chains. a barrel refers to a sheet which has substantially or completely curled to define an internal volume. the term -helix refers to a helical, or spiral, configuration of a polypeptide chain in which successive turns of the helix are held together by hydrogen bonds between the amide (peptide) links, the carbonyl group of any given residue being hydrogen-bonded to the imino group of the third residue behind it in the chain. the term catalytic triad refers to the residues contributing to the catalytic mechanism of papain-like enzymes, typically cys25, asn184 and his168. the term active site or active site moiety refers to any or all of the following sites in cats: the substrate binding site, the catalytic triad and the site where the cleavage of a substrate occurs. the active site is typically characterized by at least amino acid residues 19, 23-26, 62-64, 67-71, 137, 138, 162, 163-165 and 211 using the sequence of the 217 amino acid mature protein (seq id nos: 2-5). the term binding pocket refers to a binding subsite, or portion of the binding site on the cats molecule. the s ₁ binding pocket of the cats active site is defined as the space typically surrounded by amino acid residue gln19, gly23 and cys25. asn 163 verges on the s ₁ , s ₁ and s ₂ binding pockets. the s ₂ binding pocket of the cats active site is typically defined as the space surrounded by amino acid residues met71, gly137, val138, val162,, gly165 and phe211. asn 163 verges on the s ₁ , s ₁ and s ₂ binding pockets. the s ₃ binding pocket of the cats active site is typically defined as the space surrounded by amino acid residues gly62, asn63, lys64, asn67, gly68 and gly69. the s ₁ binding pocket of the cats active site is typically defined as the space surrounded by amino acid residues ala140, phe 145 and trp186. asn 163 verges on the s ₁ , s ₁ and s ₂ binding pockets. the term structure coordinates refers to mathematical coordinates derived from mathematical equations related to the patterns obtained on diffraction of a monochromatic beam of x-rays by the atoms (scattering centers) of a cats molecule in crystal form. the diffraction data are used to calculate an electron density map of the repeating unit of the crystal. the electron density maps are used to establish the positions of the individual atoms within the unit cell of the crystal. the term heavy atom derivatization refers to the method of producing a chemically modified form of a crystal of cats. in practice, a crystal is soaked in a solution containing heavy metal atom salts, or organometallic compounds, e.g., lead chloride, gold thiomalate, thimerosal or uranyl acetate, which can diffuse through the crystal and bind to the surface of the protein. the location(s) of the bound heavy metal atom(s) can be determined by x-ray diffraction analysis of the soaked crystal. this information, in turn, is used to generate the phase information used to construct three-dimensional structure of the enzyme. blundel, t. l. and n. l. johnson, protein crystallography, academic press (1976). those of skill in the art understand that a set of structure coordinates determined by x-ray crystallography is not without standard error. for the purpose of this invention, any set of structure coordinates for cats or cats homologues or cats mutants that have a root mean square deviation of protein backbone atoms (n, c, c and 0) of less than 1.5 when superimposed, using backbone atoms, on the structure coordinates listed in table 3 shall be considered identical. the term unit cell refers to a basic parallelipiped shaped block. the entire volume of a crystal may be constructed by regular assembly of such blocks. each unit cell comprises a complete representation of the unit of pattern, the repetition of which builds up the crystal. the term space group refers to the arrangement of symmetry elements of a crystal. the term molecular replacement refers to a method that involves generating a-preliminary model of an cats crystal whose structure coordinates are unknown, by orienting and positioning a molecule whose structure coordinates are known (e.g., cats coordinates from table 3) within the unit cell of the unknown crystal so as best to account for the observed diffraction pattern of the unknown crystal. phases can then be calculated from this model and combined with the observed amplitudes to give an approximate fourier synthesis of the structure whose coordinates are unknown. this, in turn, can be subject to any of the several forms of refinement to provide a final, accurate structure of the unknown crystal. lattman, e., use of the rotation and translation functions, in methods in enzymology, 115, pp. 55-77 (1985); m. g. rossmann, ed., the molecular replacement method, int. sci. rev. ser., no. 13, gordon & breach, new york, (1972). using the structure coordinates of cats provided by this invention, molecular replacement may be used to determine the structure coordinates of a crystalline mutant or homologue of cats or of a different crystal form of cats. the term peptidomimetic inhibitors refers to an inhibitor, typically a compound resembling the peptide substrate of the cats enzyme, but derivatized by replacement of side chains, c-terminus, n-terminus or peptide bonds, to enhance binding within the active site. detailed description of the invention the present invention relates to crystalline cathepsin s enzyme (cats), the structure of cats as determined by x-ray crystallography, the use of that structure to solve the structure of cats homologues and of other crystal forms of cats, mutants and co-complexes of cats and the use of the cats structure and that of its homologues, mutants and co-complexes to design inhibitors of cats. a. the structure of cats the present invention provides, for the first time, crystals of a human cats mutant as well as the structure of cats as determined therefrom. the sequence of the mature wild-type cats enzyme (seq id no: 5) was altered by replacing cys25 with ser to generate the mutant (seq id no: 4). the crystals generated from the mutant have a rod shape and belong to the trigonal space group p3 ₁ 21 with ab80.0 , c61.5 . assuming one protein molecule in the asymmetric unit, the matthews coefficient (matthews (1968) j. mol. biol. 33(2):491-7) is 2.3 ³ /da, corresponding to a solvent content of 46%. data statistics are given in table 1. there is one protein molecule per asymmetric unit. the structure of cats is very similar to that of the plant protein papain and the c trace for the mutant and those for the papain superfamily are likewise similar (see fig. 1 ). a stereo picture of c-c trace of cathepsin s appears in fig. 2 . cathepsin s forms a monomeric structure consisting of two domains. the left domain contains three helices and a hydrophobic core, whereas the right domain consists of a series of antiparallel -sheets and two -helices ( fig. 3 ). three disulphides, two in the left and one in the right domain, play a role in maintaining the overall structure of the protein. the relative position of the two domains is stabilized by numerous hydrogen bonds between the mainly polar residues lining the two walls of the cleft. in addition, the n-terminus from the left domain crosses over to the right domain and the c-terminus of the right domain in turn crosses over to the left domain, thereby anchoring the two domains. the interface between the two domains forms a deep cleft containing the catalytic triad. the catalytic histidine 164 and the stabilizing asparagine 184 residue of the triad, are part of the polar surface formed by the wall of the right domain, with the left domain contributing the mutated serine 25 at the n-terminus of the main helix in this domain. in the active site a number of well-defined water molecules were identified, which are involved in an intricate hydrogen bonding network ( fig. 4 ). the mutated ser 25 residue hydrogen bonds to the backbone amide nitrogen of the catalytic histidine residue and to a water molecule which in turn forms hydrogen bonds to the side chain nitrogen of gln19 and a second water molecule. this second water molecule hydrogen bonds to one of the side chain nitrogens of the catalytic histidine and to a third water molecule forming hydrogen bonds to the second water and the side chain of trp186, which closes the network back to the side chain oxygen of gln19. it is this gln19 which forms part of the oxyanion hole, a structural feature believed to stabilize the tetrahedral intermediate in the reaction pathway. the hydrogen bond between the catalytic histidine and the asn 184 is 2.7 , in accordance with the distance observed in other catalytic triads. in a number of uncomplexed structures of serine proteases this hydrogen bond was thought not to be present (matthews et al. (1977) j biol chem 252(24): 8875-83). more recent evidence suggests there may be a weak hydrogen bond (tsukada & blow (1985) j mol biol 184(4): 703-11) as present in this mutant structure. the observed network may provide a mechanism for correct orientation of the catalytic residue side chains prior to substrate hydrolysis. as the two main catalytic residues are part of opposing walls of the catalytic cleft, it is very likely that relative movement of the walls modulates the interaction between the cysteine and histidine moieties in the active enzyme, thus playing a role in the catalytic mechanism. the position of the inactive mutant cathepsin s catalytic triad side chains superimposes with the catalytic triad of the active cathepsin k cysteine residue (compared to the oxygen in the cathepsin s cys25ser serine hydroxyl) that imparts proteolytic activity in the observed structural context ( fig. 5 ). the pk ₐ of the active site cysteine in papain-like proteinases has been measured at 4.5 (rullmann et al. (1989) j mol biol 206(1): 101-18) which is far lower than that expected for serine in the equivalent position. this allows a proton to be pulled from the cysteine sulphidyl by the asn polarized active site his, whereas a catalytic triad aspartic acid residue is required for the histidine polarization necessary for proton abstraction from a serine residue (tsukada and blow (1985) j mol biol 184(4): 703-11). the substrate binding site, formed between the two domains, extends on either side of the catalytic residues, with three binding pockets s3, s2 and s 1 for substrate residues on the amino-terminal side of the scissile bond (schechter & berger (1967) biochem biophys res commun 27(2): 157-62) and a clear binding pocket s ₁ and an extended area s ₂ at the substrate carboxyterminal side ( fig. 6 ). the previously described cathepsin s structure gave a general description of the peptide-binding cleft, but did not show the cathepsin s-specific loop containing residues 58-61. this region of the enzyme can clearly be seen shaping the back of the s3 pocket and has important implications for the design of selective inhibitors. for example, unlike the open cleft s3 binding region found in cathepsin k (bossard et al. (1999) biochemistry 38(48): 15983-902); marquis et al. (2001) j med chem 44(9): 1380-1395); marquis et al. (2001) j med chem 44(5): 725-36), cathepsin s has a small pocket which could be exploited for selectivity in drug design, for instance by the use of a small cyclic capping group at the n-terminus of a peptidomimetic inhibitor, such as those elaborated in wo00/69855. the s3 pocket lined by the residues gly68, gly69 at the base with phe70, gly62, asn63 and lys64 forming the sides and rear of the binding region ( fig. 7 ). the relatively large open s2 pocket of cathepsin s, which also contributes to enzyme substrate selectivity, has been extensively studied (bromme et al. (1994) j biol chem 269(48): 30238-42; bromme et al. (1996) biochem j 315(pt 1): 85-9; mcgrath et al. (1998) protein sci 7(6) 1294-302) and is composed of residues met71, gly 137, val138, val162, gly165 and phe211. this region has been shown to prefer branched hydrophobic side chains with gly133 appearing to provide more space relative to the alanine residue found in the equivalent position in cathepsin k and l ( fig. 7 ). b. uses of the structure coordinates of cats the present invention permits the use of molecular design techniques to design, select and synthesize chemical entities and compounds, including inhibitory compounds, capable of binding to the active site or accessory binding site of cats, in whole or in part. one approach enabled by this invention, is to use the structure coordinates of cats to design compounds that bind to the enzyme and alter the physical properties of the compounds in different ways, e.g., solubility. for example, this invention enables the design of compounds that act as competitive inhibitors of the cats enzyme by binding to all or a portion of the active site of cats. this invention also enables the design of compounds that act as uncompetitive inhibitors of the cats enzyme. these inhibitors may bind to all or a portion of the accessory binding site of a cats already bound to its substrate and may be more potent and less non-specific than known competitive inhibitors that compete only for the cats active site. similarly, non-competitive inhibitors that bind to and inhibit cats whether or not it is bound to another chemical entity may be designed using the structure coordinates of cats of this invention. a second design approach is to probe a cats crystal with molecules composed of a variety of different chemical entities to determine optimal sites for interaction between candidate cats inhibitors and the enzyme. for example, high resolution x-ray diffraction data collected from crystals saturated with solvent allows the determination of where each type of solvent molecule sticks. small molecules that bind tightly to those sites can then be designed and synthesized and tested for their cats inhibitor activity (travis (1993) science 262: 1374). this invention also enables the development of compounds that can isomerize to short-lived reaction intermediates in the chemical reaction of a substrate or other compound that binds to cats, with cats. thus, the time-dependent analysis of structural changes in cats during its interaction with other molecules is enabled. the reaction intermediates of cats can also be deduced from the reaction product in co-complex with cats. such information is useful to design improved analogues of known cats inhibitors or to design novel classes of inhibitors based on the reaction intermediates of the cats enzyme and cats-inhibitor co-complex. this provides a novel route for designing cats inhibitors with both high specificity and stability. another approach made possible and enabled by this invention, is to screen computationally small molecule databases for chemical entities or compounds that can bind in whole, or in part, to the cats enzyme. in this screening, the quality of fit of such entities or compounds to the binding site may be judged either by shape complementarity or by estimated interaction energy. meng et al. (1992) j. comp. chem. 13: 505-524). because cats may crystallize in more than one crystal form, the structure coordinates of cats, or portions thereof, as provided by this invention are particularly useful to solve the structure of those other crystal forms of cats. they may also be used to solve the structure of cats mutants, cays co-complexes, or of the crystalline form of any other protein with significant amino acid sequence homology to any functional domain of cats. one method that may be employed for this purpose is molecular replacement. in this method, the unknown crystal structure, whether it is another crystal form of cats, a cats mutant, or a cats co-complex, or the crystal of some other protein with significant amino acid sequence homology to any functional domain of cats, may be determined using the cats structure coordinates of this invention as provided in table 3. this method will provide an accurate structural form for the unknown crystal more quickly and efficiently than attempting to determine such information ab initio. in addition, in accordance with this invention, cats mutants may be crystallized in co-complex with known cats inhibitors, the crystal structures of a series of such complexes may then be solved by molecular replacement and compared with that of wild-type cats. potential sites for modification within the various binding sites of the enzyme may thus be identified. this information provides an additional tool for determining the most efficient binding interactions, for example, increased hydrophobic interactions, between cats and a chemical entity or compound. all of the complexes referred to above may be studied using well-known x-ray diffraction techniques and may be refined versus 2-3 resolution x-ray data to an r value of about 0.20 or less using computer software, such as x-plor (yale university, copyright 1992, distributed by molecular simulations, inc.). see, e.g., blundel & johnson, supra; methods in enzymology, vol. 114 & 115, h. w. wyckoff et al., eds., academic press (1985). this information may thus be used to optimize known classes of cats inhibitors, and more importantly, to design and synthesize novel classes of cats inhibitors. the structure coordinates of cats mutant provided in this invention also facilitates the identification of related proteins or enzymes analogous to cats in function, structure or both, thereby further leading to novel therapeutic modes for treating or preventing autoimmune diseases. the design of compounds that bind to or inhibit cats according to this invention generally involves consideration of two factors. first, the compound must be capable of physically and structurally associating with cats. non-covalent molecular interactions important in the association of cats with its substrate include hydrogen bonding, van der waals and hydrophobic interactions. second, the compound must be able to assume a conformation that allows it to associate with cats. although certain portions of the compound will not directly participate in this association with cats, those portions may still influence the overall conformation of the molecule. this, in turn, may have a significant impact on potency. such conformational requirements include the overall three-dimensional structure and orientation of the chemical entity or compound in relation to all or a portion of the binding site, e.g., active site or accessory binding site of cats, or the spacing between functional groups of a compound comprising several chemical entities that directly interact with cats. the potential inhibitory or binding effect of a chemical compound on cats may be analyzed prior to its actual synthesis and testing by the use of computer modeling techniques. if the theoretical structure of the given compound suggests insufficient interaction and association between it and cats, synthesis and testing of the compound is obviated. however, if computer modeling indicates a strong interaction, the molecule may then be synthesized and tested for its ability to bind to cats and inhibit by using the assay of bromme et al., supra. in this manner, synthesis of inoperative compounds may be avoided. for example, the amino acids used to define the binding pockets are in effect critical to the design of an inhibitor which is selective for cathepsin s and yet substantially unreactive to other enzymes of the papain superfamily. consequently, computer modeling can predict tight interactions between the putative inhibitor and the pocket residues that do not intrude into their respective volumes. an inhibitory or other binding compound of cats may be computationally evaluated and designed by means of a series of steps in which chemical entities or fragments are screened and selected for their ability to associate with the individual binding pockets or other areas of cats. one skilled in the art may use one of several methods to screen chemical entities or fragments for their ability to associate with cats and more particularly with the individual binding pockets of the cats active site or accessory binding site. this process may begin by visual inspection of, for example, the active site on the computer screen based on the cats coordinates in table 3. selected fragments or chemical entities may then be positioned in a variety of orientations, or docked, within an individual binding pocket of cats as defined supra. docking may be accomplished using software such as quanta and sybyl, followed by energy minimization and molecular dynamics with standard molecular mechanics forcefields, such as charmm and amber. for example, the molecular similarity application permits comparisons between different structures, different conformations of the same structure, and different parts of the same structure. the procedure used in molecular similarity to compare structures is divided into four: 1) load the structures to be compared; 2) define the atom equivalences in these structures; 3) perform a fitting operation; and 4) analyze the results. each structure is identified by a name. one structure is identified as the target (i.e., the fixed structure); all remaining structures are working structures (i.e., moving structures). since atom equivalency within quanta is defined by user input, for the purpose of this invention we will define equivalent atoms as protein backbone atoms (n, ca, c and o) for all conserved residues between the two structures being compared. we will also consider only rigid fitting operations. when a rigid fitting method is used, the working structure is translated and rotated to obtain an optimum fit with the target structure. the fitting operation uses an algorithm that computes the optimum translation and rotation to be applied to the moving structure, such that the root mean square difference of the fit over the specified pairs of equivalent atom is an absolute minimum. this number, given in angstroms, is reported by quanta. for the purpose of this invention, any molecule or molecular complex or binding pocket thereof that has a root mean square deviation of conserved residue backbone atoms (n, ca, c, o) of less than 1.5 , preferably between 1.5 and 0.3 , more preferably between 1.0 and 0.3 , even more preferably between 0.8, 0.75, 0.6 and 0.5, and 0.3 when superimposed on the relevant backbone atoms described by structure coordinates listed in table 3 are considered identical. most preferably, the root mean square deviation is between 0.45, 0.4 or 0.35 and 0.3 . therefore, according to one embodiment, the present invention provides a molecule or molecular complex comprising all or any parts of the binding pocket defined by structure coordinates of cats amino acids, i.e., amino acids 19, 23-26, 62-64, 67, 68, 69, 70, 71, 137, 138, 162, 163, 164, 165, 186 and/or 211 according to table 3, or a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 . more preferred are molecules or molecular complexes that are defined by the entire set of structure coordinates in table 3 / a root mean square deviation from the conserved backbone atoms of those amino acids of not more than 1.5 . in order to use the structure coordinates generated for the cats enzyme, one of its binding pockets or homologues thereof, it is sometimes necessary to convert them into a three-dimensional shape. this may be achieved through the use of commercially available software that is capable of generating three-dimensional graphical representations of molecules or portions thereof from a set of structure coordinates. therefore, according to another embodiment, the present invention provides an apparatus and a method for generating and displaying a graphical three-dimensional representation of a molecule or molecular complex comprising all or any parts of a binding pocket defined by structure coordinates of cats amino acids, i.e., amino acids 19, 23-26, 62-64, 67, 68, 69, 70, 71, 137, 138, 162, 163, 164, 165, 186 and/or 211 according to table 3, or a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 . according to another embodiment, the present invention provides a machine-readable data storage medium, comprising a data storage material encoded with machine readable instructions which are executable by a machine to generate and display a graphical three-dimensional representation of a molecule or molecular complex comprising all or any parts of a binding pocket defined by structure coordinates of cats amino acids, i.e., amino acids 19, 23-26, 62-64, 67, 68, 69, 70, 71, 137, 138, 162, 163, 164, 165, 186 and/or 211 according to table 3, or a homologue of said molecule or molecular complex, wherein said homologue comprises a binding pocket that has a root mean square deviation from the backbone atoms of said amino acids of not more than 1.5 . even more preferred is a machine-readable data storage medium that stores encoded machine readable instructions that are executable by a machine to generate and display a graphical three-dimensional representation of a molecule or molecular complex that is defined by the structure coordinates of all of the amino acids in table 3 / a root mean square deviation from the backbone atoms of those amino acids of not more than 1.5 . according to an alternate embodiment, the machine-readable data storage medium comprises a data storage material encoded with a first set of machine readable data which comprises the fourier transform of the structure coordinates set forth in table 3, and which, when accessed by a machine programmed with instructions for using said data, can be combined with a second set of machine readable data comprising the x-ray diffraction pattern of a molecule or molecular complex to determine at least a portion of the structure coordinates corresponding to the second set of machine readable data. fig. 8 demonstrates one version of these embodiments. system 10 includes a computer 11 comprising a central processing unit (cpu) 20 , a working memory 22 which may be, e.g, ram (random-access memory) or core memory, mass storage memory 24 (such as one or more disk drives or cd-rom drives), one or more cathode-ray tube (crt) display terminals 26 , one or more keyboards 28 , one or more input lines 30 , and one or more output lines 40 , all of which are interconnected by a conventional bidirectional system bus 50 . input hardware 36 , coupled to computer 11 by input lines 30 , may be implemented in a variety of ways. machine-readable data of this invention may be inputted via the use of a modem or modems 32 connected by a telephone line or dedicated data line 34 . alternatively or additionally, the input hardware 36 may comprise cd-rom drives or disk drives 24 . in conjunction with display terminal 26 , keyboard 28 may also be used as an input device. output hardware 46 , coupled to computer 11 by output lines 40 , may similarly be implemented by conventional devices. by way of example, output hardware 46 may include crt display terminal 26 for displaying a graphical representation of a binding pocket of this invention using a program such as quanta as described herein. output hardware might also include a printer 42 , so that hard copy output may be produced, or a disk drive 24 , to store system output for later use. in operation, cpu 20 coordinates the use of the various input and output devices 36 , 46 , coordinates data accesses from mass storage 24 and accesses to and from working memory 22 , and determines the sequence of data processing steps. a number of programs may be used to process the machine-readable data of this invention. such programs are discussed in reference to the computational methods of drug discovery as described herein. specific references to components of the hardware system 10 are included as appropriate throughout the following description of the data storage medium. fig. 9 shows a cross section of a magnetic data storage medium 100 which can be encoded with a machine-readable data that can be carried out by a system such as system 10 of fig. 8 . medium 100 can be a conventional floppy diskette or hard disk, having a suitable substrate 101 , which may be conventional, and a suitable coating 102 , which may be conventional, on one or both sides, containing magnetic domains (not visible) whose polarity or orientation can be altered magnetically. medium 100 may also have an opening (not shown) for receiving the spindle of a disk drive or other data storage device 24 . the magnetic domains of coating 102 of medium 100 are polarized or oriented so as to encode in manner which may be conventional, machine readable data such as that described herein, for execution by a system such as system 10 of fig. 8 . fig. 10 shows a cross section of an optically-readable data storage medium 110 which also can be encoded with such a machine-readable data, or set of instructions, which can be carried out by a system such as system 10 of fig. 9 . medium 110 can be a conventional compact disk read only memory (cd-rom) or a rewritable medium such as a magneto-optical disk which is optically readable and magneto-optically writable. medium 100 preferably has a suitable substrate 111 , which may be conventional, and a suitable coating 112 , which may be conventional, usually of one side of substrate 111 . in the case of cd-rom, as is well known, coating 112 is reflective and is impressed with a plurality of pits 113 to encode the machine-readable data. the arrangement of pits is read by reflecting laser light off the surface of coating 112 . a protective coating 114 , which preferably is substantially transparent, is provided on top of coating 112 . in the case of a magneto-optical disk, as is well known, coating 112 has no pits 113 , but has a plurality of magnetic domains whose polarity or orientation can be changed magnetically when heated above a certain temperature, as by a laser (not shown). the orientation of the domains can be read by measuring the polarization of laser light reflected from coating 112 . the arrangement of the domains encodes the data as described above. thus, in accordance an embodiment of the present invention, data capable of displaying the three dimensional structure of cats and portions thereof and their structurally similar homologues is stored in a machine-readable storage medium, which also stores instructions for using such data that are executable by a machine to display a graphical three-dimensional representation of the structure. such data may be used for a variety of purposes, such as drug discovery. for example, the structure encoded by the data may be computationally evaluated for its ability to associate with chemical entities. chemical entities that associate with cats may inhibit cats, and are potential drug candidates. alternatively, the structure encoded by the data may be displayed in a graphical three-dimensional representation on a computer screen. this allows visual inspection of the structure, as well as visual inspection of the structure's association with chemical entities. thus, according to another embodiment, the invention relates to a method for evaluating the potential of a chemical entity to associate with any of the molecules or molecular complexes set forth above. this method comprises the steps of: a) employing computational means to perform a fitting operation between the chemical entity and a binding pocket of the molecule or molecular complex; and b) analyzing the results of said fitting operation to quantify the association between the chemical entity and the binding pocket. the term chemical entity, as used herein, refers to chemical compounds, complexes of at least two chemical compounds, and fragments of such compounds or complexes. for the first time, the present invention permits the use of molecular design techniques to identify, select and design chemical entities, including inhibitory compounds, capable of binding to cats-like binding pockets. applicants' elucidation of the binding sites on cats provides the necessary information for designing new chemical entities and compounds that may interact with at least one cats-like binding pockets, in whole or in part. this elucidation also enables the evaluation of structure-activity data for analogs of mpa or other compounds which bind to cats-like binding pockets. throughout this section, discussions about the ability of an entity to bind to, associate with or inhibit a cats-like binding pocket refers to features of the entity alone. assays to determine if a compound binds to cats are disclosed in eurj 1997250:745-750, wo00/69855, wo01/9808, wo0119796, and wo0109160 and other patent specifications relating to cathepsin s inhibitors the design of compounds that bind to or inhibit cats-like binding pockets according to this invention generally involves consideration of two factors. first, the entity must be capable of physically and structurally associating with parts or all of the cats-like binding pockets. non-covalent molecular interactions important in this association include hydrogen bonding, van der waals interactions, hydrophobic interactions and electrostatic interactions. second, the entity must be able to assume a conformation that allows it to associate with the cats-like binding pocket directly. although certain portions of the entity will not directly participate in these associations, those portions of the entity may still influence the overall conformation of the molecule. this, in turn, may have a significant impact on potency. such conformational requirements include the overall three-dimensional structure and orientation of the chemical entity in relation to all or a portion of the binding pocket, or the spacing between functional groups of an entity comprising several chemical entities that directly interact with the cats-like binding pocket or homologues thereof. the potential inhibitory or binding effect of a chemical entity on a cats-like binding pocket may be analyzed prior to its actual synthesis and testing by the use of computer modeling techniques. if the theoretical structure of the given entity suggests insufficient interaction and association between it and the cats-like binding pocket, testing of the entity is obviated. however, if computer modeling indicates a strong interaction, the molecule may then be synthesized and tested for its ability to bind to a cats-like binding pocket. this may be achieved by testing the ability of the molecule to inhibit cats using the assays described in the examples. in this manner, synthesis of inoperative compounds may be avoided. a potential inhibitor of a cats-like binding pocket may be computationally evaluated by means of a series of steps in which chemical entities or fragments are screened and selected for their ability to associate with the cats binding pockets. one skilled in the art may use one of several methods to screen chemical entities or fragments for their ability to associate with a cats-like binding pocket. this process may begin by visual inspection of, for example, a cats-like binding pocket on the computer screen based on the cats structure coordinates in table 3 or other coordinates which define a similar shape generated from the machine-readable storage medium. selected fragments or chemical entities may then be positioned in a variety of orientations, or docked, within that binding pocket as defined supra. docking may be accomplished using software such as quanta and sybyl, followed by energy minimization and molecular dynamics with standard molecular mechanics force fields, such as charmm and amber. specialized computer programs may also assist in the process of selecting fragments or chemical entities. these include: 1. grid (goodford (1985)a computational procedure for determining energetically favorable binding sites on biologically important macromolecules, j. med. chem 28: 849-857). grid is available from oxford university, oxford, uk. 2. mcss (miranker and karplus (1991) functionality maps of binding sites: a multiple copy simultaneous search method. proteins: structure. function and genetics, 11, pp. 29-34). mcss is available from molecular simulations, burlington, mass. 3. autodock (goodsell and olsen (1990) automated docking of substrates to proteins by simulated annealing, proteins: structure. function, and genetics, 8, pp. 195-202). autodock is available from scripps research institute, la jolla, calif. 4. dock (kuntz et al. (1982) a geometric approach to macromolecule-ligand interactions, j. mol. biol. 161: 269-288). dock is available from university of california, san francisco, calif. once suitable chemical entities or fragments have been selected, they can be assembled into a single compound or inhibitor. assembly may be proceed by visual inspection of the relationship of the fragments to each other on the three-dimensional image displayed on a computer screen in relation to the structure coordinates of cats. this would be followed by manual model building using software such as quanta or sybyl. once suitable chemical entities or fragments have been selected, they can be assembled into a single compound or complex. assembly may be preceded by visual inspection of the relationship of the fragments to each other on the three-dimensional image displayed on a computer screen in relation to the structure coordinates of cats. this would be followed by manual model building using software such as quanta or sybyl tripos associates, st. louis, mo.. useful programs to aid one of skill in the art in connecting the individual chemical entities or fragments include: 1. caveat (bartlett et al. (1989) caveat: a program to facilitate the structure-dervived design of biologically active molecules. in molecular recognition in chemical and biological problems, special pub., royal chem. soc. 78: 182-196). caveat is available from the university of california, berkeley, calif. 2. 3d database systems such as maccs-3d and isis (mdl information systems, san leandro, calif.). this area is reviewed in martin (1992) 3d database searching in drug design, j. med. chem. 35: 2145-2154). 3. hook (available from molecular simulations, burlington, mass.). 4. sprout (v. gillet et al. (1993) sprout: a program for structure generation, j. comput. aided mol. design, 7: 127-153.). sprout is available from the university of leeds, uk. instead of proceeding to build a cats inhibitor in a step-wise fashion one fragment or chemical entity at a time as described above, inhibitory or other cats binding compounds may be designed as a whole or de novo using either an empty active site or optionally including some portion(s) of a known inhibitor(s). these methods include: 1. ludi (bohm (1992) the computer program ludi: a new method for the de novo design of enzyme inhibitors, j. comp. aid. molec. design 6: 61-78). ludi is available from biosym technologies, san diego, calif. 2. legend (nishibata and itai (1991) tetrahedron 47: 8985). legend is available from molecular simulations, burlington, mass. 3. leapfrog (available from tripos associates, st. louis, mo.). other molecular modeling techniques may also be employed in accordance with this invention. see, e.g., cohen, n. c. et al., molecular modeling software and methods for medicinal chemistry, j. med. chem., 33, pp. 883-894 (1990). see also, navia and murcko, (1992)the use of structural information in drug design, current opinions in structural biology 2: 202-210. once a compound has been designed or selected by the above methods, the efficiency with which that compound may bind to cats may be tested and optimized by computational evaluation. for example, a compound that has been designed or selected to function as an cats-inhibitor must also preferably traverse a volume not overlapping that occupied by the active site when it is bound to the native substrate. an effective cats inhibitor must preferably demonstrate a relatively small difference in energy between its bound and free states (i.e., a small deformation energy of binding). thus, the most efficient cats inhibitors should preferably be designed with a deformation energy of binding of not greater than about 10 kcal/mole, preferably, not greater than 7 kcal/mole. cats inhibitors may interact with the enzyme in more than one conformation that is similar in overall binding energy. in those cases, the deformation energy of binding is taken to be the difference between the energy of the free compound and the average energy of the conformations observed when the inhibitor binds to the enzyme. a compound designed or selected as binding to cats may be further computationally optimized so that in its bound state it would preferably lack repulsive electrostatic interaction with the target enzyme. such non-complementary (e.g., electrostatic) interactions include repulsive charge-charge, dipole-dipole and charge-dipole interactions. specifically, the sum of all electrostatic interactions between the inhibitor and the enzyme when the inhibitor is bound to cats, preferably make a neutral or favorable contribution to the enthalpy of binding. specific computer software is available in the art to evaluate compound deformation energy and electrostatic interaction. examples of programs designed for such uses include: gaussian 92, revision cm. j. frisch, gaussian, inc., pittsburgh, pa. 1992; amber, version 4.0p. a. kollman, university of california at san francisco, 1994; quanta/charmmmolecular simulations, inc., burlington, mass. 1994; and insight ii/discover (biosysm technologies inc., san diego, calif. 1994). these programs may be implemented, for instance, using a silicon graphics workstation, iris 4d/35 or ibm risc/6000 workstation model 550. other hardware systems and software packages will be known to those skilled in the art. once a cats-binding compound has been optimally selected or designed, as described above, substitutions may then be made in some of its atoms or side groups in order to improve or modify its binding properties. generally, initial substitutions are conservative, i.e., the replacement group will have approximately the same size, shape, hydrophobicity and charge as the original group. it should, of course, be understood that components known in the art to alter conformation should be avoided. such substituted chemical compounds may then be analyzed for efficiency of fit to cats by the same computer methods described in detail, above. another approach enabled by this invention, is the computational screening of small molecule databases for chemical entities or compounds that can bind in whole, or in part, to a cats binding pocket. in this screening, the quality of fit of such entities to the binding site may be judged either by shape complementarity or by estimated interaction energy (e. c. meng et al. (1992) j. comp. chem. 13: 505-524). thus, enabled by this invention are compounds that inhibit cats by associating directly with the cat binding site. the term immunosuppressant refers to a compound or drug that possesses immune response inhibitory activity. examples of such agents include cyclosporin a, fk506, rapamycin, leflunomide, deoxyspergualin, prednisone, azathioprine, mycophenolate mofetil, okt3, atag and mizoribine. cats-mediated disease refers to any disease state in which the cats enzyme plays a regulatory role in the metabolic pathway of that disease. examples of cats-mediated disease include rheumatoid arthritis, asthma, atherosclerosis, copd and multiple sclerosis. see also wo97/40066 relating to the identification of the role of cathepsin s in mhc processing. the invention allows the identification and characterization of cats inhibitors, which will typically comprise a cats inhibitor as identified and characterized herein or a pharmaceutically acceptable salt thereof; and a pharmaceutically acceptable carrier, adjuvant or vehicle. such composition may optionally comprise an additional agent selected from an immunosuppressant, an anti-cancer agent, an anti-viral agent, or an anti-vascular hyperproliferation compound. c. mutants of cats the present invention also enables mutants of cats and the solving of their crystal structure. more particularly, by virtue of the present invention, the location of the active site, accessory binding site and interface of cats based on its crystal structure permits the identification of desirable sites for mutation. for example, mutation may be directed to a particular site or combination of sites of wild-type cats, i.e., the accessory binding site or only the active site, or a location on the interface site may be chosen for mutagenesis. similarly, only a location on, at or near the enzyme surface may be replaced, resulting in an altered surface charge of one or more charge units, as compared to the wild-type enzyme. alternatively, an amino acid residue in cats may be chosen for replacement based on its hydrophilic or hydrophobic characteristics. such mutants may be characterized by any one of several different properties as compared with wild-type cats. for example, such mutants may have altered surface charge of one or more charge units, or have an increased stability to subunit dissociation. or such mutants may have an altered substrate specificity in comparison with, or a higher specific activity than, wild-type ice. the mutants of cats prepared by this invention may be prepared in a number of ways. for example, the wild-type sequence of cats may be mutated in those sites identified using this invention as desirable for mutation, by means of oligonucleotide-directed mutagenesis or other conventional methods, e.g. deletion. alternatively, mutants of cats may be generated by the site specific replacement of a particular amino acid with an unnaturally occurring amino acid. in addition, cats mutants may be generated through replacement of an amino acid residue, or a particular cysteine or methionine residue, with selenocysteine or selenomethionine. this may be achieved by growing a host organism capable of expressing either the wild-type or mutant polypeptide on a growth medium depleted of either natural cysteine or methionine (or both) but enriched in selenocysteine or selenomethionine (or both). mutations may be introduced into a dna sequence coding for cats using synthetic oligonucleotides. these oligonucleotides contain nucleotide sequences flanking the desired mutation sites. mutations may be generated in the full-length dna sequence of cats (seq id: 1). according to this invention, a mutated cats dna sequence produced by the methods described above, or any alternative methods known in the art, can be expressed using an expression vector. an expression vector, as is well known in the art, typically includes elements that permit autonomous replication in a host cell independent of the host genome, and one or more phenotypic markers for selection purposes. either prior to or after insertion of the dna sequences surrounding the desired cats mutant coding sequence, an expression vector also will include control sequences encoding a promoter, operator, ribosome binding site, translation initiation signal, and, optionally, a repressor gene or various activator genes and a signal for termination. in some embodiments, where secretion of the produced mutant is desired, nucleotides encoding a signal sequence may be inserted prior to the cats mutant coding sequence. for expression under the direction of the control sequences, a desired dna sequence must be operatively linked to the control sequences. that is, they must have an appropriate start signal in front of the dna sequence encoding the cats mutant and must maintain the correct reading frame to permit expression of that sequence under the control of the control sequences and production of the desired product encoded by that cats sequence. any of a wide variety of well known available expression vectors are useful to express the mutated cats coding sequences of this invention. these include, for example, vectors consisting of segments of chromosomal, non-chromosomal and synthetic dna sequences, such as various known derivatives of sv40, known bacterial plasmids, e.g., plasmids from e. coli including col e1, pcr1, pbr322, pmb9 and their derivatives, wider host range plasmids, e.g., rp4, phage dnas, e.g., the numerous derivatives of phage lambda, e.g., nm 989, and other dna phages, e.g., m13 and filamentous single stranded dna phages, yeast plasmids such as the 2 82 plasmid or derivatives thereof, and vectors derived from combinations of plasmids and phage dnas, such as plasmids which have been modified to employ phage dna or other expression control sequences. in the preferred embodiments of this invention, we employ baculovirus vectors in sf9 insect cells. in addition, any of a wide variety of expression control sequences (i.e. sequences that control the expression of a dna sequence when operatively linked to it) may be used in these vectors to express the mutated dna sequences according to this invention. such useful expression control sequences, include, for example, the early and late promoters of sv40 for animal cells, the lac system, the trp system the tac or trc system, the major operator and promoter regions of phage lambda the control regions of fd coat protein, all for e. coli , the promoter for 3-phosphoglycerate kinase or other glycolytic enzymes, the promoters of acid phosphatase, e.g., pho5, the promoters of the yeast -mating factors for yeast, and, other sequences known to control the expression of genes of prokaryotic or eukaryotic cells or their viruses, and vanous combinations thereof. in the preferred embodiments of this invention, we used baculovirus vectors in sf9 insect cells. a wide variety of hosts are also useful for producing mutated cats for this invention. these hosts include, for example, bacteria, such as e. coli, bacillus and streptomyces, fungi, such as yeasts, and animal cells, such as cho and cos-1 cells, plant cells, insect cells and transgenic host cells. in preferred embodiments of this invention, the host cells are sf9 insect cells. it should be understood that not all expression vectors and expression systems function in the same way to express mutated dna sequences of this invention and to produce modified cats or cats mutants. neither do all hosts function equally well with the same expression system. however, one of skill in the art may make a selection among these vectors, expression control sequences and hosts without undue experimentation and without departing from the scope of this invention. for example, an important consideration in selecting a vector, will be the ability of the vector to replicate in a given host. the copy number of the vector, the ability to control that copy number, and the expression of any other proteins encoded by the vector, such as antibiotic markers, should also be considered. in selecting an expression control sequence, a variety of factors should also be considered. these include, for example, the relative strength of the system, its controllability, its compatibility with the dna sequence encoding the modified cats of this invention, particularly with regard to potential secondary structures. hosts should be selected by consideration of their compatibility with the chosen vector, the toxicity of the modified cats to them, their ability to secrete mature products, their ability to fold proteins correctly, their fermentation requirements, the ease of the purification of the modified cats from them and safety. within these parameters, one of skill in the art may select various vector/expression control system/host combinations that will produce useful amounts of the mutant cats. the mutant cats produced in these systems may be purified by a variety of conventional steps and strategies, including those used to purify wild-type cats. once the cats mutants have been generated in the desired location, i.e., active site or accessory binding site, the mutants may be tested for any one of several properties of interest. for example, mutants may be screened for an altered charge at physiological ph. this is determined by measuring the mutant cats isoelectric point (pi) in comparison with that of the wild-type parent. isoelectric point may be measured by gel-electrophoresis according to the method of wellner (1971) analyt. chem. 43: 597. a mutant with an altered surface charge is an cats polypeptide containing a replacement amino acid located at the surface of the enzyme, as provided by the structural information of this invention, and an altered pi. furthermore, mutants may be screened for altered specific activity in relation to the wild-type cats. a mutant would be tested for altered cats substrate specificity by measuring the hydrolysis of fluorgenic peptide substrates or unmodified cats peptide substrates such as abz-leu-thr-bal-hyp-tyr(no ₂ )-asp-nh ₂ . further properties of interest also include mutants with a broader range of ph stability. a cats mutant with a broader range of ph stability would demonstrate no loss of enzymatic activity at ph in the range of 5-7. in order that the invention described herein may be more fully understood, the following examples are set forth. it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting this invention in any manner. example 1 crystal structure of cats the cdna encoding the precursor of active human cats (shi et al. (1994) j biol chem 269(15): 11530-36) was cloned into a baculovirus expression vector and expressed in sf9 insect cells. the mutant cys25ser was expressed at levels approaching 35 mg/l as pro-enzyme with approximately half secreted and half kept inside the cells (vernet et al. (1990) j biol chem 265(27): 16661-6). crystallization was performed by the hanging-drop vapor diffusion method. equal volumes cathepsin s (cys25ser) at 7 mg/ml, including the peptide as abz-leu-thr-bal-hyp-tyr(no ₂ )-asp-nh ₂ at 1 mm and well solution were combined and placed over a well containing 20% isopropanol, 20% peg 2000 and 0.1 m sodium citrate, ph 4.13. rod-shaped crystals appeared after 10 days. those of skill in the art will appreciate that the aforesaid crystallization conditions can be varied. such variations may be used alone or in combination, and include final protein/inhibitor complex; all combinations of cats/inhibitor to precipitant ratios; citrate concentrations between 0.01 mm and 200 mm; any concentration of -mercaptoethanol; ph ranges between 4.0 and 9.5; peg concentrations between 10% and 25% (g/100 ml); peg weights between 2000 and 8000; any concentration or type of detergent; any temperature between 5 c. and 300 c. and crystallization of cats/inhibitor complexes by batch, liquid bridge, or dialysis method using these conditions or variations thereof. the cathepsin s (cys25ser) data were collected from a crystal with dimensions of 0.20.10.1 mm ³ using a mar345 imaging plate detector, mounted on a ru-h3r rigaku rotating anode x-ray generator operating at 50 kv and 100 ma, equipped with osmic multilayers. the data were processed using the programs denzo and scalepack (otwinowsi & minor, 1997). the crystals belong to the trigonal space group p3121 with ab80.0 , c61.5 . assuming one protein molecule in the asymmetric unit, the matthews coefficient is 2.3 ³ /da, corresponding to a solvent content of 46%. data statistics are given in table 1. table 1 data collection and refinement statistics space group p3 ₁ 2i resolution range () 20-2.2 outer resolution shell () 2.24-2.20 rsym (%): overall (outer shell) 7.5 (27.0) completeness (%): overall 99.4 (98.8) (outer shell) number of observations 39038 number of unique reflections 11969 cross-validation method throughout free r value test set selection random r value (working test set) 0.197 r value (working) 0.194 free r value 0.251 free r value test set size (%) 5.0 number of reflections in free 597 r value test set number of non-hydrogen atoms 1841 used in refinement model statistics rms sigma bond length () 0.013 0.021 bond angle () 1.754 1.942 torsion angles, period 1() 4.176 3.0 torsion angles, period 3() 17.488 15.0 chiral-center restraints () 0.121 0.20 plane restrain () 0.006 0.020 vdw repulsions () 0.234 0.30 hbonds () 0.141 0.50 the following tables (table 2 and 3) summarize the crystallographic coordinate transformation data and the x-ray crystallography data sets of cats derivatives that were used to determine the structure of cats according to this invention. table 2 crystallographic coordinate transformation data record alpha beta gamma space name a (angstroms) b (angstroms) c (angstroms) (degrees) (degrees) (degrees) group cryst 1 79.989 79.989 61.517 90.00 90.00 120.00 p3121 record name sn1 sn2 sn3 un scale1 0.012502 0.007218 0.000000 0.00000 scale2 0.000000 0.014436 0.000000 0.00000 scale3 0.000000 0.000000 0.016256 0.00000 table 3 atom chn res. temp atomic element description type res. i.d. x coord. y coord. z coord. occ. fact symbol atom 1 n leu a 1 10.950 18.311 9.373 1.00 37.95 7 n atom 2 ca leu a 1 11.173 17.084 8.521 1.00 37.35 6 c atom 3 c leu a 1 10.316 17.197 7.273 1.00 35.18 6 c atom 4 o leu a 1 10.782 17.443 6.142 1.00 34.02 8 o atom 5 cb leu a 1 10.949 15.891 9.439 1.00 40.82 6 c atom 6 cg leu a 1 11.373 14.476 9.009 1.00 42.31 6 c atom 7 cd1 leu a 1 11.105 13.512 10.187 1.00 43.06 6 c atom 8 cd2 leu a 1 10.488 14.042 7.823 1.00 43.00 6 c atom 9 n pro a 2 9.003 17.036 7.402 1.00 32.83 7 n atom 10 ca pro a 2 8.118 17.157 6.249 1.00 30.90 6 c atom 11 c pro a 2 8.209 18.546 5.633 1.00 30.00 6 c atom 12 o pro a 2 8.489 19.556 6.291 1.00 28.06 8 o atom 13 cb pro a 2 6.751 16.801 6.783 1.00 31.24 6 c atom 14 cg pro a 2 6.860 16.525 8.231 1.00 30.69 6 c atom 15 cd pro a 2 8.285 16.712 8.650 1.00 32.33 6 c atom 16 n asp a 3 7.968 18.698 4.330 1.00 28.88 7 n atom 17 ca asp a 3 8.043 19.999 3.683 1.00 28.98 6 c atom 18 c asp a 3 6.816 20.902 3.874 1.00 27.92 6 c atom 19 o asp a 3 6.918 22.121 3.725 1.00 26.64 8 o atom 20 cb asp a 3 8.273 19.889 2.184 1.00 29.50 6 c atom 21 cg asp a 3 9.737 19.805 1.814 1.00 31.71 6 c atom 22 od1 asp a 3 10.629 19.915 2.671 1.00 33.75 8 o atom 23 od2 asp a 3 9.927 19.611 0.597 1.00 30.01 8 o atom 24 n ser a 4 5.677 20.319 4.140 1.00 27.22 7 n atom 25 ca ser a 4 4.417 21.007 4.366 1.00 27.40 6 c atom 26 c ser a 4 3.645 20.233 5.431 1.00 25.48 6 c atom 27 o ser a 4 3.810 19.015 5.387 1.00 23.18 8 o atom 28 cb ser a 4 3.546 20.951 3.102 1.00 27.47 6 c atom 29 og ser a 4 4.117 21.709 2.054 1.00 31.75 8 o atom 30 n val a 5 2.972 20.875 6.374 1.00 25.14 7 n atom 31 ca val a 5 2.104 20.188 7.292 1.00 24.37 6 c atom 32 c val a 5 0.837 21.052 7.446 1.00 23.65 6 c atom 33 o val a 5 0.893 22.267 7.551 1.00 22.57 8 o atom 34 cb val a 5 2.546 19.847 8.713 1.00 26.17 6 c atom 35 cg1 val a 5 3.532 18.649 8.728 1.00 27.21 6 c atom 36 cg2 val a 5 3.140 21.024 9.444 1.00 26.93 6 c atom 37 n asp a 6 0.262 20.319 7.419 1.00 22.38 7 n atom 38 ca asp a 6 1.544 21.000 7.641 1.00 22.53 6 c atom 39 c asp a 6 2.250 20.091 8.639 1.00 22.05 6 c atom 40 o asp a 6 2.660 18.980 8.321 1.00 19.08 8 o atom 41 cb asp a 6 2.260 21.289 6.338 1.00 22.86 6 c atom 42 cg asp a 6 3.545 22.053 6.618 1.00 24.23 6 c atom 43 od1 asp a 6 3.824 22.335 7.803 1.00 25.03 8 o atom 44 od2 asp a 6 4.270 22.370 5.668 1.00 25.31 8 o atom 45 n trp a 7 2.383 20.593 9.874 1.00 21.56 7 n atom 46 ca trp a 7 2.985 19.811 10.953 1.00 21.32 6 c atom 47 c trp a 7 4.496 19.684 10.796 1.00 21.32 6 c atom 48 o trp a 7 5.159 18.823 11.383 1.00 20.11 8 o atom 49 cb trp a 7 2.609 20.350 12.338 1.00 20.99 6 c atom 50 cg trp a 7 1.244 19.901 12.774 1.00 22.17 6 c atom 51 cd1 trp a 7 0.078 20.606 12.748 1.00 22.04 6 c atom 52 cd2 trp a 7 0.914 18.612 13.309 1.00 23.17 6 c atom 53 ne1 trp a 7 0.955 19.850 13.229 1.00 23.04 7 n atom 54 ce2 trp a 7 0.474 18.614 13.578 1.00 23.29 6 c atom 55 ce3 trp a 7 1.651 17.456 13.582 1.00 23.22 6 c atom 56 cz2 trp a 7 1.128 17.509 14.108 1.00 22.89 6 c atom 57 cz3 trp a 7 0.997 16.359 14.117 1.00 24.30 6 c atom 58 ch2 trp a 7 0.390 16.388 14.372 1.00 23.98 6 c atom 59 n arg a 8 5.068 20.457 9.891 1.00 21.33 7 n atom 60 ca arg a 8 6.469 20.333 9.512 1.00 22.68 6 c atom 61 c arg a 8 6.623 18.974 8.822 1.00 22.92 6 c atom 62 o arg a 8 7.619 18.297 9.110 1.00 20.36 8 o atom 63 cb arg a 8 6.916 21.554 8.709 1.00 23.11 6 c atom 64 cg arg a 8 6.693 22.889 9.419 1.00 25.30 6 c atom 65 cd arg a 8 6.997 24.066 8.512 1.00 26.01 6 c atom 66 ne arg a 8 6.153 24.141 7.326 1.00 25.53 7 n atom 67 cz arg a 8 6.430 24.949 6.296 1.00 24.61 6 c atom 68 nh1 arg a 8 7.506 25.723 6.302 1.00 22.60 7 n atom 69 nh2 arg a 8 5.581 24.922 5.275 1.00 24.29 7 n atom 70 n glu a 9 5.632 18.455 8.098 1.00 22.56 7 n atom 71 ca glu a 9 5.717 17.154 7.462 1.00 23.87 6 c atom 72 c glu a 9 5.719 15.981 8.429 1.00 23.76 6 c atom 73 o glu a 9 6.292 14.947 8.065 1.00 22.03 8 o atom 74 cb glu a 9 4.619 16.995 6.375 1.00 24.23 6 c atom 75 cg glu a 9 4.869 18.024 5.288 1.00 24.59 6 c atom 76 cd glu a 9 3.798 18.357 4.279 1.00 26.81 6 c atom 77 oe1 glu a 9 2.656 17.883 4.330 1.00 25.19 8 o atom 78 oe2 glu a 9 4.135 19.162 3.356 1.00 27.08 8 o atom 79 n lys a 10 5.363 16.163 9.697 1.00 23.11 7 n atom 80 ca lys a 10 5.396 15.080 10.670 1.00 25.39 6 c atom 81 c lys a 10 6.602 15.171 11.585 1.00 24.35 6 c atom 82 o lys a 10 6.658 14.490 12.608 1.00 24.83 8 o atom 83 cb lys a 10 4.086 15.098 11.504 1.00 26.85 6 c atom 84 cg lys a 10 2.957 14.583 10.612 1.00 30.32 6 c atom 85 cd lys a 10 1.565 14.890 11.082 1.00 33.59 6 c atom 86 ce lys a 10 0.899 13.748 11.846 1.00 36.10 6 c atom 87 nz lys a 10 0.582 13.993 11.925 1.00 36.86 7 n atom 88 n gly a 11 7.533 16.056 11.251 1.00 23.07 7 n atom 89 ca gly a 11 8.729 16.279 12.072 1.00 21.28 6 c atom 90 c gly a 11 8.380 16.850 13.440 1.00 19.50 6 c atom 91 o gly a 11 9.092 16.561 14.405 1.00 19.20 8 o atom 92 n cys a 12 7.376 17.719 13.580 1.00 18.82 7 n atom 93 ca cys a 12 6.932 18.176 14.903 1.00 18.52 6 c atom 94 c cys a 12 7.216 19.640 15.189 1.00 19.49 6 c atom 95 o cys a 12 6.768 20.233 16.194 1.00 18.88 8 o atom 96 cb cys a 12 5.413 17.988 15.045 1.00 19.68 6 c atom 97 sg cys a 12 4.842 16.291 15.275 1.00 18.40 16 s atom 98 n val a 13 7.941 20.266 14.262 1.00 18.11 7 n atom 99 ca val a 13 8.236 21.686 14.335 1.00 17.21 6 c atom 100 c val a 13 9.731 21.962 14.253 1.00 17.55 6 c atom 101 o val a 13 10.368 21.639 13.235 1.00 16.08 8 o atom 102 cb val a 13 7.498 22.432 13.214 1.00 17.46 6 c atom 103 cg1 val a 13 7.651 23.946 13.381 1.00 16.11 6 c atom 104 cg2 val a 13 5.998 22.115 13.152 1.00 16.93 6 c atom 105 n thr a 14 10.290 22.532 15.313 1.00 17.07 7 n atom 106 ca thr a 14 11.723 22.850 15.310 1.00 18.75 6 c atom 107 c thr a 14 11.977 24.057 14.402 1.00 19.10 6 c atom 108 o thr a 14 11.062 24.722 13.918 1.00 17.60 8 o atom 109 cb thr a 14 12.269 23.193 16.704 1.00 18.82 6 c atom 110 og1 thr a 14 11.602 24.365 17.218 1.00 18.72 8 o atom 111 cg2 thr a 14 12.008 22.047 17.691 1.00 19.27 6 c atom 112 n glu a 15 13.250 24.348 14.169 1.00 20.16 7 n atom 113 ca glu a 15 13.625 25.497 13.371 1.00 22.18 6 c atom 114 c glu a 15 13.077 26.825 13.926 1.00 20.98 6 c atom 115 o glu a 15 12.789 26.955 15.101 1.00 19.01 8 o atom 116 cb glu a 15 15.142 25.669 13.355 1.00 25.70 6 c atom 117 cg glu a 15 15.811 24.368 12.964 1.00 29.97 6 c atom 118 cd glu a 15 16.871 24.605 11.915 1.00 32.30 6 c atom 119 oe1 glu a 15 16.505 25.111 10.825 1.00 33.10 8 o atom 120 oe2 glu a 15 18.032 24.282 12.228 1.00 33.52 8 o atom 121 n val a 16 13.064 27.788 13.025 1.00 20.03 7 n atom 122 ca val a 16 12.594 29.131 13.272 1.00 18.96 6 c atom 123 c val a 16 13.672 29.818 14.113 1.00 18.13 6 c atom 124 o val a 16 14.869 29.675 13.882 1.00 16.52 8 o atom 125 cb val a 16 12.332 29.865 11.954 1.00 19.26 6 c atom 126 cg1 val a 16 12.071 31.341 12.214 1.00 21.03 6 c atom 127 cg2 val a 16 11.170 29.231 11.201 1.00 20.95 6 c atom 128 n lys a 17 13.194 30.499 15.135 1.00 17.20 7 n atom 129 ca lys a 17 14.022 31.172 16.106 1.00 16.66 6 c atom 130 c lys a 17 13.977 32.665 15.821 1.00 18.89 6 c atom 131 o lys a 17 13.114 33.097 15.059 1.00 17.59 8 o atom 132 cb lys a 17 13.564 30.879 17.531 1.00 16.04 6 c atom 133 cg lys a 17 13.426 29.398 17.892 1.00 15.96 6 c atom 134 cd lys a 17 14.814 28.735 17.889 1.00 14.73 6 c atom 135 ce lys a 17 14.762 27.288 18.346 1.00 13.76 6 c atom 136 nz lys a 17 13.749 26.441 17.691 1.00 12.41 7 n atom 137 n tyr a 18 14.938 33.388 16.368 1.00 19.84 7 n atom 138 ca tyr a 18 15.025 34.828 16.167 1.00 20.37 6 c atom 139 c tyr a 18 14.923 35.541 17.504 1.00 19.90 6 c atom 140 o tyr a 18 15.876 35.513 18.307 1.00 17.52 8 o atom 141 cb tyr a 18 16.353 35.119 15.447 1.00 21.90 6 c atom 142 cg tyr a 18 16.563 36.598 15.208 1.00 24.25 6 c atom 143 cd1 tyr a 18 15.913 37.244 14.160 1.00 24.47 6 c atom 144 cd2 tyr a 18 17.397 37.334 16.040 1.00 24.72 6 c atom 145 ce1 tyr a 18 16.100 38.595 13.968 1.00 26.92 6 c atom 146 ce2 tyr a 18 17.607 38.689 15.822 1.00 26.06 6 c atom 147 cz tyr a 18 16.950 39.315 14.794 1.00 26.81 6 c atom 148 oh tyr a 18 17.109 40.663 14.554 1.00 28.17 8 o atom 149 n gln a 19 13.770 36.189 17.768 1.00 18.35 7 n atom 150 ca gln a 19 13.632 36.825 19.086 1.00 18.17 6 c atom 151 c gln a 19 14.517 38.055 19.257 1.00 17.45 6 c atom 152 o gln a 19 14.822 38.476 20.382 1.00 16.12 8 o atom 153 cb gln a 19 12.175 37.178 19.400 1.00 17.03 6 c atom 154 cg gln a 19 11.494 38.142 18.452 1.00 17.78 6 c atom 155 cd gln a 19 9.989 38.229 18.740 1.00 18.48 6 c atom 156 oe1 gln a 19 9.229 37.475 18.134 1.00 16.79 8 o atom 157 ne2 gln a 19 9.561 39.125 19.629 1.00 16.10 7 n atom 158 n gly a 20 14.897 38.707 18.175 1.00 17.57 7 n atom 159 ca gly a 20 15.691 39.937 18.290 1.00 19.48 6 c atom 160 c gly a 20 14.821 41.075 18.817 1.00 20.35 6 c atom 161 o gly a 20 13.586 41.062 18.656 1.00 20.41 8 o atom 162 n ser a 21 15.438 42.019 19.526 1.00 20.71 7 n atom 163 ca ser a 21 14.713 43.160 20.063 1.00 23.14 6 c atom 164 c ser a 21 13.926 42.858 21.326 1.00 24.44 6 c atom 165 o ser a 21 12.992 43.607 21.658 1.00 26.92 8 o atom 166 cb ser a 21 15.651 44.367 20.242 1.00 23.92 6 c atom 167 og ser a 21 16.759 44.065 21.045 1.00 27.49 8 o atom 168 n cys a 22 14.106 41.706 21.951 1.00 22.26 7 n atom 169 ca cys a 22 13.350 41.256 23.108 1.00 21.48 6 c atom 170 c cys a 22 11.945 40.796 22.705 1.00 22.09 6 c atom 171 o cys a 22 11.829 39.925 21.840 1.00 21.19 8 o atom 172 cb cys a 22 14.080 40.099 23.784 1.00 20.91 6 c atom 173 sg cys a 22 13.219 39.203 25.087 1.00 19.30 16 s atom 174 n gly a 23 10.905 41.312 23.337 1.00 22.16 7 n atom 175 ca gly a 23 9.520 40.949 23.019 1.00 23.52 6 c atom 176 c gly a 23 9.027 39.738 23.812 1.00 22.55 6 c atom 177 o gly a 23 8.098 39.854 24.600 1.00 22.31 8 o atom 178 n ala a 24 9.588 38.594 23.491 1.00 20.78 7 n atom 179 ca ala a 24 9.381 37.322 24.131 1.00 22.25 6 c atom 180 c ala a 24 8.606 36.348 23.251 1.00 21.73 6 c atom 181 o ala a 24 8.604 35.133 23.477 1.00 22.17 8 o atom 182 cb ala a 24 10.770 36.696 24.361 1.00 19.41 6 c atom 183 n cys a 25 8.006 36.839 22.173 1.00 21.50 7 n atom 184 ca cys a 25 7.289 35.967 21.237 1.00 21.90 6 c atom 185 c cys a 25 6.233 35.129 21.947 1.00 19.92 6 c atom 186 o cys a 25 6.046 33.974 21.548 1.00 19.41 8 o atom 187 cb cys a 25 6.710 36.813 20.107 1.00 21.33 6 c atom 188 sg cys a 25 5.315 37.751 20.742 1.00 26.09 16 s atom 189 n trp a 26 5.672 35.568 23.070 1.00 17.52 7 n atom 190 ca trp a 26 4.801 34.727 23.877 1.00 18.18 6 c atom 191 c trp a 26 5.571 33.457 24.255 1.00 16.85 6 c atom 192 o trp a 26 5.008 32.382 24.189 1.00 17.48 8 o atom 193 cb trp a 26 4.313 35.435 25.137 1.00 15.96 6 c atom 194 cg trp a 26 5.404 35.886 26.061 1.00 15.80 6 c atom 195 cd1 trp a 26 6.185 37.002 25.915 1.00 15.70 6 c atom 196 cd2 trp a 26 5.810 35.269 27.292 1.00 15.90 6 c atom 197 ne1 trp a 26 7.063 37.094 26.970 1.00 17.03 7 n atom 198 ce2 trp a 26 6.870 36.031 27.829 1.00 15.76 6 c atom 199 ce3 trp a 26 5.406 34.115 27.970 1.00 16.45 6 c atom 200 cz2 trp a 26 7.505 35.694 29.019 1.00 15.69 6 c atom 201 cz3 trp a 26 6.040 33.781 29.153 1.00 15.24 6 c atom 202 ch2 trp a 26 7.079 34.570 29.665 1.00 15.78 6 c atom 203 n ala a 27 6.833 33.574 24.663 1.00 16.45 7 n atom 204 ca ala a 27 7.658 32.428 25.019 1.00 16.92 6 c atom 205 c ala a 27 7.988 31.552 23.814 1.00 16.86 6 c atom 206 o ala a 27 7.857 30.334 23.908 1.00 17.19 8 o atom 207 cb ala a 27 8.960 32.917 25.669 1.00 15.94 6 c atom 208 n phe a 28 8.420 32.122 22.688 1.00 15.97 7 n atom 209 ca phe a 28 8.601 31.344 21.460 1.00 18.38 6 c atom 210 c phe a 28 7.363 30.566 21.054 1.00 18.19 6 c atom 211 o phe a 28 7.370 29.370 20.699 1.00 17.48 8 o atom 212 cb phe a 28 9.138 32.265 20.342 1.00 17.61 6 c atom 213 cg phe a 28 10.587 32.608 20.629 1.00 17.23 6 c atom 214 cd1 phe a 28 10.946 33.881 21.029 1.00 17.29 6 c atom 215 cd2 phe a 28 11.561 31.630 20.518 1.00 17.14 6 c atom 216 ce1 phe a 28 12.261 34.188 21.307 1.00 16.44 6 c atom 217 ce2 phe a 28 12.881 31.930 20.798 1.00 16.53 6 c atom 218 cz phe a 28 13.223 33.210 21.187 1.00 16.26 6 c atom 219 n ser a 29 6.209 31.227 21.083 1.00 17.38 7 n atom 220 ca ser a 29 4.923 30.616 20.795 1.00 17.21 6 c atom 221 c ser a 29 4.640 29.430 21.716 1.00 17.03 6 c atom 222 o ser a 29 4.221 28.360 21.262 1.00 16.44 8 o atom 223 cb ser a 29 3.754 31.617 20.956 1.00 16.27 6 c atom 224 og ser a 29 2.523 31.035 20.620 1.00 17.21 8 o atom 225 n ala a 30 4.739 29.614 23.030 1.00 16.51 7 n atom 226 ca ala a 30 4.494 28.558 24.008 1.00 16.93 6 c atom 227 c ala a 30 5.423 27.368 23.748 1.00 17.67 6 c atom 228 o ala a 30 4.965 26.220 23.590 1.00 17.18 8 o atom 229 cb ala a 30 4.774 29.082 25.419 1.00 15.31 6 c atom 230 n val a 31 6.736 27.653 23.639 1.00 15.78 7 n atom 231 ca val a 31 7.612 26.484 23.421 1.00 16.05 6 c atom 232 c val a 31 7.327 25.776 22.111 1.00 16.60 6 c atom 233 o val a 31 7.375 24.537 22.106 1.00 16.65 8 o atom 234 cb val a 31 9.115 26.767 23.633 1.00 15.32 6 c atom 235 cg1 val a 31 9.281 27.202 25.092 1.00 13.75 6 c atom 236 cg2 val a 31 9.735 27.775 22.688 1.00 13.21 6 c atom 237 n gly a 32 7.020 26.454 21.018 1.00 16.40 7 n atom 238 ca gly a 32 6.681 25.786 19.771 1.00 15.93 6 c atom 239 c gly a 32 5.530 24.805 19.984 1.00 15.74 6 c atom 240 o gly a 32 5.643 23.653 19.584 1.00 16.98 8 o atom 241 n ala a 33 4.470 25.226 20.645 1.00 15.94 7 n atom 242 ca ala a 33 3.327 24.336 20.882 1.00 17.89 6 c atom 243 c ala a 33 3.802 23.112 21.655 1.00 17.24 6 c atom 244 o ala a 33 3.507 21.990 21.237 1.00 18.77 8 o atom 245 cb ala a 33 2.200 25.052 21.595 1.00 16.12 6 c atom 246 n leu a 34 4.576 23.329 22.719 1.00 16.31 7 n atom 247 ca leu a 34 5.024 22.215 23.542 1.00 15.76 6 c atom 248 c leu a 34 6.001 21.299 22.822 1.00 16.19 6 c atom 249 o leu a 34 5.953 20.087 23.056 1.00 14.67 8 o atom 250 cb leu a 34 5.562 22.673 24.888 1.00 14.39 6 c atom 251 cg leu a 34 5.846 21.529 25.887 1.00 16.48 6 c atom 252 cd1 leu a 34 4.628 20.643 26.138 1.00 16.05 6 c atom 253 cd2 leu a 34 6.331 22.122 27.201 1.00 14.15 6 c atom 254 n glu a 35 6.789 21.808 21.885 1.00 17.32 7 n atom 255 ca glu a 35 7.739 21.002 21.131 1.00 17.92 6 c atom 256 c glu a 35 7.053 19.951 20.273 1.00 17.29 6 c atom 257 o glu a 35 7.511 18.805 20.193 1.00 16.83 8 o atom 258 cb glu a 35 8.629 21.871 20.219 1.00 17.41 6 c atom 259 cg glu a 35 9.596 22.688 21.066 1.00 17.30 6 c atom 260 cd glu a 35 10.191 23.916 20.407 1.00 17.73 6 c atom 261 oe1 glu a 35 9.787 24.246 19.260 1.00 17.63 8 o atom 262 oe2 glu a 35 11.011 24.593 21.050 1.00 15.27 8 o atom 263 n ala a 36 5.931 20.333 19.664 1.00 17.72 7 n atom 264 ca ala a 36 5.181 19.415 18.814 1.00 18.29 6 c atom 265 c ala a 36 4.622 18.266 19.657 1.00 18.92 6 c atom 266 o ala a 36 4.705 17.097 19.307 1.00 17.72 8 o atom 267 cb ala a 36 4.011 20.082 18.116 1.00 17.84 6 c atom 268 n gln a 37 4.132 18.665 20.831 1.00 19.59 7 n atom 269 ca gln a 37 3.574 17.734 21.799 1.00 19.74 6 c atom 270 c gln a 37 4.664 16.814 22.317 1.00 20.59 6 c atom 271 o gln a 37 4.479 15.597 22.406 1.00 18.18 8 o atom 272 cb gln a 37 2.869 18.473 22.932 1.00 21.11 6 c atom 273 cg gln a 37 1.571 19.185 22.571 1.00 20.44 6 c atom 274 cd gln a 37 0.609 18.366 21.748 1.00 22.15 6 c atom 275 oe1 gln a 37 0.159 17.298 22.168 1.00 21.04 8 o atom 276 ne2 gln a 37 0.249 18.838 20.555 1.00 22.05 7 n atom 277 n leu a 38 5.892 17.335 22.554 1.00 20.72 7 n atom 278 ca leu a 38 6.948 16.463 23.026 1.00 20.79 6 c atom 279 c leu a 38 7.395 15.502 21.926 1.00 22.46 6 c atom 280 o leu a 38 7.694 14.342 22.208 1.00 22.04 8 o atom 281 cb leu a 38 8.148 17.269 23.523 1.00 21.43 6 c atom 282 cg leu a 38 9.316 16.411 24.034 1.00 22.45 6 c atom 283 cd1 leu a 38 8.946 15.693 25.333 1.00 21.59 6 c atom 284 cd2 leu a 38 10.524 17.299 24.219 1.00 22.97 6 c atom 285 n lys a 39 7.338 15.957 20.675 1.00 22.59 7 n atom 286 ca lys a 39 7.644 15.084 19.564 1.00 24.59 6 c atom 287 c lys a 39 6.621 13.949 19.511 1.00 24.30 6 c atom 288 o lys a 39 7.005 12.785 19.403 1.00 23.82 8 o atom 289 cb lys a 39 7.607 15.809 18.218 1.00 24.89 6 c atom 290 cg lys a 39 8.494 15.128 17.199 1.00 26.54 6 c atom 291 cd lys a 39 7.941 13.844 16.618 1.00 26.35 6 c atom 292 ce lys a 39 8.884 13.346 15.527 1.00 27.02 6 c atom 293 nz lys a 39 8.087 12.728 14.424 1.00 26.16 7 n atom 294 n leu a 40 5.349 14.329 19.576 1.00 24.86 7 n atom 295 ca leu a 40 4.265 13.372 19.524 1.00 26.98 6 c atom 296 c leu a 40 4.395 12.320 20.630 1.00 26.87 6 c atom 297 o leu a 40 4.152 11.168 20.318 1.00 25.13 8 o atom 298 cb leu a 40 2.867 13.994 19.607 1.00 26.48 6 c atom 299 cg leu a 40 2.094 14.431 18.367 1.00 27.33 6 c atom 300 gd1 leu a 40 2.665 13.926 17.047 1.00 26.43 6 c atom 301 cd2 leu a 40 1.903 15.944 18.328 1.00 27.09 6 c atom 302 n lys a 41 4.876 12.649 21.826 1.00 29.03 7 n atom 303 ca lys a 41 4.899 11.684 22.912 1.00 30.09 6 c atom 304 c lys a 41 6.201 10.886 22.988 1.00 30.38 6 c atom 305 o lys a 41 6.139 9.699 23.323 1.00 30.29 8 o atom 306 cb lys a 41 4.718 12.410 24.245 1.00 31.73 6 c atom 307 cg lys a 41 4.425 11.541 25.457 1.00 35.82 6 c atom 308 cd lys a 41 2.915 11.433 25.693 1.00 37.62 6 c atom 309 ce lys a 41 2.555 10.542 26.877 1.00 38.14 6 c atom 310 nz lys a 41 2.898 11.223 28.162 1.00 39.87 7 n atom 311 n thr a 42 7.339 11.513 22.725 1.00 29.06 7 n atom 312 ca thr a 42 8.615 10.829 22.853 1.00 29.05 6 c atom 313 c thr a 42 9.263 10.346 21.564 1.00 28.87 6 c atom 314 o thr a 42 9.989 9.360 21.535 1.00 28.82 8 o atom 315 cb thr a 42 9.644 11.751 23.549 1.00 29.64 6 c atom 316 og1 thr a 42 9.852 12.939 22.780 1.00 28.26 8 o atom 317 cg2 thr a 42 9.133 12.094 24.941 1.00 30.34 6 c atom 318 n gly a 43 8.885 10.983 20.460 1.00 29.52 7 n atom 319 ca gly a 43 9.440 10.699 19.142 1.00 28.57 6 c atom 320 c gly a 43 10.634 11.621 18.886 1.00 28.49 6 c atom 321 o gly a 43 11.313 11.670 17.846 1.00 28.02 8 o atom 322 n lys a 44 10.936 12.456 19.888 1.00 27.55 7 n atom 323 ca lys a 44 12.055 13.368 19.776 1.00 28.20 6 c atom 324 c lys a 44 11.651 14.827 19.551 1.00 26.36 6 c atom 325 o lys a 44 10.843 15.430 20.242 1.00 24.53 8 o atom 326 cb lys a 44 13.025 13.392 20.952 1.00 30.93 6 c atom 327 cg lys a 44 13.525 12.083 21.501 1.00 35.12 6 c atom 328 cd lys a 44 14.483 12.316 22.659 1.00 37.99 6 c atom 329 ce lys a 44 15.887 12.738 22.285 1.00 40.19 6 c atom 330 nz lys a 44 16.222 14.171 22.486 1.00 40.87 7 n atom 331 n leu a 45 12.328 15.396 18.569 1.00 23.85 7 n atom 332 ca leu a 45 12.197 16.771 18.159 1.00 23.20 6 c atom 333 c leu a 45 13.348 17.560 18.779 1.00 23.59 6 c atom 334 o leu a 45 14.505 17.398 18.406 1.00 24.24 8 o atom 335 cb leu a 45 12.289 16.971 16.642 1.00 21.33 6 c atom 336 cg leu a 45 11.996 18.414 16.193 1.00 20.74 6 c atom 337 cd1 leu a 45 10.622 18.872 16.656 1.00 19.65 6 c atom 338 cd2 leu a 45 12.039 18.494 14.669 1.00 20.45 6 c atom 339 n val a 46 13.035 18.364 19.777 1.00 24.57 7 n atom 340 ca val a 46 13.976 19.138 20.542 1.00 24.31 6 c atom 341 c val a 46 13.466 20.551 20.817 1.00 22.73 6 c atom 342 o val a 46 12.279 20.726 21.154 1.00 22.54 8 o atom 343 cb val a 46 14.366 18.514 21.895 1.00 26.41 6 c atom 344 cg1 val a 46 14.971 17.116 21.771 1.00 27.91 6 c atom 345 cg2 val a 46 13.286 18.454 22.944 1.00 28.91 6 c atom 346 n ser a 47 14.317 21.545 20.624 1.00 19.05 7 n atom 347 ca ser a 47 13.960 22.936 20.860 1.00 18.99 6 c atom 348 c ser a 47 13.947 23.245 22.359 1.00 18.85 6 c atom 349 o ser a 47 14.930 23.066 23.069 1.00 18.08 8 o atom 350 cb ser a 47 14.866 23.942 20.158 1.00 18.32 6 c atom 351 og ser a 47 14.740 23.941 18.751 1.00 17.10 8 o atom 352 n leu a 48 12.786 23.730 22.830 1.00 17.49 7 n atom 353 ca leu a 48 12.677 24.039 24.254 1.00 16.34 6 c atom 354 c leu a 48 13.155 25.427 24.628 1.00 17.70 6 c atom 355 o leu a 48 13.196 26.338 23.792 1.00 16.84 8 o atom 356 cb leu a 48 11.232 23.779 24.712 1.00 17.83 6 c atom 357 cg leu a 48 10.824 22.318 24.448 1.00 18.14 6 c atom 358 cd1 leu a 48 9.342 22.056 24.683 1.00 17.67 6 c atom 359 cd2 leu a 48 11.669 21.439 25.392 1.00 18.70 6 c atom 360 n ser a 49 13.433 25.653 25.918 1.00 15.90 7 n atom 361 ca ser a 49 13.933 26.933 26.369 1.00 18.00 6 c atom 362 c ser a 49 12.896 28.046 26.478 1.00 17.99 6 c atom 363 o ser a 49 12.189 28.151 27.474 1.00 17.35 8 o atom 364 cb ser a 49 14.623 26.778 27.746 1.00 18.02 6 c atom 365 og ser a 49 15.129 28.046 28.144 1.00 18.86 8 o atom 366 n ala a 50 12.960 29.021 25.570 1.00 18.67 7 n atom 367 ca ala a 50 12.153 30.224 25.629 1.00 18.60 6 c atom 368 c ala a 50 12.619 31.174 26.724 1.00 17.87 6 c atom 369 o ala a 50 11.815 31.901 27.322 1.00 16.25 8 o atom 370 cb ala a 50 12.123 30.981 24.300 1.00 11.21 6 c atom 371 n gln a 51 13.922 31.177 26.988 1.00 18.60 7 n atom 372 ca gln a 51 14.542 31.983 28.024 1.00 18.40 6 c atom 373 c gln a 51 14.076 31.556 29.411 1.00 18.48 6 c atom 374 o gln a 51 13.943 32.321 30.358 1.00 18.80 8 o atom 375 cb gln a 51 16.080 31.808 27.962 1.00 20.13 6 c atom 376 cg gln a 51 16.783 32.937 28.702 1.00 18.55 6 c atom 377 cd gln a 51 16.661 34.326 28.120 1.00 17.07 6 c atom 378 oe1 gln a 51 16.824 34.535 26.923 1.00 14.91 8 o atom 379 ne2 gln a 51 16.460 35.288 29.011 1.00 18.51 7 n atom 380 n asn a 52 13.963 30.225 29.575 1.00 19.47 7 n atom 381 ca asn a 52 13.460 29.631 30.815 1.00 20.71 6 c atom 382 c asn a 52 12.124 30.280 31.181 1.00 20.45 6 c atom 383 o asn a 52 11.944 30.762 32.303 1.00 17.25 8 o atom 384 cb asn a 52 13.383 28.114 30.673 1.00 20.87 6 c atom 385 cg asn a 52 12.974 27.281 31.848 1.00 20.23 6 c atom 386 od1 asn a 52 13.035 26.042 31.784 1.00 20.32 8 o atom 387 nd2 asn a 52 12.517 27.875 32.946 1.00 21.50 7 n atom 388 n leu a 53 11.198 30.420 30.215 1.00 21.47 7 n atom 389 ca leu a 53 9.912 31.043 30.494 1.00 21.14 6 c atom 390 c leu a 53 10.107 32.536 30.727 1.00 21.35 6 c atom 391 o leu a 53 9.471 33.134 31.587 1.00 18.78 8 o atom 392 cb leu a 53 8.921 30.819 29.359 1.00 21.56 6 c atom 393 cg leu a 53 8.456 29.377 29.114 1.00 20.07 6 c atom 394 cd1 leu a 53 7.771 29.374 27.757 1.00 19.70 6 c atom 395 cd2 leu a 53 7.599 28.877 30.261 1.00 18.58 6 c atom 396 n val a 54 10.993 33.152 29.946 1.00 22.68 7 n atom 397 ca val a 54 11.254 34.588 30.057 1.00 23.62 6 c atom 398 c val a 54 11.728 34.982 31.448 1.00 24.36 6 c atom 399 o val a 54 11.226 35.919 32.085 1.00 23.55 8 o atom 400 cb val a 54 12.248 35.049 28.978 1.00 23.79 6 c atom 401 cg1 val a 54 12.803 36.440 29.246 1.00 24.54 6 c atom 402 cg2 val a 54 11.545 35.029 27.619 1.00 24.34 6 c atom 403 n asp a 55 12.688 34.213 31.951 1.00 26.26 7 n atom 404 ca asp a 55 13.231 34.456 33.279 1.00 26.05 6 c atom 405 c asp a 55 12.428 33.847 34.427 1.00 25.32 6 c atom 406 o asp a 55 12.645 34.315 35.554 1.00 25.80 8 o atom 407 cb asp a 55 14.600 33.775 33.426 1.00 25.71 6 c atom 408 cg asp a 55 15.603 34.072 32.344 1.00 25.74 6 c atom 409 od1 asp a 55 15.467 35.111 31.668 1.00 24.78 8 o atom 410 od2 asp a 55 16.507 33.210 32.219 1.00 24.52 8 o atom 411 n cys a 56 11.662 32.793 34.201 1.00 23.81 7 n atom 412 ca cys a 56 11.012 32.164 35.354 1.00 23.78 6 c atom 413 c cys a 56 9.501 32.282 35.408 1.00 23.35 6 c atom 414 o cys a 56 8.918 32.128 36.477 1.00 21.47 8 o atom 415 cb cys a 56 11.414 30.683 35.404 1.00 23.68 6 c atom 416 sg cys a 56 13.190 30.368 35.221 1.00 22.70 16 s atom 417 n ser a 57 8.835 32.493 34.281 1.00 22.84 7 n atom 418 ca ser a 57 7.366 32.608 34.322 1.00 23.73 6 c atom 419 c ser a 57 7.071 34.101 34.398 1.00 24.63 6 c atom 420 o ser a 57 6.849 34.727 33.367 1.00 26.03 8 o atom 421 cb ser a 57 6.793 31.920 33.096 1.00 21.04 6 c atom 422 og ser a 57 5.422 32.154 32.935 1.00 19.66 8 o atom 423 n thr a 58 7.302 34.714 35.549 1.00 26.44 7 n atom 424 ca thr a 58 7.254 36.172 35.613 1.00 28.22 6 c atom 425 c thr a 58 5.961 36.646 36.248 1.00 28.24 6 c atom 426 o thr a 58 4.871 36.239 35.841 1.00 27.63 8 o atom 427 cb thr a 58 8.524 36.736 36.266 1.00 28.11 6 c atom 428 og1 thr a 58 8.677 36.209 37.582 1.00 28.90 8 o atom 429 cg2 thr a 58 9.756 36.367 35.448 1.00 28.10 6 c atom 430 n glu a 59 6.047 37.550 37.200 1.00 29.07 7 n atom 431 ca glu a 59 4.971 38.180 37.914 1.00 29.69 6 c atom 432 c glu a 59 3.748 37.343 38.226 1.00 29.57 6 c atom 433 o glu a 59 2.616 37.789 38.002 1.00 27.85 8 o atom 434 cb glu a 59 5.480 38.705 39.283 1.00 30.22 6 c atom 435 cg glu a 59 4.525 39.351 40.197 1.00 20.00 6 c atom 436 cd glu a 59 5.160 39.754 41.508 1.00 20.00 6 c atom 437 oe1 glu a 59 4.490 40.384 42.314 1.00 20.00 8 o atom 438 oe2 glu a 59 6.328 39.431 41.715 1.00 20.00 8 o atom 439 n lys a 60 3.927 36.137 38.777 1.00 30.46 7 n atom 440 ca lys a 60 2.794 35.303 39.152 1.00 30.95 6 c atom 441 c lys a 60 1.904 34.881 37.995 1.00 28.55 6 c atom 442 o lys a 60 0.785 34.468 38.236 1.00 28.35 8 o atom 443 cb lys a 60 3.242 33.999 39.830 1.00 31.93 6 c atom 444 cg lys a 60 4.331 34.139 40.872 1.00 33.59 6 c atom 445 cd lys a 60 4.246 33.139 41.909 1.00 47.84 6 c atom 446 ce lys a 60 4.061 31.694 41.491 1.00 49.56 6 c atom 447 nz lys a 60 3.084 30.880 42.263 1.00 51.15 7 n atom 448 n tyr a 61 2.395 34.911 36.768 1.00 28.73 7 n atom 449 ca tyr a 61 1.638 34.493 35.586 1.00 27.32 6 c atom 450 c tyr a 61 1.289 35.697 34.729 1.00 25.61 6 c atom 451 o tyr a 61 1.163 35.568 33.507 1.00 26.14 8 o atom 452 cb tyr a 61 2.531 33.479 34.848 1.00 26.85 6 c atom 453 cg tyr a 61 2.893 32.299 35.734 1.00 27.97 6 c atom 454 cd1 tyr a 61 4.083 32.271 36.447 1.00 28.40 6 c atom 455 cd2 tyr a 61 2.026 31.230 35.885 1.00 27.30 6 c atom 456 ce1 tyr a 61 4.410 31.209 37.276 1.00 29.07 6 c atom 457 ce2 tyr a 61 2.323 30.162 36.696 1.00 27.86 6 c atom 458 cz tyr a 61 3.521 30.151 37.383 1.00 29.19 6 c atom 459 oh tyr a 61 3.797 29.082 38.191 1.00 28.61 8 o atom 460 n gly a 62 1.544 36.887 35.258 1.00 24.11 7 n atom 461 ca gly a 62 1.322 38.145 34.567 1.00 24.11 6 c atom 462 c gly a 62 2.211 38.377 33.357 1.00 24.84 6 c atom 463 o gly a 62 1.857 39.169 32.478 1.00 25.32 8 o atom 464 n asn a 63 3.347 37.711 33.279 1.00 24.05 7 n atom 465 ca asn a 63 4.299 37.817 32.191 1.00 25.04 6 c atom 466 c asn a 63 5.419 38.790 32.560 1.00 25.68 6 c atom 467 o asn a 63 5.860 38.832 33.705 1.00 25.85 8 o atom 468 cb asn a 63 4.897 36.438 31.865 1.00 24.60 6 c atom 469 cg asn a 63 3.790 35.499 31.409 1.00 25.30 6 c atom 470 od1 asn a 63 2.863 36.025 30.785 1.00 23.98 8 o atom 471 nd2 asn a 63 3.881 34.212 31.716 1.00 23.73 7 n atom 472 n lys a 64 5.848 39.591 31.600 1.00 26.83 7 n atom 473 ca lys a 64 6.905 40.557 31.862 1.00 29.03 6 c atom 474 c lys a 64 8.145 40.425 30.994 1.00 26.94 6 c atom 475 o lys a 64 8.688 41.414 30.515 1.00 23.94 8 o atom 476 cb lys a 64 6.366 41.986 31.799 1.00 31.45 6 c atom 477 cg lys a 64 4.951 42.150 31.300 1.00 34.48 6 c atom 478 cd lys a 64 4.374 43.468 31.796 1.00 36.59 6 c atom 479 ce lys a 64 3.941 43.380 33.247 1.00 38.18 6 c atom 480 nz lys a 64 3.789 44.751 33.836 1.00 39.69 7 n atom 481 n gly a 65 8.652 39.205 30.874 1.00 26.14 7 n atom 482 ca gly a 65 9.905 38.924 30.188 1.00 25.32 6 c atom 483 c gly a 65 9.950 39.464 28.776 1.00 25.36 6 c atom 484 o gly a 65 9.088 39.160 27.950 1.00 23.67 8 o atom 485 n cys a 66 10.930 40.328 28.492 1.00 23.74 7 n atom 486 ca cys a 66 11.081 40.926 27.176 1.00 23.88 6 c atom 487 c cys a 66 10.051 42.024 26.939 1.00 25.35 6 c atom 488 o cys a 66 9.951 42.541 25.819 1.00 27.33 8 o atom 489 cb cys a 66 12.485 41.490 26.912 1.00 22.99 6 c atom 490 sg cys a 66 13.782 40.217 26.798 1.00 20.78 16 s atom 491 n asn a 67 9.190 42.325 27.902 1.00 25.39 7 n atom 492 ca asn a 67 8.101 43.261 27.688 1.00 24.98 6 c atom 493 c asn a 67 6.780 42.534 27.449 1.00 23.86 6 c atom 494 o asn a 67 5.720 43.151 27.562 1.00 22.02 8 o atom 495 cb asn a 67 8.037 44.271 28.831 1.00 26.60 6 c atom 496 cg asn a 67 9.185 45.261 28.730 1.00 29.73 6 c atom 497 od1 asn a 67 9.581 45.672 27.636 1.00 31.40 8 o atom 498 nd2 asn a 67 9.724 45.670 29.869 1.00 30.23 7 n atom 499 n gly a 68 6.803 41.249 27.099 1.00 22.75 7 n atom 500 ca gly a 68 5.543 40.589 26.755 1.00 23.82 6 c atom 501 c gly a 68 5.019 39.668 27.841 1.00 24.11 6 c atom 502 o gly a 68 5.545 39.564 28.948 1.00 25.80 8 o atom 503 n gly a 69 3.988 38.908 27.446 1.00 23.67 7 n atom 504 ca gly a 69 3.415 37.927 28.370 1.00 23.59 6 c atom 505 c gly a 69 2.368 37.026 27.735 1.00 22.71 6 c atom 506 o gly a 69 1.880 37.295 26.627 1.00 23.06 8 o atom 507 n phe a 70 2.040 35.925 28.417 1.00 21.84 7 n atom 508 ca phe a 70 0.985 35.045 27.942 1.00 20.02 6 c atom 509 c phe a 70 1.441 33.614 27.673 1.00 19.58 6 c atom 510 o phe a 70 2.020 32.987 28.565 1.00 18.51 8 o atom 511 cb phe a 70 0.120 34.982 29.009 1.00 21.03 6 c atom 512 cg phe a 70 0.686 36.311 29.430 1.00 22.23 6 c atom 513 cd1 phe a 70 0.317 36.909 30.617 1.00 23.39 6 c atom 514 cd2 phe a 70 1.566 36.983 28.616 1.00 22.82 6 c atom 515 ce1 phe a 70 0.843 38.125 31.005 1.00 23.39 6 c atom 516 ce2 phe a 70 2.095 38.227 28.996 1.00 24.65 6 c atom 517 cz phe a 70 1.742 38.795 30.210 1.00 23.07 6 c atom 518 n met a 71 0.991 33.056 26.541 1.00 18.47 7 n atom 519 ca met a 71 1.259 31.630 26.295 1.00 18.99 6 c atom 520 c met a 71 0.529 30.728 27.301 1.00 18.18 6 c atom 521 o met a 71 1.071 29.694 27.712 1.00 17.50 8 o atom 522 cb met a 71 0.922 31.207 24.871 1.00 18.74 6 c atom 523 cg met a 71 1.791 31.818 23.776 1.00 18.37 6 c atom 524 sd met a 71 1.216 33.440 23.244 1.00 18.63 16 s atom 525 ce met a 71 0.343 32.988 22.505 1.00 18.77 6 c atom 526 n thr a 72 0.727 31.021 27.622 1.00 18.05 7 n atom 527 ca thr a 72 1.471 30.174 28.548 1.00 20.31 6 c atom 528 c thr a 72 0.785 30.118 29.911 1.00 20.07 6 c atom 529 o thr a 72 0.622 29.054 30.503 1.00 19.51 8 o atom 530 cb thr a 72 2.930 30.597 28.743 1.00 21.33 6 c atom 531 og1 thr a 72 2.975 31.999 29.079 1.00 22.82 8 o atom 532 cg2 thr a 72 3.831 30.406 27.534 1.00 21.24 6 c atom 533 n thr a 73 0.357 31.257 30.457 1.00 21.16 7 n atom 534 ca thr a 73 0.286 31.292 31.764 1.00 22.38 6 c atom 535 c thr a 73 1.721 30.785 31.692 1.00 22.86 6 c atom 536 o thr a 73 2.248 30.214 32.649 1.00 22.70 8 o atom 537 cb thr a 73 0.263 32.670 32.435 1.00 23.50 6 c atom 538 og1 thr a 73 1.106 33.563 31.698 1.00 23.93 8 o atom 539 cg2 thr a 73 1.157 33.227 32.500 1.00 23.17 6 c atom 540 n ala a 74 2.321 30.888 30.503 1.00 21.66 7 n atom 541 ca ala a 74 3.598 30.218 30.260 1.00 21.26 6 c atom 542 c ala a 74 3.391 28.717 30.492 1.00 20.84 6 c atom 543 o ala a 74 4.157 28.084 31.222 1.00 19.57 8 o atom 544 cb ala a 74 4.100 30.489 28.858 1.00 20.60 6 c atom 545 n phe a 75 2.299 28.158 29.955 1.00 20.34 7 n atom 546 ca phe a 75 2.044 26.730 30.158 1.00 21.42 6 c atom 547 c phe a 75 1.813 26.393 31.634 1.00 22.13 6 c atom 548 o phe a 75 2.331 25.360 32.110 1.00 21.75 8 o atom 549 cb phe a 75 0.900 26.222 29.292 1.00 19.45 6 c atom 550 cg phe a 75 1.024 26.378 27.801 1.00 19.54 6 c atom 551 cd1 phe a 75 2.197 26.063 27.132 1.00 17.93 6 c atom 552 cd2 phe a 75 0.040 26.884 27.073 1.00 17.78 6 c atom 553 ce1 phe a 75 2.291 26.192 25.760 1.00 17.68 6 c atom 554 ce2 phe a 75 0.063 27.033 25.702 1.00 18.90 6 c atom 555 cz phe a 75 1.242 26.707 25.039 1.00 17.67 6 c atom 556 n gln a 76 0.990 27.187 32.318 1.00 21.66 7 n atom 557 ca gln a 76 0.778 26.987 33.756 1.00 21.72 6 c atom 558 c gln a 76 2.124 26.931 34.468 1.00 22.32 6 c atom 559 o gln a 76 2.367 25.991 35.241 1.00 23.61 8 o atom 560 cb gln a 76 0.156 28.057 34.340 1.00 20.67 6 c atom 561 cg gln a 76 0.700 27.683 35.729 1.00 20.28 6 c atom 562 cd gln a 76 1.544 26.424 35.663 1.00 20.05 6 c atom 563 oe1 gln a 76 2.454 26.331 34.841 1.00 20.80 8 o atom 564 ne2 gln a 76 1.283 25.413 36.476 1.00 20.51 7 n atom 565 n tyr a 77 3.025 27.885 34.222 1.00 21.54 7 n atom 566 ca tyr a 77 4.362 27.854 34.805 1.00 22.83 6 c atom 567 c tyr a 77 4.974 26.478 34.559 1.00 23.93 6 c atom 568 o tyr a 77 5.345 25.767 35.497 1.00 25.67 8 o atom 569 cb tyr a 77 5.281 28.973 34.256 1.00 20.59 6 c atom 570 cg tyr a 77 6.737 28.725 34.595 1.00 20.16 6 c atom 571 cd1 tyr a 77 7.307 28.990 35.838 1.00 19.43 6 c atom 572 cd2 tyr a 77 7.531 28.124 33.623 1.00 20.20 6 c atom 573 ce1 tyr a 77 8.625 28.645 36.101 1.00 20.19 6 c atom 574 ce2 tyr a 77 8.846 27.796 33.880 1.00 19.65 6 c atom 575 cz tyr a 77 9.391 28.056 35.123 1.00 19.11 6 c atom 576 oh tyr a 77 10.698 27.720 35.313 1.00 19.26 8 o atom 577 n ile a 78 4.993 26.011 33.303 1.00 23.48 7 n atom 578 ca ile a 78 5.553 24.696 33.031 1.00 24.75 6 c atom 579 c ile a 78 4.871 23.622 33.881 1.00 24.56 6 c atom 580 o ile a 78 5.576 22.739 34.385 1.00 22.23 8 o atom 581 cb ile a 78 5.508 24.290 31.546 1.00 24.41 6 c atom 582 cg1 ile a 78 6.109 25.404 30.697 1.00 24.65 6 c atom 583 cg2 ile a 78 6.248 22.973 31.349 1.00 24.29 6 c atom 584 cd1 ile a 78 6.084 25.172 29.207 1.00 24.15 6 c atom 585 n ile a 79 3.542 23.675 33.975 1.00 25.05 7 n atom 586 ca ile a 79 2.824 22.700 34.781 1.00 25.66 6 c atom 587 c ile a 79 3.261 22.812 36.242 1.00 26.91 6 c atom 588 o ile a 79 3.813 21.869 36.803 1.00 27.41 8 o atom 589 cb ile a 79 1.293 22.830 34.664 1.00 25.49 6 c atom 590 cg1 ile a 79 0.767 22.600 33.247 1.00 24.63 6 c atom 591 cg2 ile a 79 0.661 21.817 35.628 1.00 24.28 6 c atom 592 cd1 ile a 79 0.636 23.153 33.038 1.00 24.70 6 c atom 593 n asp a 80 3.211 24.000 36.834 1.00 28.62 7 n atom 594 ca asp a 80 3.578 24.223 38.220 1.00 29.91 6 c atom 595 c asp a 80 5.009 23.831 38.569 1.00 30.38 6 c atom 596 o asp a 80 5.287 23.292 39.647 1.00 30.30 8 o atom 597 cb asp a 80 3.474 25.714 38.591 1.00 30.68 6 c atom 598 cg asp a 80 2.087 26.277 38.430 1.00 31.07 6 c atom 599 od1 asp a 80 1.122 25.489 38.310 1.00 30.77 8 o atom 600 od2 asp a 80 1.951 27.518 38.415 1.00 31.39 8 o atom 601 n asn a 81 5.922 24.166 37.657 1.00 28.48 7 n atom 602 ca asn a 81 7.342 23.956 37.797 1.00 27.10 6 c atom 603 c asn a 81 7.738 22.510 37.576 1.00 27.44 6 c atom 604 o asn a 81 8.858 22.095 37.860 1.00 25.88 8 o atom 605 cb asn a 81 8.064 24.764 36.692 1.00 26.97 6 c atom 606 cg asn a 81 9.556 24.852 36.910 1.00 26.16 6 c atom 607 od1 asn a 81 9.936 25.213 38.018 1.00 26.37 8 o atom 608 nd2 asn a 81 10.385 24.575 35.920 1.00 25.24 7 n atom 609 n lys a 82 6.816 21.740 37.028 1.00 27.92 7 n atom 610 ca lys a 82 6.943 20.370 36.609 1.00 28.87 6 c atom 611 c lys a 82 8.171 20.162 35.722 1.00 28.70 6 c atom 612 o lys a 82 8.800 19.107 35.708 1.00 28.98 8 o atom 613 cb lys a 82 6.773 19.289 37.648 1.00 30.46 6 c atom 614 cg lys a 82 7.215 19.418 39.072 1.00 31.11 6 c atom 615 cd lys a 82 6.175 18.839 40.038 1.00 31.43 6 c atom 616 ce lys a 82 6.323 18.231 41.298 1.00 42.55 6 c atom 617 nz lys a 82 6.739 19.021 42.455 1.00 42.93 7 n atom 618 n gly a 83 8.348 21.082 34.763 1.00 28.83 7 n atom 619 ca gly a 83 9.338 20.926 33.731 1.00 26.57 6 c atom 620 c gly a 83 9.818 22.202 33.069 1.00 26.03 6 c atom 621 o gly a 83 9.640 23.329 33.515 1.00 25.30 8 o atom 622 n ile a 84 10.463 21.962 31.920 1.00 25.05 7 n atom 623 ca ile a 84 11.126 23.031 31.179 1.00 22.45 6 c atom 624 c ile a 84 12.381 22.432 30.531 1.00 22.16 6 c atom 625 o ile a 84 12.339 21.353 29.972 1.00 22.15 8 o atom 626 cb ile a 84 10.183 23.680 30.163 1.00 22.23 6 c atom 627 cg1 ile a 84 10.934 24.726 29.339 1.00 21.20 6 c atom 628 cg2 ile a 84 9.548 22.630 29.259 1.00 19.22 6 c atom 629 cd1 ile a 84 10.037 25.790 28.744 1.00 22.01 6 c atom 630 n asp a 85 13.461 23.206 30.653 1.00 21.30 7 n atom 631 ca asp a 85 14.748 22.812 30.128 1.00 22.61 6 c atom 632 c asp a 85 14.765 22.874 28.602 1.00 23.42 6 c atom 633 o asp a 85 14.005 23.685 28.050 1.00 22.85 8 o atom 634 cb asp a 85 15.893 23.715 30.609 1.00 22.02 6 c atom 635 cg asp a 85 16.143 23.584 32.102 1.00 21.23 6 c atom 636 od1 asp a 85 15.879 22.489 32.632 1.00 21.06 8 o atom 637 od2 asp a 85 16.524 24.587 32.716 1.00 20.77 8 o atom 638 n ser a 86 15.791 22.266 28.028 1.00 22.72 7 n atom 639 ca ser a 86 15.974 22.390 26.589 1.00 22.22 6 c atom 640 c ser a 86 16.579 23.765 26.329 1.00 22.57 6 c atom 641 o ser a 86 17.156 24.386 27.230 1.00 21.45 8 o atom 642 cb ser a 86 16.962 21.329 26.089 1.00 22.24 6 c atom 643 og ser a 86 18.221 21.694 26.665 1.00 24.14 8 o atom 644 n asp a 87 16.496 24.155 25.060 1.00 21.28 7 n atom 645 ca asp a 87 17.094 25.413 24.621 1.00 22.89 6 c atom 646 c asp a 87 18.615 25.302 24.720 1.00 23.24 6 c atom 647 o asp a 87 19.305 26.271 25.045 1.00 22.12 8 o atom 648 cb asp a 87 16.627 25.675 23.193 1.00 22.42 6 c atom 649 cg asp a 87 17.321 26.845 22.531 1.00 23.15 6 c atom 650 od1 asp a 87 18.233 26.628 21.708 1.00 22.34 8 o atom 651 od2 asp a 87 16.921 27.979 22.869 1.00 23.10 8 o atom 652 n ala a 88 19.143 24.102 24.484 1.00 24.49 7 n atom 653 ca ala a 88 20.577 23.865 24.611 1.00 26.40 6 c atom 654 c ala a 88 20.989 24.094 26.071 1.00 26.92 6 c atom 655 o ala a 88 21.998 24.796 26.177 1.00 27.55 8 o atom 656 cb ala a 88 20.972 22.499 24.100 1.00 25.55 6 c atom 657 n ser a 89 20.309 23.597 27.077 1.00 27.31 7 n atom 658 ca ser a 89 20.611 23.775 28.479 1.00 29.30 6 c atom 659 c ser a 89 20.529 25.235 28.967 1.00 29.01 6 c atom 660 o ser a 89 21.163 25.665 29.935 1.00 30.36 8 o atom 661 cb ser a 89 19.626 23.022 29.377 1.00 29.91 6 c atom 662 og ser a 89 18.430 22.558 28.819 1.00 33.23 8 o atom 663 n tyr a 90 19.551 25.966 28.461 1.00 28.62 7 n atom 664 ca tyr a 90 19.202 27.320 28.921 1.00 26.48 6 c atom 665 c tyr a 90 18.961 28.148 27.669 1.00 25.65 6 c atom 666 o tyr a 90 17.836 28.215 27.159 1.00 23.88 8 o atom 667 cb tyr a 90 17.941 27.091 29.736 1.00 26.03 6 c atom 668 cg tyr a 90 17.539 28.168 30.704 1.00 26.25 6 c atom 669 cd1 tyr a 90 17.977 29.477 30.578 1.00 26.03 6 c atom 670 cd2 tyr a 90 16.666 27.868 31.743 1.00 25.94 6 c atom 671 ce1 tyr a 90 17.583 30.446 31.483 1.00 25.96 6 c atom 672 ce2 tyr a 90 16.273 28.826 32.651 1.00 25.75 6 c atom 673 cz tyr a 90 16.735 30.117 32.513 1.00 24.66 6 c atom 674 oh tyr a 90 16.314 31.063 33.406 1.00 24.26 8 o atom 675 n pro a 91 20.042 28.682 27.119 1.00 24.16 7 n atom 676 ca pro a 91 20.007 29.366 25.844 1.00 22.38 6 c atom 677 c pro a 91 19.347 30.720 25.876 1.00 21.65 6 c atom 678 o pro a 91 19.439 31.456 26.846 1.00 20.61 8 o atom 679 cb pro a 91 21.480 29.418 25.434 1.00 22.64 6 c atom 680 cg pro a 91 22.181 29.567 26.755 1.00 24.11 6 c atom 681 cd pro a 91 21.423 28.630 27.675 1.00 24.27 6 c atom 682 n tyr a 92 18.793 31.090 24.731 1.00 20.39 7 n atom 683 ca tyr a 92 18.093 32.335 24.525 1.00 20.26 6 c atom 684 c tyr a 92 19.023 33.528 24.394 1.00 20.72 6 c atom 685 o tyr a 92 19.872 33.569 23.519 1.00 20.05 8 o atom 686 cb tyr a 92 17.252 32.237 23.241 1.00 21.16 6 c atom 687 cg tyr a 92 16.470 33.527 23.106 1.00 22.39 6 c atom 688 cd1 tyr a 92 15.462 33.789 24.043 1.00 21.79 6 c atom 689 cd2 tyr a 92 16.702 34.443 22.100 1.00 22.14 6 c atom 690 ce1 tyr a 92 14.712 34.939 23.964 1.00 22.27 6 c atom 691 ce2 tyr a 92 15.927 35.588 22.013 1.00 21.89 6 c atom 692 cz tyr a 92 14.917 35.820 22.927 1.00 22.27 6 c atom 693 oh tyr a 92 14.191 36.982 22.847 1.00 21.59 8 o atom 694 n lys a 93 18.868 34.487 25.301 1.00 22.15 7 n atom 695 ca lys a 93 19.746 35.642 25.399 1.00 22.54 6 c atom 696 c lys a 93 19.141 36.957 24.958 1.00 20.79 6 c atom 697 o lys a 93 19.855 37.966 24.905 1.00 18.83 8 o atom 698 cb lys a 93 20.182 35.851 26.879 1.00 22.50 6 c atom 699 cg lys a 93 20.731 34.551 27.457 1.00 23.95 6 c atom 700 cd lys a 93 22.024 34.153 26.785 1.00 25.94 6 c atom 701 ce lys a 93 23.143 35.160 27.030 1.00 26.02 6 c atom 702 nz lys a 93 24.449 34.566 26.604 1.00 26.53 7 n atom 703 n ala a 94 17.851 36.909 24.649 1.00 19.89 7 n atom 704 ca ala a 94 17.122 38.112 24.253 1.00 19.34 6 c atom 705 c ala a 94 17.224 39.241 25.282 1.00 19.71 6 c atom 706 o ala a 94 17.261 40.424 24.927 1.00 17.68 8 o atom 707 cb ala a 94 17.595 38.584 22.886 1.00 18.14 6 c atom 708 n met a 95 16.953 38.903 26.534 1.00 21.05 7 n atom 709 ca met a 95 16.907 39.847 27.637 1.00 24.45 6 c atom 710 c met a 95 16.495 39.171 28.940 1.00 24.65 6 c atom 711 o met a 95 16.800 37.972 29.115 1.00 24.37 8 o atom 712 cb met a 95 18.298 40.477 27.838 1.00 26.81 6 c atom 713 cg met a 95 19.359 39.424 28.209 1.00 26.79 6 c atom 714 sd met a 95 21.029 40.005 27.871 1.00 30.72 16 s atom 715 ce met a 95 21.972 39.122 29.099 1.00 29.49 6 c atom 716 n asp a 96 15.962 39.940 29.876 1.00 25.99 7 n atom 717 ca asp a 96 15.590 39.382 31.169 1.00 27.97 6 c atom 718 c asp a 96 16.818 38.900 31.926 1.00 28.50 6 c atom 719 o asp a 96 17.838 39.575 31.939 1.00 28.69 8 o atom 720 cb asp a 96 14.807 40.443 31.955 1.00 29.78 6 c atom 721 cg asp a 96 13.626 40.858 31.075 1.00 32.20 6 c atom 722 od1 asp a 96 12.870 39.954 30.664 1.00 31.39 8 o atom 723 od2 asp a 96 13.479 42.037 30.718 1.00 34.54 8 o atom 724 n leu a 97 16.733 37.756 32.569 1.00 28.84 7 n atom 725 ca leu a 97 17.800 37.158 33.359 1.00 29.61 6 c atom 726 c leu a 97 17.083 36.598 34.609 1.00 29.21 6 c atom 727 o leu a 97 15.877 36.345 34.565 1.00 27.54 8 o atom 728 cb leu a 97 18.575 36.028 32.728 1.00 29.72 6 c atom 729 cg leu a 97 19.250 35.651 31.447 1.00 30.88 6 c atom 730 cd1 leu a 97 18.989 34.166 31.073 1.00 30.72 6 c atom 731 cd2 leu a 97 20.784 35.654 31.423 1.00 31.20 6 c atom 732 n lys a 98 17.831 36.399 35.685 1.00 27.84 7 n atom 733 ca lys a 98 17.252 35.788 36.880 1.00 27.09 6 c atom 734 c lys a 98 16.829 34.380 36.493 1.00 27.55 6 c atom 735 o lys a 98 17.465 33.788 35.609 1.00 27.68 8 o atom 736 cb lys a 98 18.341 35.689 37.956 1.00 28.62 6 c atom 737 cg lys a 98 17.548 34.862 39.319 1.00 39.81 6 c atom 738 cd lys a 98 18.150 35.112 40.684 1.00 41.59 6 c atom 739 ce lys a 98 17.708 34.025 41.672 1.00 42.03 6 c atom 740 nz lys a 98 18.353 34.248 43.004 1.00 43.18 7 n atom 741 n cys a 99 15.809 33.815 37.114 1.00 27.58 7 n atom 742 ca cys a 99 15.426 32.454 36.750 1.00 27.48 6 c atom 743 c cys a 99 16.656 31.566 36.957 1.00 29.46 6 c atom 744 o cys a 99 17.302 31.659 38.006 1.00 29.32 8 o atom 745 cb cys a 99 14.270 31.949 37.606 1.00 26.02 6 c atom 746 sg cys a 99 13.792 30.277 37.192 1.00 25.37 16 s atom 747 n gln a 100 16.959 30.725 35.978 1.00 29.42 7 n atom 748 ca gln a 100 18.055 29.776 36.114 1.00 29.28 6 c atom 749 c gln a 100 17.610 28.341 35.855 1.00 29.19 6 c atom 750 o gln a 100 18.429 27.530 35.421 1.00 27.17 8 o atom 751 cb gln a 100 19.174 30.147 35.136 1.00 29.06 6 c atom 752 cg gln a 100 20.484 29.931 35.520 1.00 46.34 6 c atom 753 cd gln a 100 21.458 29.877 34.342 1.00 48.63 6 c atom 754 oe1 gln a 100 22.029 28.797 34.129 1.00 50.35 8 o atom 755 ne2 gln a 100 21.562 30.990 33.624 1.00 48.58 7 n atom 756 n tyr a 101 16.315 28.054 36.012 1.00 29.02 7 n atom 757 ca tyr a 101 15.839 26.699 35.731 1.00 29.46 6 c atom 758 c tyr a 101 16.705 25.689 36.471 1.00 30.77 6 c atom 759 o tyr a 101 17.258 26.008 37.519 1.00 31.93 8 o atom 760 cb tyr a 101 14.358 26.530 36.072 1.00 28.65 6 c atom 761 cg tyr a 101 13.859 25.101 35.991 1.00 29.07 6 c atom 762 cd1 tyr a 101 13.748 24.489 34.746 1.00 28.89 6 c atom 763 cd2 tyr a 101 13.525 24.361 37.121 1.00 28.14 6 c atom 764 ce1 tyr a 101 13.326 23.179 34.646 1.00 30.02 6 c atom 765 ce2 tyr a 101 13.073 23.069 37.018 1.00 28.90 6 c atom 766 cz tyr a 101 12.981 22.472 35.780 1.00 29.41 6 c atom 767 oh tyr a 101 12.548 21.172 35.646 1.00 29.60 8 o atom 768 n asp a 102 16.887 24.507 35.897 1.00 31.15 7 n atom 769 ca asp a 102 17.678 23.447 36.506 1.00 30.68 6 c atom 770 c asp a 102 17.059 22.126 36.092 1.00 30.56 6 c atom 771 o asp a 102 17.072 21.747 34.917 1.00 30.33 8 o atom 772 cb asp a 102 19.150 23.555 36.110 1.00 30.88 6 c atom 773 cg asp a 102 20.018 22.423 36.634 1.00 30.35 6 c atom 774 od1 asp a 102 19.510 21.461 37.230 1.00 29.42 8 o atom 775 od2 asp a 102 21.244 22.454 36.436 1.00 31.11 8 o atom 776 n ser a 103 16.549 21.356 37.039 1.00 31.50 7 n atom 777 ca ser a 103 15.935 20.064 36.756 1.00 32.32 6 c atom 778 c ser a 103 16.854 19.076 36.062 1.00 33.09 6 c atom 779 o ser a 103 16.332 18.213 35.345 1.00 31.59 8 o atom 780 cb ser a 103 15.320 19.428 38.008 1.00 32.37 6 c atom 781 og ser a 103 16.173 19.527 39.138 1.00 31.98 8 o atom 782 n lys a 104 18.179 19.151 36.160 1.00 35.76 7 n atom 783 ca lys a 104 19.053 18.202 35.463 1.00 37.80 6 c atom 784 c lys a 104 18.851 18.236 33.950 1.00 37.33 6 c atom 785 o lys a 104 19.038 17.241 33.251 1.00 35.66 8 o atom 786 cb lys a 104 20.524 18.471 35.798 1.00 39.75 6 c atom 787 cg lys a 104 21.532 17.557 35.121 1.00 42.27 6 c atom 788 cd lys a 104 22.980 17.947 35.402 1.00 43.54 6 c atom 789 ce lys a 104 23.957 16.905 34.865 1.00 43.83 6 c atom 790 nz lys a 104 23.982 15.669 35.708 1.00 45.07 7 n atom 791 n tyr a 105 18.536 19.414 33.409 1.00 37.05 7 n atom 792 ca tyr a 105 18.382 19.612 31.979 1.00 36.81 6 c atom 793 c tyr a 105 16.943 19.729 31.504 1.00 35.99 6 c atom 794 o tyr a 105 16.673 20.287 30.429 1.00 33.12 8 o atom 795 cb tyr a 105 19.227 20.836 31.611 1.00 38.96 6 c atom 796 cg tyr a 105 20.694 20.672 31.965 1.00 41.55 6 c atom 797 cd1 tyr a 105 21.210 21.176 33.149 1.00 42.60 6 c atom 798 cd2 tyr a 105 21.552 19.983 31.125 1.00 42.60 6 c atom 799 ce1 tyr a 105 22.541 21.005 33.483 1.00 44.25 6 c atom 800 ce2 tyr a 105 22.886 19.811 31.445 1.00 43.94 6 c atom 801 cz tyr a 105 23.379 20.323 32.627 1.00 44.66 6 c atom 802 oh tyr a 105 24.711 20.121 32.925 1.00 45.49 8 o atom 803 n arg a 106 15.982 19.220 32.284 1.00 35.58 7 n atom 804 ca arg a 106 14.585 19.274 31.881 1.00 35.22 6 c atom 805 c arg a 106 14.428 18.483 30.575 1.00 33.66 6 c atom 806 o arg a 106 14.848 17.317 30.544 1.00 32.71 8 o atom 807 cb arg a 106 13.596 18.692 32.885 1.00 37.05 6 c atom 808 cg arg a 106 12.195 18.554 32.329 1.00 39.12 6 c atom 809 cd arg a 106 11.197 17.832 33.187 1.00 41.38 6 c atom 810 ne arg a 106 11.744 17.036 34.270 1.00 43.12 7 n atom 811 cz arg a 106 11.774 17.509 35.515 1.00 45.18 6 c atom 812 nh1 arg a 106 11.276 18.723 35.741 1.00 46.74 7 n atom 813 nh2 arg a 106 12.286 16.820 36.516 1.00 45.39 7 n atom 814 n ala a 107 13.727 19.086 29.616 1.00 30.82 7 n atom 815 ca ala a 107 13.555 18.345 28.358 1.00 29.53 6 c atom 816 c ala a 107 12.092 18.012 28.133 1.00 28.50 6 c atom 817 o ala a 107 11.796 17.176 27.292 1.00 29.94 8 o atom 818 cb ala a 107 14.125 19.200 27.231 1.00 29.16 6 c atom 819 n ala a 108 11.144 18.630 28.833 1.00 28.04 7 n atom 820 ca ala a 108 9.729 18.348 28.637 1.00 27.60 6 c atom 821 c ala a 108 8.870 18.770 29.829 1.00 27.82 6 c atom 822 o ala a 108 9.330 19.529 30.674 1.00 28.33 8 o atom 823 cb ala a 108 9.165 19.093 27.420 1.00 26.00 6 c atom 824 n thr a 109 7.643 18.270 29.843 1.00 28.37 7 n atom 825 ca thr a 109 6.685 18.648 30.886 1.00 30.12 6 c atom 826 c thr a 109 5.297 18.948 30.328 1.00 29.00 6 c atom 827 o thr a 109 5.029 18.586 29.179 1.00 30.28 8 o atom 828 cb thr a 109 6.537 17.485 31.890 1.00 30.39 6 c atom 829 og1 thr a 109 5.493 17.830 32.806 1.00 33.72 8 o atom 830 cg2 thr a 109 6.181 16.207 31.158 1.00 29.62 6 c atom 831 n cys a 110 4.387 19.478 31.134 1.00 28.87 7 n atom 832 ca cys a 110 3.019 19.727 30.697 1.00 28.09 6 c atom 833 c cys a 110 2.025 19.414 31.803 1.00 29.30 6 c atom 834 o cys a 110 2.238 19.782 32.961 1.00 29.59 8 o atom 835 cb cys a 110 2.861 21.183 30.233 1.00 27.11 6 c atom 836 sg cys a 110 1.262 21.583 29.499 1.00 24.00 16 s atom 837 n ser a 111 0.928 18.739 31.481 1.00 30.28 7 n atom 838 ca ser a 111 0.080 18.404 32.470 1.00 30.99 6 c atom 839 c ser a 111 1.276 19.348 32.408 1.00 31.45 6 c atom 840 o ser a 111 1.940 19.484 33.425 1.00 31.58 8 o atom 841 cb ser a 111 0.647 16.999 32.216 1.00 31.38 6 c atom 842 og ser a 111 0.405 16.192 31.722 1.00 33.93 8 o atom 843 n lys a 112 1.610 19.806 31.195 1.00 31.38 7 n atom 844 ca lys a 112 2.797 20.625 31.012 1.00 30.62 6 c atom 845 c lys a 112 2.704 21.538 29.795 1.00 29.73 6 c atom 846 o lys a 112 2.062 21.186 28.803 1.00 30.73 8 o atom 847 cb lys a 112 4.050 19.753 30.870 1.00 31.67 6 c atom 848 cg lys a 112 4.243 18.944 29.614 1.00 33.08 6 c atom 849 cd lys a 112 5.683 18.790 29.174 1.00 33.67 6 c atom 850 ce lys a 112 6.584 18.089 30.163 1.00 34.48 6 c atom 851 nz lys a 112 8.159 18.200 29.948 1.00 46.23 7 n atom 852 n tyr a 113 3.314 22.706 29.842 1.00 28.03 7 n atom 853 ca tyr a 113 3.366 23.489 28.593 1.00 26.64 6 c atom 854 c tyr a 113 4.837 23.658 28.265 1.00 26.44 6 c atom 855 o tyr a 113 5.682 23.518 29.154 1.00 24.84 8 o atom 856 cb tyr a 113 2.541 24.744 28.680 1.00 25.60 6 c atom 857 cg tyr a 113 3.057 25.824 29.582 1.00 25.86 6 c atom 858 cd1 tyr a 113 3.926 26.743 29.006 1.00 26.36 6 c atom 859 cd2 tyr a 113 2.712 25.972 30.909 1.00 25.51 6 c atom 860 ce1 tyr a 113 4.454 27.795 29.739 1.00 25.64 6 c atom 861 ce2 tyr a 113 3.210 27.029 31.641 1.00 26.27 6 c atom 862 cz tyr a 113 4.076 27.924 31.052 1.00 26.55 6 c atom 863 oh tyr a 113 4.579 28.979 31.776 1.00 29.49 8 o atom 864 n thr a 114 5.157 23.928 27.006 1.00 26.59 7 n atom 865 ca thr a 114 6.540 24.120 26.585 1.00 27.79 6 c atom 866 c thr a 114 6.647 25.343 25.662 1.00 27.79 6 c atom 867 o thr a 114 5.999 25.432 24.622 1.00 26.59 8 o atom 868 cb thr a 114 7.118 22.925 25.800 1.00 28.47 6 c atom 869 og1 thr a 114 7.022 21.716 26.565 1.00 28.45 8 o atom 870 cg2 thr a 114 8.548 23.203 25.363 1.00 27.01 6 c atom 871 n glu a 115 7.546 26.244 26.027 1.00 28.03 7 n atom 872 ca glu a 115 7.806 27.444 25.253 1.00 28.31 6 c atom 873 c glu a 115 9.077 27.287 24.415 1.00 26.45 6 c atom 874 o glu a 115 10.065 26.828 24.966 1.00 24.11 8 o atom 875 cb glu a 115 8.101 28.637 26.157 1.00 30.49 6 c atom 876 cg glu a 115 7.372 28.589 27.485 1.00 34.67 6 c atom 877 cd glu a 115 7.705 29.814 28.317 1.00 36.29 6 c atom 878 oe1 glu a 115 6.957 30.802 28.181 1.00 38.25 8 o atom 879 oe2 glu a 115 8.696 29.769 29.069 1.00 39.15 8 o atom 880 n leu a 116 9.018 27.700 23.167 1.00 25.14 7 n atom 881 ca leu a 116 10.135 27.608 22.263 1.00 25.16 6 c atom 882 c leu a 116 11.054 28.824 22.320 1.00 24.89 6 c atom 883 o leu a 116 10.641 29.898 22.746 1.00 23.04 8 o atom 884 cb leu a 116 9.659 27.416 20.826 1.00 25.43 6 c atom 885 cg leu a 116 8.784 26.187 20.579 1.00 25.71 6 c atom 886 cd1 leu a 116 8.481 26.106 19.100 1.00 25.82 6 c atom 887 cd2 leu a 116 9.421 24.914 21.103 1.00 27.18 6 c atom 888 n pro a 117 12.304 28.641 21.888 1.00 24.28 7 n atom 889 ca pro a 117 13.293 29.697 21.877 1.00 23.98 6 c atom 890 c pro a 117 12.868 30.877 21.019 1.00 22.49 6 c atom 891 o pro a 117 12.365 30.759 19.915 1.00 22.50 8 o atom 892 cb pro a 117 14.596 29.038 21.412 1.00 24.47 6 c atom 893 cg pro a 117 14.319 27.579 21.360 1.00 25.14 6 c atom 894 cd pro a 117 12.829 27.364 21.356 1.00 24.60 6 c atom 895 n tyr a 118 13.002 32.087 21.547 1.00 21.36 7 n atom 896 ca tyr a 118 12.691 33.318 20.861 1.00 21.59 6 c atom 897 c tyr a 118 13.203 33.390 19.431 1.00 21.06 6 c atom 898 o tyr a 118 14.396 33.232 19.195 1.00 19.33 8 o atom 899 cb tyr a 118 13.326 34.528 21.591 1.00 22.46 6 c atom 900 cg tyr a 118 12.895 35.829 20.938 1.00 23.39 6 c atom 901 cd1 tyr a 118 13.564 36.453 19.901 1.00 22.31 6 c atom 902 cd2 tyr a 118 11.711 36.406 21.407 1.00 23.67 6 c atom 903 ce1 tyr a 118 13.086 37.624 19.337 1.00 22.81 6 c atom 904 ce2 tyr a 118 11.229 37.578 20.862 1.00 21.86 6 c atom 905 cz tyr a 118 11.907 38.179 19.831 1.00 22.33 6 c atom 906 oh tyr a 118 11.373 39.337 19.327 1.00 20.93 8 o atom 907 n gly a 119 12.328 33.728 18.484 1.00 20.73 7 n atom 908 ca gly a 119 12.645 33.926 17.100 1.00 19.44 6 c atom 909 c gly a 119 13.143 32.750 16.293 1.00 19.69 6 c atom 910 o gly a 119 13.361 32.930 15.084 1.00 19.60 8 o atom 911 n arg a 120 13.223 31.549 16.857 1.00 19.84 7 n atom 912 ca arg a 120 13.778 30.391 16.166 1.00 19.67 6 c atom 913 c arg a 120 12.741 29.672 15.321 1.00 19.06 6 c atom 914 o arg a 120 11.965 28.800 15.691 1.00 16.52 8 o atom 915 cb arg a 120 14.532 29.510 17.162 1.00 20.06 6 c atom 916 cg arg a 120 15.877 30.088 17.624 1.00 19.22 6 c atom 917 cd arg a 120 16.895 30.186 16.507 1.00 18.90 6 c atom 918 ne arg a 120 17.321 28.905 15.948 1.00 19.77 7 n atom 919 cz arg a 120 18.239 28.106 16.500 1.00 20.36 6 c atom 920 nh1 arg a 120 18.578 26.951 15.950 1.00 21.29 7 n atom 921 nh2 arg a 120 18.834 28.449 17.634 1.00 19.03 7 n atom 922 n glu a 121 12.814 30.009 14.021 1.00 19.45 7 n atom 923 ca glu a 121 11.799 29.549 13.063 1.00 19.61 6 c atom 924 c glu a 121 11.992 28.082 12.709 1.00 20.60 6 c atom 925 o glu a 121 11.037 27.345 12.414 1.00 20.89 8 o atom 926 cb glu a 121 11.747 30.492 11.865 1.00 18.24 6 c atom 927 cg glu a 121 11.051 31.811 12.220 1.00 18.86 6 c atom 928 cd glu a 121 10.797 32.663 10.989 1.00 19.96 6 c atom 929 oe1 glu a 121 9.770 32.439 10.315 1.00 19.81 8 o atom 930 oe2 glu a 121 11.600 33.557 10.629 1.00 20.40 8 o atom 931 n asp a 122 13.241 27.626 12.716 1.00 19.89 7 n atom 932 ca asp a 122 13.586 26.218 12.529 1.00 19.72 6 c atom 933 c asp a 122 13.072 25.400 13.705 1.00 19.29 6 c atom 934 o asp a 122 12.484 24.338 13.521 1.00 19.52 8 o atom 935 cb asp a 122 15.108 26.049 12.434 1.00 20.29 6 c atom 936 cg asp a 122 15.867 26.754 13.552 1.00 20.53 6 c atom 937 od1 asp a 122 15.432 27.748 14.169 1.00 19.33 8 o atom 938 od2 asp a 122 16.985 26.284 13.843 1.00 20.00 8 o atom 939 n val a 123 13.218 25.896 14.932 1.00 19.63 7 n atom 940 ca val a 123 12.683 25.167 16.082 1.00 20.15 6 c atom 941 c val a 123 11.160 25.117 16.069 1.00 19.82 6 c atom 942 o val a 123 10.581 24.080 16.393 1.00 21.01 8 o atom 943 cb val a 123 13.224 25.708 17.409 1.00 20.72 6 c atom 944 cg1 val a 123 12.741 24.865 18.586 1.00 19.61 6 c atom 945 cg2 val a 123 14.751 25.666 17.374 1.00 21.00 6 c atom 946 n leu a 124 10.482 26.192 15.684 1.00 19.45 7 n atom 947 ca leu a 124 9.034 26.204 15.543 1.00 17.29 6 c atom 948 c leu a 124 8.587 25.205 14.466 1.00 16.81 6 c atom 949 o leu a 124 7.617 24.483 14.630 1.00 14.06 8 o atom 950 cb leu a 124 8.528 27.595 15.109 1.00 16.10 6 c atom 951 cg leu a 124 6.994 27.693 14.930 1.00 15.09 6 c atom 952 cd1 leu a 124 6.303 27.248 16.214 1.00 13.15 6 c atom 953 cd2 leu a 124 6.568 29.112 14.549 1.00 14.30 6 c atom 954 n lys a 125 9.288 25.174 13.336 1.00 17.30 7 n atom 955 ca lys a 125 9.003 24.247 12.254 1.00 19.43 6 c atom 956 c lys a 125 9.005 22.811 12.770 1.00 20.30 6 c atom 957 o lys a 125 8.017 22.090 12.617 1.00 18.99 8 o atom 958 cb lys a 125 9.998 24.386 11.103 1.00 20.04 6 c atom 959 cg lys a 125 9.724 23.440 9.948 1.00 21.22 6 c atom 960 cd lys a 125 10.641 23.668 8.758 1.00 22.50 6 c atom 961 ce lys a 125 10.871 22.373 7.989 1.00 23.62 6 c atom 962 nz lys a 125 11.506 22.596 6.661 1.00 23.20 7 n atom 963 n glu a 126 10.085 22.462 13.474 1.00 21.92 7 n atom 964 ca glu a 126 10.163 21.145 14.093 1.00 25.66 6 c atom 965 c glu a 126 9.047 20.904 15.103 1.00 24.45 6 c atom 966 o glu a 126 8.436 19.816 15.077 1.00 23.61 8 o atom 967 cb glu a 126 11.552 20.915 14.703 1.00 29.31 6 c atom 968 cg glu a 126 11.616 19.797 15.737 1.00 33.75 6 c atom 969 cd glu a 126 13.042 19.478 16.159 1.00 37.53 6 c atom 970 oe1 glu a 126 13.252 18.340 16.645 1.00 39.17 8 o atom 971 oe2 glu a 126 13.944 20.342 16.014 1.00 38.33 8 o atom 972 n ala a 127 8.716 21.855 15.976 1.00 22.89 7 n atom 973 ca ala a 127 7.595 21.610 16.892 1.00 22.42 6 c atom 974 c ala a 127 6.263 21.373 16.189 1.00 21.97 6 c atom 975 o ala a 127 5.478 20.498 16.574 1.00 22.41 8 o atom 976 cb ala a 127 7.437 22.761 17.870 1.00 22.20 6 c atom 977 n val a 128 5.945 22.173 15.183 1.00 21.64 7 n atom 978 ca val a 128 4.736 22.073 14.402 1.00 21.56 6 c atom 979 c val a 128 4.639 20.693 13.766 1.00 22.59 6 c atom 980 o val a 128 3.553 20.109 13.756 1.00 23.86 8 o atom 981 cb val a 128 4.638 23.147 13.294 1.00 21.77 6 c atom 982 cg1 val a 128 3.486 22.862 12.337 1.00 19.24 6 c atom 983 cg2 val a 128 4.452 24.530 13.925 1.00 20.70 6 c atom 984 n ala a 129 5.729 20.203 13.181 1.00 22.80 7 n atom 985 ca ala a 129 5.674 18.880 12.565 1.00 22.75 6 c atom 986 c ala a 129 5.511 17.787 13.616 1.00 22.71 6 c atom 987 o ala a 129 4.780 16.822 13.389 1.00 23.44 8 o atom 988 cb ala a 129 6.910 18.527 11.740 1.00 20.00 6 c atom 989 n asn a 130 6.328 17.837 14.658 1.00 24.07 7 n atom 990 ca asn a 130 6.382 16.693 15.561 1.00 25.89 6 c atom 991 c asn a 130 5.479 16.733 16.768 1.00 25.42 6 c atom 992 o asn a 130 5.295 15.626 17.269 1.00 27.13 8 o atom 993 cb asn a 130 7.836 16.485 16.015 1.00 27.47 6 c atom 994 cg asn a 130 8.720 16.119 14.840 1.00 29.35 6 c atom 995 od1 asn a 130 8.249 15.475 13.893 1.00 30.70 8 o atom 996 nd2 asn a 130 9.956 16.584 14.865 1.00 29.01 7 n atom 997 n lys a 131 5.028 17.871 17.268 1.00 24.28 7 n atom 998 ca lys a 131 4.168 17.931 18.435 1.00 23.51 6 c atom 999 c lys a 131 2.697 18.234 18.126 1.00 22.64 6 c atom 1000 o lys a 131 1.799 17.601 18.697 1.00 21.17 8 o atom 1001 cb lys a 131 4.641 19.061 19.367 1.00 24.90 6 c atom 1002 cg lys a 131 5.606 18.688 20.465 1.00 26.15 6 c atom 1003 cd lys a 131 6.781 17.881 20.010 1.00 27.86 6 c atom 1004 ce lys a 131 7.879 17.742 21.050 1.00 29.68 6 c atom 1005 nz lys a 131 7.867 16.402 21.691 1.00 29.96 7 n atom 1006 n gly a 132 2.484 19.237 17.279 1.00 20.55 7 n atom 1007 ca gly a 132 1.147 19.657 16.863 1.00 20.25 6 c atom 1008 c gly a 132 1.136 21.181 16.695 1.00 19.24 6 c atom 1009 o gly a 132 2.181 21.836 16.816 1.00 19.27 8 o atom 1010 n pro a 133 0.036 21.745 16.470 1.00 17.37 7 n atom 1011 ca pro a 133 0.218 23.175 16.371 1.00 17.05 6 c atom 1012 c pro a 133 0.364 23.942 17.552 1.00 16.38 6 c atom 1013 o pro a 133 0.274 23.546 18.715 1.00 13.98 8 o atom 1014 cb pro a 133 1.737 23.341 16.283 1.00 16.46 6 c atom 1015 cg pro a 133 2.213 22.045 15.676 1.00 16.62 6 c atom 1016 cd pro a 133 1.323 21.016 16.320 1.00 17.85 6 c atom 1017 n val a 134 0.996 25.086 17.280 1.00 15.75 7 n atom 1018 ca val a 134 1.680 25.863 18.309 1.00 15.90 6 c atom 1019 c val a 134 1.117 27.259 18.499 1.00 15.95 6 c atom 1020 o val a 134 0.833 27.984 17.540 1.00 16.80 8 o atom 1021 cb val a 134 3.190 25.953 18.021 1.00 14.77 6 c atom 1022 cg1 val a 134 3.933 26.824 19.031 1.00 12.60 6 c atom 1023 cg2 val a 134 3.821 24.565 17.985 1.00 15.02 6 c atom 1024 n ser a 135 0.904 27.605 19.762 1.00 16.37 7 n atom 1025 ca ser a 135 0.384 28.926 20.111 1.00 15.61 6 c atom 1026 c ser a 135 1.488 29.963 19.988 1.00 15.26 6 c atom 1027 o ser a 135 2.618 29.763 20.487 1.00 14.54 8 o atom 1028 cb ser a 135 0.163 28.944 21.539 1.00 15.74 6 c atom 1029 og ser a 135 1.155 27.954 21.737 1.00 14.29 8 o atom 1030 n val a 136 1.199 31.002 19.191 1.00 13.15 7 n atom 1031 ca val a 136 2.175 32.073 19.017 1.00 12.51 6 c atom 1032 c val a 136 1.472 33.420 19.084 1.00 12.80 6 c atom 1033 o val a 136 0.239 33.475 18.907 1.00 12.74 8 o atom 1034 cb val a 136 2.863 32.017 17.633 1.00 11.40 6 c atom 1035 cg1 val a 136 3.675 30.719 17.490 1.00 11.79 6 c atom 1036 cg2 val a 136 1.830 32.124 16.528 1.00 10.93 6 c atom 1037 n gly a 137 2.269 34.469 19.213 1.00 13.13 7 n atom 1038 ca gly a 137 1.721 35.816 19.066 1.00 12.05 6 c atom 1039 c gly a 137 2.240 36.390 17.740 1.00 14.27 6 c atom 1040 o gly a 137 3.323 36.044 17.240 1.00 13.27 8 o atom 1041 n val a 138 1.515 37.378 17.188 1.00 13.76 7 n atom 1042 ca val a 138 1.974 38.086 16.014 1.00 15.53 6 c atom 1043 c val a 138 1.616 39.566 16.237 1.00 16.13 6 c atom 1044 o val a 138 0.827 39.920 17.116 1.00 15.77 8 o atom 1045 cb val a 138 1.451 37.665 14.629 1.00 15.17 6 c atom 1046 cg1 val a 138 1.782 36.237 14.225 1.00 12.68 6 c atom 1047 cg2 val a 138 0.070 37.808 14.646 1.00 15.85 6 c atom 1048 n asp a 139 2.312 40.405 15.510 1.00 16.45 7 n atom 1049 ca asp a 139 2.074 41.839 15.404 1.00 16.56 6 c atom 1050 c asp a 139 1.011 41.945 14.299 1.00 16.67 6 c atom 1051 o asp a 139 1.388 41.827 13.127 1.00 15.17 8 o atom 1052 cb asp a 139 3.295 42.642 14.970 1.00 14.71 6 c atom 1053 cg asp a 139 3.060 44.125 14.782 1.00 17.17 6 c atom 1054 od1 asp a 139 1.962 44.621 15.138 1.00 17.02 8 o atom 1055 od2 asp a 139 3.975 44.838 14.289 1.00 14.60 8 o atom 1056 n ala a 140 0.238 42.128 14.704 1.00 17.09 7 n atom 1057 ca ala a 140 1.331 42.201 13.745 1.00 17.51 6 c atom 1058 c ala a 140 1.852 43.633 13.590 1.00 19.31 6 c atom 1059 o ala a 140 2.924 43.808 12.982 1.00 18.42 8 o atom 1060 cb ala a 140 2.485 41.373 14.276 1.00 16.94 6 c atom 1061 n arg a 141 1.138 44.596 14.168 1.00 17.62 7 n atom 1062 ca arg a 141 1.604 45.973 14.121 1.00 21.70 6 c atom 1063 c arg a 141 1.295 46.741 12.861 1.00 21.24 6 c atom 1064 o arg a 141 0.491 47.683 12.908 1.00 23.78 8 o atom 1065 cb arg a 141 1.022 46.763 15.324 1.00 22.98 6 c atom 1066 cg arg a 141 1.524 46.205 16.646 1.00 25.16 6 c atom 1067 cd arg a 141 1.173 47.074 17.838 1.00 25.54 6 c atom 1068 ne arg a 141 1.756 46.493 19.054 1.00 26.83 7 n atom 1069 cz arg a 141 1.457 46.813 20.306 1.00 27.15 6 c atom 1070 nh1 arg a 141 0.595 47.780 20.573 1.00 27.93 7 n atom 1071 nh2 arg a 141 2.027 46.200 21.335 1.00 28.15 7 n atom 1072 n his a 142 1.664 46.307 11.680 1.00 20.53 7 n atom 1073 ca his a 142 1.408 46.985 10.406 1.00 20.76 6 c atom 1074 c his a 142 2.644 46.813 9.537 1.00 20.78 6 c atom 1075 o his a 142 3.082 45.648 9.467 1.00 21.08 8 o atom 1076 cb his a 142 0.180 46.315 9.723 1.00 20.65 6 c atom 1077 cg his a 142 1.075 46.606 10.506 1.00 21.46 6 c atom 1078 nd1 his a 142 1.623 45.689 11.384 1.00 20.82 7 n atom 1079 cd2 his a 142 1.759 47.757 10.676 1.00 20.06 6 c atom 1080 ce1 his a 142 2.636 46.251 12.001 1.00 20.89 6 c atom 1081 ne2 his a 142 2.727 47.509 11.599 1.00 20.80 7 n atom 1082 n pro a 143 3.119 47.802 8.804 1.00 20.03 7 n atom 1083 ca pro a 143 4.245 47.631 7.897 1.00 20.34 6 c atom 1084 c pro a 143 4.094 46.365 7.082 1.00 18.65 6 c atom 1085 o pro a 143 5.029 45.598 6.930 1.00 17.09 8 o atom 1086 cb pro a 143 4.256 48.895 7.039 1.00 20.31 6 c atom 1087 cg pro a 143 3.706 49.932 7.978 1.00 19.99 6 c atom 1088 cd pro a 143 2.646 49.201 8.793 1.00 19.76 6 c atom 1089 n ser a 144 2.938 46.186 6.498 1.00 17.95 7 n atom 1090 ca ser a 144 2.419 45.007 5.852 1.00 18.06 6 c atom 1091 c ser a 144 3.012 43.711 6.433 1.00 18.09 6 c atom 1092 o ser a 144 3.293 42.752 5.698 1.00 17.56 8 o atom 1093 cb ser a 144 0.995 45.087 6.439 1.00 18.08 6 c atom 1094 og ser a 144 0.052 44.459 5.893 1.00 18.27 8 o atom 1095 n phe a 145 2.861 43.559 7.756 1.00 16.72 7 n atom 1096 ca phe a 145 3.259 42.308 8.406 1.00 17.71 6 c atom 1097 c phe a 145 4.773 42.168 8.311 1.00 18.02 6 c atom 1098 o phe a 145 5.194 41.202 7.649 1.00 17.64 8 o atom 1099 cb phe a 145 2.743 42.211 9.839 1.00 17.73 6 c atom 1100 cg phe a 145 2.918 40.852 10.436 1.00 17.54 6 c atom 1101 cd1 phe a 145 1.838 39.999 10.535 1.00 18.10 6 c atom 1102 cd2 phe a 145 4.159 40.436 10.881 1.00 18.89 6 c atom 1103 ce1 phe a 145 1.973 38.737 11.089 1.00 18.91 6 c atom 1104 ce2 phe a 145 4.303 39.169 11.428 1.00 20.49 6 c atom 1105 cz phe a 145 3.210 38.326 11.536 1.00 19.41 6 c atom 1106 n phe a 146 5.595 43.019 8.878 1.00 19.20 7 n atom 1107 ca phe a 146 7.053 42.937 8.812 1.00 22.75 6 c atom 1108 c phe a 146 7.573 42.683 7.404 1.00 22.08 6 c atom 1109 o phe a 146 8.406 41.808 7.137 1.00 21.21 8 o atom 1110 cb phe a 146 7.759 44.177 9.373 1.00 28.40 6 c atom 1111 cg phe a 146 9.255 44.207 9.497 1.00 34.22 6 c atom 1112 cd1 phe a 146 9.899 43.812 10.664 1.00 35.82 6 c atom 1113 cd2 phe a 146 10.054 44.647 8.454 1.00 35.66 6 c atom 1114 ce1 phe a 146 11.285 43.862 10.770 1.00 37.01 6 c atom 1115 ce2 phe a 146 11.426 44.687 8.544 1.00 36.85 6 c atom 1116 cz phe a 146 12.054 44.301 9.711 1.00 37.74 6 c atom 1117 n leu a 147 6.970 43.271 6.376 1.00 19.53 7 n atom 1118 ca leu a 147 7.392 43.181 5.011 1.00 18.93 6 c atom 1119 c leu a 147 6.889 42.004 4.186 1.00 17.46 6 c atom 1120 o leu a 147 7.326 41.908 3.034 1.00 15.50 8 o atom 1121 cb leu a 147 6.967 44.484 4.283 1.00 18.33 6 c atom 1122 cg leu a 147 7.787 45.739 4.564 1.00 21.73 6 c atom 1123 cd1 leu a 147 8.298 45.872 5.978 1.00 21.70 6 c atom 1124 cd2 leu a 147 6.918 46.976 4.244 1.00 21.76 6 c atom 1125 n tyr a 148 5.946 41.203 4.662 1.00 16.56 7 n atom 1126 ca tyr a 148 5.434 40.069 3.905 1.00 16.70 6 c atom 1127 c tyr a 148 6.501 39.170 3.289 1.00 16.77 6 c atom 1128 o tyr a 148 7.432 38.781 4.023 1.00 17.96 8 o atom 1129 cb tyr a 148 4.554 39.282 4.890 1.00 16.18 6 c atom 1130 cg tyr a 148 4.168 37.916 4.354 1.00 17.56 6 c atom 1131 cd1 tyr a 148 4.924 36.802 4.688 1.00 17.15 6 c atom 1132 cd2 tyr a 148 3.071 37.745 3.528 1.00 16.54 6 c atom 1133 ce1 tyr a 148 4.585 35.556 4.201 1.00 16.90 6 c atom 1134 ce2 tyr a 148 2.684 36.493 3.081 1.00 17.60 6 c atom 1135 cz tyr a 148 3.470 35.401 3.411 1.00 17.72 6 c atom 1136 oh tyr a 148 3.144 34.141 2.938 1.00 16.70 8 o atom 1137 n arg a 149 6.449 38.793 2.023 1.00 17.44 7 n atom 1138 ca arg a 149 7.430 37.898 1.446 1.00 19.25 6 c atom 1139 c arg a 149 6.752 36.576 1.073 1.00 19.34 6 c atom 1140 o arg a 149 7.286 35.499 1.367 1.00 18.38 8 o atom 1141 cb arg a 149 8.172 38.427 0.222 1.00 20.29 6 c atom 1142 cg arg a 149 8.986 39.688 0.387 1.00 21.48 6 c atom 1143 cd arg a 149 9.868 39.706 1.624 1.00 22.27 6 c atom 1144 ne arg a 149 10.893 38.659 1.602 1.00 22.65 7 n atom 1145 cz arg a 149 11.624 38.242 2.623 1.00 23.37 6 c atom 1146 nh1 arg a 149 11.489 38.706 3.856 1.00 24.26 7 n atom 1147 nh2 arg a 149 12.530 37.284 2.420 1.00 22.64 7 n atom 1148 n ser a 150 5.582 36.670 0.442 1.00 19.76 7 n atom 1149 ca ser a 150 4.944 35.441 0.036 1.00 21.28 6 c atom 1150 c ser a 150 3.462 35.561 0.308 1.00 21.01 6 c atom 1151 o ser a 150 2.970 36.681 0.379 1.00 20.26 8 o atom 1152 cb ser a 150 5.675 35.161 1.384 1.00 21.60 6 c atom 1153 og ser a 150 5.423 36.337 2.166 1.00 24.11 8 o atom 1154 n gly a 151 2.730 34.445 0.407 1.00 21.86 7 n atom 1155 ca gly a 151 1.303 34.525 0.711 1.00 21.56 6 c atom 1156 c gly a 151 0.437 34.476 0.542 1.00 22.52 6 c atom 1157 o gly a 151 0.940 34.152 1.618 1.00 23.36 8 o atom 1158 n val a 152 0.863 34.739 0.387 1.00 22.51 7 n atom 1159 ca val a 152 1.767 34.677 1.533 1.00 22.20 6 c atom 1160 c val a 152 1.980 36.123 1.961 1.00 22.68 6 c atom 1161 o val a 152 2.470 36.950 1.201 1.00 25.11 8 o atom 1162 cb val a 152 3.090 33.966 1.246 1.00 21.32 6 c atom 1163 cg1 val a 152 4.150 34.286 2.297 1.00 21.42 6 c atom 1164 cg2 val a 152 2.899 32.460 1.167 1.00 20.90 6 c atom 1165 n tyr a 153 1.483 36.451 3.129 1.00 21.86 7 n atom 1166 ca tyr a 153 1.478 37.770 3.720 1.00 21.18 6 c atom 1167 c tyr a 153 2.828 38.229 4.247 1.00 21.78 6 c atom 1168 o tyr a 153 3.486 37.554 5.030 1.00 22.38 8 o atom 1169 cb tyr a 153 0.471 37.751 4.877 1.00 19.74 6 c atom 1170 cg tyr a 153 0.387 39.041 5.660 1.00 19.40 6 c atom 1171 cd1 tyr a 153 0.333 40.141 5.182 1.00 18.58 6 c atom 1172 cd2 tyr a 153 1.024 39.136 6.894 1.00 17.92 6 c atom 1173 ce1 tyr a 153 0.406 41.306 5.927 1.00 16.49 6 c atom 1174 ce2 tyr a 153 0.973 40.299 7.623 1.00 16.66 6 c atom 1175 cz tyr a 153 0.247 41.387 7.137 1.00 16.66 6 c atom 1176 oh tyr a 153 0.191 42.541 7.876 1.00 13.94 8 o atom 1177 n tyr a 154 3.264 39.387 3.777 1.00 23.40 7 n atom 1178 ca tyr a 154 4.533 39.991 4.145 1.00 24.73 6 c atom 1179 c tyr a 154 4.303 41.497 4.273 1.00 24.63 6 c atom 1180 o tyr a 154 3.770 42.159 3.382 1.00 22.58 8 o atom 1181 cb tyr a 154 5.693 39.698 3.182 1.00 27.54 6 c atom 1182 cg tyr a 154 7.002 40.326 3.650 1.00 30.83 6 c atom 1183 cd1 tyr a 154 7.823 39.737 4.600 1.00 30.63 6 c atom 1184 cd2 tyr a 154 7.397 41.549 3.129 1.00 32.15 6 c atom 1185 ce1 tyr a 154 8.988 40.350 5.010 1.00 32.27 6 c atom 1186 ce2 tyr a 154 8.565 42.180 3.533 1.00 33.35 6 c atom 1187 cz tyr a 154 9.352 41.570 4.488 1.00 33.35 6 c atom 1188 oh tyr a 154 10.523 42.184 4.877 1.00 34.87 8 o atom 1189 n glu a 155 4.606 42.012 5.459 1.00 24.20 7 n atom 1190 ca glu a 155 4.409 43.420 5.767 1.00 23.96 6 c atom 1191 c glu a 155 5.731 44.048 6.181 1.00 24.30 6 c atom 1192 o glu a 155 6.246 43.826 7.274 1.00 23.95 8 o atom 1193 cb glu a 155 3.366 43.568 6.876 1.00 23.12 6 c atom 1194 cg glu a 155 3.112 44.948 7.416 1.00 21.27 6 c atom 1195 cd glu a 155 2.829 46.034 6.405 1.00 21.50 6 c atom 1196 oe1 glu a 155 1.767 46.059 5.760 1.00 18.88 8 o atom 1197 oe2 glu a 155 3.749 46.894 6.237 1.00 23.11 8 o atom 1198 n pro a 156 6.223 44.971 5.351 1.00 25.33 7 n atom 1199 ca pro a 156 7.471 45.663 5.590 1.00 25.20 6 c atom 1200 c pro a 156 7.529 46.411 6.911 1.00 25.30 6 c atom 1201 o pro a 156 8.606 46.479 7.516 1.00 25.86 8 o atom 1202 cb pro a 156 7.649 46.582 4.387 1.00 26.28 6 c atom 1203 cg pro a 156 6.692 46.115 3.341 1.00 25.91 6 c atom 1204 cd pro a 156 5.616 45.330 4.039 1.00 25.57 6 c atom 1205 n ser a 157 6.409 46.932 7.391 1.00 24.59 7 n atom 1206 ca ser a 157 6.373 47.631 8.663 1.00 24.58 6 c atom 1207 c ser a 157 6.045 46.695 9.819 1.00 23.16 6 c atom 1208 o ser a 157 5.767 47.224 10.895 1.00 22.52 8 o atom 1209 cb ser a 157 5.364 48.790 8.606 1.00 26.25 6 c atom 1210 og ser a 157 5.761 49.711 7.603 1.00 29.54 8 o atom 1211 n cys a 158 6.107 45.371 9.637 1.00 21.33 7 n atom 1212 ca cys a 158 5.776 44.500 10.755 1.00 20.07 6 c atom 1213 c cys a 158 6.942 44.521 11.742 1.00 21.01 6 c atom 1214 o cys a 158 8.095 44.705 11.342 1.00 21.51 8 o atom 1215 cb cys a 158 5.517 43.060 10.309 1.00 16.83 6 c atom 1216 sg cys a 158 3.927 42.529 10.989 1.00 15.02 16 s atom 1217 n thr a 159 6.636 44.362 13.016 1.00 21.12 7 n atom 1218 ca thr a 159 7.707 44.379 14.010 1.00 21.47 6 c atom 1219 c thr a 159 7.547 43.083 14.810 1.00 21.05 6 c atom 1220 o thr a 159 6.509 42.456 14.662 1.00 20.59 8 o atom 1221 cb thr a 159 7.643 45.484 15.066 1.00 20.41 6 c atom 1222 og1 thr a 159 6.544 45.133 15.930 1.00 19.49 8 o atom 1223 cg2 thr a 159 7.382 46.856 14.473 1.00 22.49 6 c atom 1224 n gln a 160 8.476 42.921 15.728 1.00 21.60 7 n atom 1225 ca gln a 160 8.476 41.769 16.621 1.00 22.71 6 c atom 1226 c gln a 160 7.764 41.996 17.940 1.00 20.83 6 c atom 1227 o gln a 160 7.859 41.150 18.830 1.00 19.88 8 o atom 1228 cb gln a 160 9.944 41.372 16.841 1.00 23.85 6 c atom 1229 cg gln a 160 10.527 40.967 15.487 1.00 25.84 6 c atom 1230 cd gln a 160 11.761 40.118 15.636 1.00 27.60 6 c atom 1231 oe1 gln a 160 11.965 39.457 16.657 1.00 29.03 8 o atom 1232 ne2 gln a 160 12.618 40.108 14.626 1.00 27.70 7 n atom 1233 n asn a 161 7.100 43.136 18.074 1.00 19.54 7 n atom 1234 ca asn a 161 6.282 43.407 19.257 1.00 18.99 6 c atom 1235 c asn a 161 4.952 42.685 19.015 1.00 18.67 6 c atom 1236 o asn a 161 4.067 43.319 18.420 1.00 21.11 8 o atom 1237 cb asn a 161 6.081 44.925 19.420 1.00 18.75 6 c atom 1238 cg asn a 161 7.389 45.677 19.595 1.00 20.21 6 c atom 1239 od1 asn a 161 7.761 46.581 18.811 1.00 22.37 8 o atom 1240 nd2 asn a 161 8.179 45.279 20.589 1.00 15.27 7 n atom 1241 n val a 162 4.772 41.442 19.436 1.00 16.55 7 n atom 1242 ca val a 162 3.538 40.724 19.200 1.00 17.16 6 c atom 1243 c val a 162 2.366 41.269 20.013 1.00 18.41 6 c atom 1244 o val a 162 2.507 41.695 21.176 1.00 17.26 8 o atom 1245 cb val a 162 3.646 39.194 19.416 1.00 17.83 6 c atom 1246 cg1 val a 162 4.795 38.581 18.628 1.00 15.85 6 c atom 1247 cg2 val a 162 3.825 38.879 20.903 1.00 18.28 6 c atom 1248 n asn a 163 1.163 41.245 19.414 1.00 16.20 7 n atom 1249 ca asn a 163 0.032 41.816 20.161 1.00 16.47 6 c atom 1250 c asn a 163 1.266 41.069 19.908 1.00 16.16 6 c atom 1251 o asn a 163 2.340 41.493 20.334 1.00 17.06 8 o atom 1252 cb asn a 163 0.121 43.297 19.770 1.00 16.08 6 c atom 1253 cg asn a 163 0.088 43.453 18.253 1.00 17.24 6 c atom 1254 od1 asn a 163 0.736 42.730 17.475 1.00 17.63 8 o atom 1255 nd2 asn a 163 0.819 44.312 17.795 1.00 16.45 7 n atom 1256 n his a 164 1.169 39.948 19.224 1.00 15.79 7 n atom 1257 ca his a 164 2.331 39.154 18.844 1.00 15.33 6 c atom 1258 c his a 164 1.937 37.682 18.853 1.00 15.46 6 c atom 1259 o his a 164 0.959 37.245 18.223 1.00 15.47 8 o atom 1260 cb his a 164 2.839 39.624 17.468 1.00 13.97 6 c atom 1261 cg his a 164 4.082 38.920 17.018 1.00 14.41 6 c atom 1262 nd1 his a 164 5.318 39.076 17.599 1.00 14.06 7 n atom 1263 cd2 his a 164 4.298 38.074 15.983 1.00 15.01 6 c atom 1264 ce1 his a 164 6.228 38.319 17.011 1.00 13.48 6 c atom 1265 ne2 his a 164 5.633 37.717 16.018 1.00 14.95 7 n atom 1266 n gly a 165 2.680 36.925 19.634 1.00 13.11 7 n atom 1267 ca gly a 165 2.451 35.494 19.770 1.00 13.11 6 c atom 1268 c gly a 165 3.182 34.761 18.648 1.00 13.40 6 c atom 1269 o gly a 165 4.337 35.002 18.326 1.00 11.92 8 o atom 1270 n val a 166 2.451 33.866 18.002 1.00 12.95 7 n atom 1271 ca val a 166 2.949 33.066 16.886 1.00 13.37 6 c atom 1272 c val a 156 2.417 31.640 17.048 1.00 12.90 6 c atom 1273 o val a 166 1.705 31.346 18.023 1.00 11.55 8 o atom 1274 cb val a 166 2.616 33.667 15.530 1.00 11.94 6 c atom 1275 cg1 val a 166 3.197 35.049 15.262 1.00 10.59 6 c atom 1276 cg2 val a 166 1.098 33.789 15.307 1.00 11.21 6 c atom 1277 n leu a 167 2.788 30.756 16.136 1.00 13.69 7 n atom 1278 ca leu a 167 2.414 29.349 16.235 1.00 14.04 6 c atom 1279 c leu a 167 1.733 28.906 14.938 1.00 14.23 6 c atom 1280 o leu a 167 2.333 28.991 13.880 1.00 14.35 8 o atom 1281 cb leu a 167 3.627 28.460 16.429 1.00 14.60 6 c atom 1282 cg leu a 167 3.676 27.221 17.318 1.00 18.08 6 c atom 1283 cd1 leu a 167 4.331 26.042 16.608 1.00 15.69 6 c atom 1284 cd2 leu a 167 2.382 26.803 17.986 1.00 16.33 6 c atom 1285 n val a 168 0.509 28.432 15.013 1.00 15.60 7 n atom 1286 ca val a 168 0.193 27.945 13.827 1.00 14.54 6 c atom 1287 c val a 168 0.213 26.472 13.689 1.00 16.18 6 c atom 1288 o val a 168 0.168 25.658 14.535 1.00 14.48 8 o atom 1289 cb val a 168 1.712 28.056 13.929 1.00 13.43 6 c atom 1290 cg1 val a 168 2.350 27.371 12.717 1.00 14.46 6 c atom 1291 cg2 val a 168 2.155 29.515 14.012 1.00 12.07 6 c atom 1292 n val a 169 1.051 26.187 12.685 1.00 15.86 7 n atom 1293 ca val a 169 1.555 24.836 12.461 1.00 15.27 6 c atom 1294 c val a 169 0.798 24.132 11.345 1.00 16.90 6 c atom 1295 o val a 169 0.951 22.931 11.102 1.00 16.96 8 o atom 1296 cb val a 169 3.063 24.818 12.161 1.00 14.63 6 c atom 1297 cg1 val a 169 3.850 25.372 13.345 1.00 13.34 6 c atom 1298 cg2 val a 169 3.398 25.625 10.917 1.00 12.70 6 c atom 1299 n gly a 170 0.096 24.865 10.665 1.00 17.95 7 n atom 1300 ca gly a 170 1.017 24.211 9.750 1.00 17.61 6 c atom 1301 c gly a 170 2.018 25.147 9.088 1.00 17.35 6 c atom 1302 o gly a 170 2.433 26.169 9.619 1.00 16.20 8 o atom 1303 n tyr a 171 2.632 24.564 8.037 1.00 17.22 7 n atom 1304 ca tyr a 171 3.548 25.356 7.218 1.00 17.14 6 c atom 1305 c tyr a 171 3.652 24.784 5.807 1.00 17.19 6 c atom 1306 o tyr a 171 3.243 23.658 5.546 1.00 14.93 8 o atom 1307 cb tyr a 171 4.919 25.455 7.876 1.00 16.29 6 c atom 1308 cg tyr a 171 5.615 24.125 8.120 1.00 17.70 6 c atom 1309 cd1 tyr a 171 6.289 23.446 7.108 1.00 16.54 6 c atom 1310 cd2 tyr a 171 5.607 23.550 9.386 1.00 17.49 6 c atom 1311 ce1 tyr a 171 6.908 22.231 7.369 1.00 17.16 6 c atom 1312 ce2 tyr a 171 6.237 22.348 9.636 1.00 17.68 6 c atom 1313 cz tyr a 171 6.897 21.679 8.627 1.00 17.44 6 c atom 1314 oh tyr a 171 7.538 20.473 8.845 1.00 18.24 8 o atom 1315 n gly a 172 4.200 25.574 4.892 1.00 17.34 7 n atom 1316 ca gly a 172 4.458 25.038 3.556 1.00 21.15 6 c atom 1317 c gly a 172 5.181 26.092 2.731 1.00 24.74 6 c atom 1318 o gly a 172 5.864 27.013 3.201 1.00 22.56 8 o atom 1319 n asp a 173 4.764 26.121 1.471 1.00 27.84 7 n atom 1320 ca asp a 173 5.390 26.992 0.484 1.00 32.33 6 c atom 1321 c asp a 173 4.450 27.197 0.694 1.00 33.93 6 c atom 1322 o asp a 173 3.875 26.262 1.245 1.00 33.57 8 o atom 1323 cb asp a 173 6.726 26.322 0.152 1.00 35.77 6 c atom 1324 cg asp a 173 7.031 26.392 1.330 1.00 37.36 6 c atom 1325 od1 asp a 173 6.536 25.496 2.041 1.00 36.96 8 o atom 1326 od2 asp a 173 7.695 27.373 1.708 1.00 39.64 8 o atom 1327 n leu a 174 4.254 28.459 1.018 1.00 35.00 7 n atom 1328 ca leu a 174 3.399 28.910 2.100 1.00 38.08 6 c atom 1329 c leu a 174 4.252 29.425 3.259 1.00 39.09 6 c atom 1330 o leu a 174 4.669 30.585 3.221 1.00 38.29 8 o atom 1331 cb leu a 174 2.511 30.040 1.555 1.00 38.22 6 c atom 1332 cg leu a 174 1.173 30.291 2.237 1.00 39.46 6 c atom 1333 cd1 leu a 174 0.332 31.322 1.495 1.00 39.18 6 c atom 1334 cd2 leu a 174 1.355 30.748 3.680 1.00 39.84 6 c atom 1335 n asn a 175 4.624 28.562 4.195 1.00 40.67 7 n atom 1336 ca asn a 175 5.408 28.947 5.366 1.00 42.16 6 c atom 1337 c asn a 175 6.697 29.663 4.988 1.00 42.41 6 c atom 1338 o asn a 175 6.964 30.829 5.284 1.00 43.04 8 o atom 1339 cb asn a 175 4.560 29.804 6.309 1.00 43.20 6 c atom 1340 cg asn a 175 3.397 29.033 6.912 1.00 44.56 6 c atom 1341 gd1 asn a 175 2.267 29.523 6.853 1.00 44.33 8 o atom 1342 nd2 asn a 175 3.705 27.865 7.477 1.00 45.34 7 n atom 1343 n gly a 176 7.517 28.980 4.192 1.00 41.86 7 n atom 1344 ca gly a 176 8.739 29.541 3.652 1.00 40.44 6 c atom 1345 c gly a 176 8.591 30.376 2.390 1.00 38.18 6 c atom 1346 o gly a 176 9.626 30.654 1.773 1.00 38.68 8 o atom 1347 n lys a 177 7.394 30.755 1.962 1.00 35.10 7 n atom 1348 ca lys a 177 7.269 31.573 0.761 1.00 32.21 6 c atom 1349 c lys a 177 6.771 30.754 0.436 1.00 28.29 6 c atom 1350 o lys a 177 5.615 30.433 0.670 1.00 27.65 8 o atom 1351 cb lys a 177 6.450 32.837 0.969 1.00 33.72 6 c atom 1352 cg lys a 177 6.833 33.757 2.108 1.00 35.81 6 c atom 1353 cd lys a 177 7.591 35.016 1.754 1.00 37.22 6 c atom 1354 ce lys a 177 9.097 34.886 1.745 1.00 39.10 6 c atom 1355 nz lys a 177 9.789 36.044 2.400 1.00 39.84 7 n atom 1356 n glu a 178 7.759 30.472 1.286 1.00 24.46 7 n atom 1357 ca glu a 178 7.610 29.784 2.546 1.00 22.50 6 c atom 1358 c glu a 178 6.635 30.529 3.455 1.00 18.46 6 c atom 1359 o glu a 178 6.736 31.726 3.604 1.00 15.36 8 o atom 1360 cb glu a 178 8.959 29.601 3.267 1.00 24.33 6 c atom 1361 cg glu a 178 9.930 28.749 2.453 1.00 26.00 6 c atom 1362 cd glu a 178 11.076 28.212 3.286 1.00 27.06 6 c atom 1363 oe1 glu a 178 11.434 28.854 4.287 1.00 27.85 8 o atom 1364 oe2 glu a 178 11.606 27.130 2.955 1.00 28.93 8 o atom 1365 n tyr a 179 5.672 29.836 4.032 1.00 17.29 7 n atom 1366 ca tyr a 179 4.774 30.471 4.988 1.00 17.64 6 c atom 1367 c tyr a 179 4.516 29.592 6.207 1.00 15.62 6 c atom 1368 o tyr a 179 4.794 28.402 6.176 1.00 13.21 8 o atom 1369 cb tyr a 179 3.411 30.758 4.327 1.00 18.27 6 c atom 1370 cg tyr a 179 2.738 29.471 3.876 1.00 20.52 6 c atom 1371 cd1 tyr a 179 2.018 28.698 4.767 1.00 20.72 6 c atom 1372 cd2 tyr a 179 2.756 29.079 2.543 1.00 21.28 6 c atom 1373 ce1 tyr a 179 1.381 27.533 4.379 1.00 22.12 6 c atom 1374 ce2 tyr a 179 2.104 27.931 2.133 1.00 22.09 6 c atom 1375 cz tyr a 179 1.435 27.152 3.051 1.00 22.22 6 c atom 1376 oh tyr a 179 0.798 26.008 2.646 1.00 21.39 8 o atom 1377 n trp a 180 3.854 30.207 7.170 1.00 15.61 7 n atom 1378 ca trp a 180 3.295 29.578 8.353 1.00 16.38 6 c atom 1379 c trp a 180 1.762 29.623 8.235 1.00 16.72 6 c atom 1380 o trp a 180 1.215 30.720 8.033 1.00 16.17 8 o atom 1381 cb trp a 180 3.656 30.415 9.594 1.00 15.46 6 c atom 1382 cg trp a 180 5.097 30.294 9.994 1.00 16.15 6 c atom 1383 cd1 trp a 180 6.022 31.306 9.967 1.00 15.97 6 c atom 1384 cd2 trp a 180 5.796 29.136 10.482 1.00 16.39 6 c atom 1385 ne1 trp a 180 7.238 30.855 10.414 1.00 15.50 7 n atom 1386 ce2 trp a 180 7.130 29.529 10.744 1.00 16.18 6 c atom 1387 ce3 trp a 180 5.432 27.808 10.735 1.00 15.39 6 c atom 1388 cz2 trp a 180 8.099 28.639 11.222 1.00 16.42 6 c atom 1389 cz3 trp a 180 6.380 26.946 11.239 1.00 14.76 6 c atom 1390 ch2 trp a 180 7.709 27.355 11.477 1.00 15.13 6 c atom 1391 n leu a 181 1.065 28.500 8.305 1.00 16.97 7 n atom 1392 ca leu a 181 0.406 28.491 8.193 1.00 14.53 6 c atom 1393 c leu a 181 1.017 28.881 9.526 1.00 15.04 6 c atom 1394 o leu a 181 0.865 28.155 10.519 1.00 16.01 8 o atom 1395 cb leu a 181 0.801 27.060 7.761 1.00 12.54 6 c atom 1396 cg leu a 181 2.292 26.806 7.526 1.00 12.47 6 c atom 1397 cd1 leu a 181 2.885 27.752 6.494 1.00 10.12 6 c atom 1398 cd2 leu a 181 2.572 25.353 7.146 1.00 13.57 6 c atom 1399 n val a 182 1.619 30.066 9.599 1.00 15.67 7 n atom 1400 ca val a 182 2.136 30.572 10.874 1.00 15.34 6 c atom 1401 c val a 182 3.657 30.555 10.944 1.00 16.57 6 c atom 1402 o val a 182 4.366 30.998 10.033 1.00 15.01 8 o atom 1403 cb val a 182 1.661 32.039 11.041 1.00 15.50 6 c atom 1404 cg1 val a 182 2.086 32.625 12.368 1.00 13.96 6 c atom 1405 cg2 val a 182 0.148 32.108 10.852 1.00 14.73 6 c atom 1406 n lys a 183 4.178 29.969 12.012 1.00 15.60 7 n atom 1407 ca lys a 183 5.590 29.975 12.323 1.00 15.18 6 c atom 1408 c lys a 183 5.825 31.243 13.158 1.00 14.69 6 c atom 1409 o lys a 183 5.159 31.432 14.178 1.00 13.60 8 o atom 1410 cb lys a 183 6.002 28.761 13.154 1.00 14.92 6 c atom 1411 cg lys a 183 7.505 28.610 13.307 1.00 14.25 6 c atom 1412 cd lys a 183 7.826 27.594 14.403 1.00 15.02 6 c atom 1413 ce lys a 183 9.333 27.333 14.442 1.00 15.19 6 c atom 1414 nz lys a 183 9.781 26.510 15.594 1.00 16.20 7 n atom 1415 n asn a 184 6.689 32.119 12.701 1.00 13.87 7 n atom 1416 ca asn a 184 6.997 33.342 13.440 1.00 13.73 6 c atom 1417 c asn a 184 8.281 33.107 14.235 1.00 13.70 6 c atom 1418 o asn a 184 8.895 32.056 14.053 1.00 12.97 8 o atom 1419 cb asn a 184 7.185 34.510 12.488 1.00 12.85 6 c atom 1420 cg asn a 184 7.039 35.876 13.128 1.00 14.41 6 c atom 1421 od1 asn a 184 6.754 36.061 14.305 1.00 14.25 8 o atom 1422 nd2 asn a 184 7.162 36.922 12.330 1.00 13.86 7 n atom 1423 n ser a 185 8.782 34.116 14.933 1.00 14.88 7 n atom 1424 ca ser a 185 10.053 33.976 15.671 1.00 15.71 6 c atom 1425 c ser a 185 10.905 35.173 15.278 1.00 17.28 6 c atom 1426 o ser a 185 11.582 35.831 16.061 1.00 18.08 8 o atom 1427 cb ser a 185 9.754 33.878 17.165 1.00 13.97 6 c atom 1428 og ser a 185 8.880 34.956 17.544 1.00 14.91 8 o atom 1429 n trp a 186 10.900 35.480 13.975 1.00 18.64 7 n atom 1430 ca trp a 186 11.626 36.637 13.444 1.00 19.40 6 c atom 1431 c trp a 186 12.789 36.200 12.583 1.00 19.87 6 c atom 1432 o trp a 186 13.275 36.935 11.717 1.00 19.64 8 o atom 1433 cb trp a 186 10.676 37.599 12.701 1.00 19.39 6 c atom 1434 cg trp a 186 9.884 38.499 13.617 1.00 21.79 6 c atom 1435 cd1 trp a 186 9.854 38.479 14.984 1.00 21.06 6 c atom 1436 cd2 trp a 186 8.908 39.484 13.230 1.00 21.63 6 c atom 1437 ne1 trp a 186 8.986 39.408 15.470 1.00 21.86 7 n atom 1438 ce2 trp a 186 8.351 40.010 14.412 1.00 21.21 6 c atom 1439 ce3 trp a 186 8.459 39.966 11.996 1.00 21.18 6 c atom 1440 cz2 trp a 186 7.435 41.055 14.403 1.00 20.81 6 c atom 1441 cz3 trp a 186 7.532 41.016 12.000 1.00 21.65 6 c atom 1442 ch2 trp a 186 7.034 41.552 13.197 1.00 19.62 6 c atom 1443 n gly a 187 13.290 34.987 12.823 1.00 20.15 7 n atom 1444 ca gly a 187 14.435 34.493 12.074 1.00 20.66 6 c atom 1445 c gly a 187 13.985 33.932 10.718 1.00 23.32 6 c atom 1446 o gly a 187 12.874 34.115 10.234 1.00 21.54 8 o atom 1447 n his a 188 14.955 33.341 10.023 1.00 25.27 7 n atom 1448 ca his a 188 14.684 32.693 8.745 1.00 28.37 6 c atom 1449 c his a 188 14.552 33.705 7.622 1.00 26.86 6 c atom 1450 o his a 188 13.845 33.388 6.653 1.00 25.55 8 o atom 1451 cb his a 188 15.671 31.574 8.493 1.00 32.95 6 c atom 1452 cg his a 188 16.996 31.794 7.859 1.00 37.55 6 c atom 1453 nd1 his a 188 17.623 30.760 7.178 1.00 39.31 7 n atom 1454 cd2 his a 188 17.827 32.871 7.766 1.00 38.66 6 c atom 1455 ce1 his a 188 18.786 31.184 6.704 1.00 39.66 6 c atom 1456 ne2 his a 188 18.925 32.455 7.052 1.00 39.70 7 n atom 1457 n asn a 189 14.994 34.947 7.757 1.00 23.83 7 n atom 1458 ca asn a 189 14.835 35.913 6.676 1.00 23.09 6 c atom 1459 c asn a 189 13.506 36.657 6.649 1.00 23.00 6 c atom 1460 o asn a 189 13.137 37.361 5.695 1.00 21.38 8 o atom 1461 cb asn a 189 16.032 36.876 6.651 1.00 24.25 6 c atom 1462 cg asn a 189 17.300 36.052 6.434 1.00 24.98 6 c atom 1463 od1 asn a 189 18.237 36.112 7.221 1.00 27.48 8 o atom 1464 nd2 asn a 189 17.256 35.174 5.446 1.00 26.05 7 n atom 1465 n phe a 190 12.643 36.387 7.618 1.00 20.07 7 n atom 1466 ca phe a 190 11.257 36.828 7.584 1.00 17.77 6 c atom 1467 c phe a 190 10.417 35.944 6.656 1.00 17.53 6 c atom 1468 o phe a 190 10.494 34.705 6.594 1.00 17.41 8 o atom 1469 cb phe a 190 10.671 36.851 9.003 1.00 16.47 6 c atom 1470 cg phe a 190 9.182 37.069 8.988 1.00 14.40 6 c atom 1471 cd1 phe a 190 8.318 35.989 9.188 1.00 14.66 6 c atom 1472 cd2 phe a 190 8.643 38.312 8.734 1.00 14.20 6 c atom 1473 ce1 phe a 190 6.954 36.181 9.151 1.00 15.22 6 c atom 1474 ce2 phe a 190 7.276 38.501 8.700 1.00 13.98 6 c atom 1475 cz phe a 190 6.419 37.424 8.907 1.00 12.99 6 c atom 1476 n gly a 191 9.553 36.582 5.863 1.00 15.91 7 n atom 1477 ca gly a 191 8.573 35.919 5.026 1.00 16.14 6 c atom 1478 c gly a 191 9.087 34.693 4.293 1.00 18.11 6 c atom 1479 o gly a 191 10.176 34.779 3.719 1.00 18.26 8 o atom 1480 n glu a 192 8.346 33.578 4.320 1.00 17.12 7 n atom 1481 ca glu a 192 8.754 32.368 3.635 1.00 17.98 6 c atom 1482 c glu a 192 9.560 31.470 4.565 1.00 17.03 6 c atom 1483 o glu a 192 9.028 30.609 5.276 1.00 16.42 8 o atom 1484 cb glu a 192 7.514 31.629 3.080 1.00 19.96 6 c atom 1485 cg glu a 192 6.641 32.515 2.214 1.00 23.37 6 c atom 1486 cd glu a 192 5.267 31.975 1.891 1.00 26.37 6 c atom 1487 oe1 glu a 192 4.557 31.515 2.811 1.00 26.96 8 o atom 1488 oe2 glu a 192 4.882 32.006 0.698 1.00 28.12 8 o atom 1489 n glu a 193 10.860 31.723 4.656 1.00 15.32 7 n atom 1490 ca glu a 193 11.773 30.999 5.521 1.00 17.56 6 c atom 1491 c glu a 193 11.334 31.111 6.981 1.00 17.17 6 c atom 1492 o glu a 193 11.379 30.116 7.716 1.00 17.09 8 o atom 1493 cb glu a 193 11.892 29.512 5.127 1.00 18.86 6 c atom 1494 cg glu a 193 12.376 29.242 3.702 1.00 23.04 6 c atom 1495 cd glu a 193 12.734 27.783 3.435 1.00 24.86 6 c atom 1496 oe1 glu a 193 13.411 27.186 4.307 1.00 27.13 8 o atom 1497 oe2 glu a 193 12.396 27.184 2.397 1.00 24.55 8 o atom 1498 n gly a 194 10.738 32.219 7.391 1.00 17.11 7 n atom 1499 ca gly a 194 10.314 32.452 8.757 1.00 16.49 6 c atom 1500 c gly a 194 8.823 32.203 8.994 1.00 16.49 6 c atom 1501 o gly a 194 8.367 32.444 10.114 1.00 14.95 8 o atom 1502 n tyr a 195 8.120 31.825 7.942 1.00 16.25 7 n atom 1503 ca tyr a 195 6.696 31.552 8.020 1.00 17.48 6 c atom 1504 c tyr a 195 5.877 32.624 7.294 1.00 17.17 6 c atom 1505 o tyr a 195 6.351 33.300 6.387 1.00 16.71 8 o atom 1506 cb tyr a 195 6.320 30.170 7.434 1.00 17.38 6 c atom 1507 cg tyr a 195 6.815 29.046 8.326 1.00 17.46 6 c atom 1508 cd1 tyr a 195 8.172 28.719 8.324 1.00 19.12 6 c atom 1509 cd2 tyr a 195 5.956 28.397 9.193 1.00 17.98 6 c atom 1510 ce1 tyr a 195 8.623 27.702 9.152 1.00 19.16 6 c atom 1511 ce2 tyr a 195 6.431 27.433 10.047 1.00 17.77 6 c atom 1512 cz tyr a 195 7.745 27.054 10.000 1.00 19.28 6 c atom 1513 oh tyr a 195 8.230 26.069 10.839 1.00 19.78 8 o atom 1514 n ile a 196 4.607 32.654 7.664 1.00 15.81 7 n atom 1515 ca ile a 196 3.646 33.523 7.003 1.00 16.14 6 c atom 1516 c ile a 196 2.317 32.805 6.878 1.00 16.66 6 c atom 1517 o ile a 196 1.834 32.123 7.789 1.00 19.33 8 o atom 1518 cb ile a 196 3.559 34.904 7.682 1.00 15.06 6 c atom 1519 cg1 ile a 196 2.544 35.842 7.026 1.00 14.70 6 c atom 1520 cg2 ile a 196 3.252 34.738 9.167 1.00 14.78 6 c atom 1521 gd1 ile a 196 2.527 37.257 7.562 1.00 14.90 6 c atom 1522 n arg a 197 1.688 32.948 5.725 1.00 18.43 7 n atom 1523 ca arg a 197 0.371 32.360 5.458 1.00 19.44 6 c atom 1524 c arg a 197 0.655 33.508 5.513 1.00 18.85 6 c atom 1525 o arg a 197 0.558 34.487 4.751 1.00 19.76 8 o atom 1526 cb arg a 197 0.287 31.662 4.129 1.00 22.07 6 c atom 1527 cg arg a 197 1.371 30.658 3.803 1.00 25.31 6 c atom 1528 cd arg a 197 0.905 29.660 2.747 1.00 27.94 6 c atom 1529 ne arg a 197 1.833 29.480 1.689 1.00 31.60 7 n atom 1530 cz arg a 197 2.514 30.055 0.745 1.00 34.65 6 c atom 1531 nh1 arg a 197 2.479 31.348 0.466 1.00 36.35 7 n atom 1532 nh2 arg a 197 3.356 29.329 0.001 1.00 34.88 7 n atom 1533 n met a 198 1.506 33.448 6.528 1.00 16.76 7 n atom 1534 ca met a 198 2.423 34.504 6.888 1.00 16.33 6 c atom 1535 c met a 198 3.842 34.089 6.525 1.00 17.05 6 c atom 1536 o met a 198 4.224 32.945 6.732 1.00 17.97 8 o atom 1537 cb met a 198 2.324 34.858 8.379 1.00 15.58 6 c atom 1538 cg met a 198 0.932 35.176 8.870 1.00 15.29 6 c atom 1539 sd met a 198 0.749 35.860 10.518 1.00 13.09 16 s atom 1540 ce met a 198 2.083 37.044 10.605 1.00 14.48 6 c atom 1541 n ala a 199 4.622 35.030 6.023 1.00 17.32 7 n atom 1542 ca ala a 199 6.002 34.750 5.614 1.00 17.26 6 c atom 1543 c ala a 199 6.782 34.027 6.709 1.00 17.79 6 c atom 1544 o ala a 199 6.806 34.523 7.833 1.00 17.37 8 o atom 1545 cb ala a 199 6.676 36.076 5.299 1.00 18.27 6 c atom 1546 n arg a 200 7.421 32.934 6.336 1.00 17.07 7 n atom 1547 ca arg a 200 8.242 32.068 7.144 1.00 17.73 6 c atom 1548 c arg a 200 9.704 32.167 6.711 1.00 18.72 6 c atom 1549 o arg a 200 9.995 32.404 5.536 1.00 17.50 8 o atom 1550 cb arg a 200 7.749 30.626 6.975 1.00 16.84 6 c atom 1551 cg arg a 200 8.506 29.516 7.664 1.00 17.84 6 c atom 1552 cd arg a 200 7.740 28.195 7.652 1.00 18.67 6 c atom 1553 ne arg a 200 7.706 27.572 6.338 1.00 17.04 7 n atom 1554 cz arg a 200 8.581 26.687 5.852 1.00 18.69 6 c atom 1555 nh1 arg a 200 9.624 26.250 6.560 1.00 17.64 7 n atom 1556 nh2 arg a 200 8.413 26.216 4.606 1.00 15.92 7 n atom 1557 n asn a 201 10.653 32.066 7.635 1.00 21.23 7 n atom 1558 ca asn a 201 12.067 32.240 7.331 1.00 23.27 6 c atom 1559 c asn a 201 12.348 33.603 6.706 1.00 23.87 6 c atom 1560 o asn a 201 13.253 33.730 5.859 1.00 23.26 8 o atom 1561 cb asn a 201 12.618 31.112 6.448 1.00 24.20 6 c atom 1562 cg asn a 201 12.646 29.799 7.216 1.00 25.89 6 c atom 1563 od1 asn a 201 12.621 29.777 8.448 1.00 28.02 8 o atom 1564 nd2 asn a 201 12.666 28.692 6.496 1.00 25.20 7 n atom 1565 n lys a 202 11.598 34.627 7.127 1.00 22.36 7 n atom 1566 ca lys a 202 11.828 35.966 6.596 1.00 23.90 6 c atom 1567 c lys a 202 12.213 36.873 7.775 1.00 23.36 6 c atom 1568 o lys a 202 11.804 38.039 7.851 1.00 24.12 8 o atom 1569 cb lys a 202 10.680 36.565 5.809 1.00 25.00 6 c atom 1570 cg lys a 202 10.478 36.055 4.394 1.00 28.96 6 c atom 1571 cd lys a 202 11.704 36.279 3.507 1.00 31.05 6 c atom 1572 ce lys a 202 11.463 35.809 2.084 1.00 32.39 6 c atom 1573 nz lys a 202 10.052 35.954 1.637 1.00 33.25 7 n atom 1574 n gly a 203 13.042 36.333 8.667 1.00 21.01 7 n atom 1575 ca gly a 203 13.520 37.074 9.829 1.00 21.03 6 c atom 1576 c gly a 203 12.484 37.199 10.940 1.00 20.44 6 c atom 1577 o gly a 203 12.255 38.296 11.460 1.00 18.71 8 o atom 1578 n asn a 204 11.766 36.114 11.249 1.00 19.47 7 n atom 1579 ca asn a 204 10.748 36.135 12.300 1.00 20.20 6 c atom 1580 c asn a 204 9.775 37.287 12.053 1.00 19.49 6 c atom 1581 o asn a 204 9.535 38.141 12.894 1.00 18.44 8 o atom 1582 cb asn a 204 11.378 36.255 13.689 1.00 21.13 6 c atom 1583 cg asn a 204 10.402 36.156 14.855 1.00 21.82 6 c atom 1584 od1 asn a 204 10.581 36.769 15.915 1.00 20.98 8 o atom 1585 nd2 asn a 204 9.379 35.335 14.715 1.00 20.50 7 n atom 1586 n his a 205 9.228 37.293 10.855 1.00 19.29 7 n atom 1587 ca his a 205 8.305 38.252 10.325 1.00 19.00 6 c atom 1588 c his a 205 7.096 38.438 11.236 1.00 17.54 6 c atom 1589 o his a 205 6.429 37.481 11.637 1.00 14.95 8 o atom 1590 cb his a 205 7.913 37.762 8.915 1.00 21.31 6 c atom 1591 cg his a 205 6.785 38.554 8.324 1.00 25.40 6 c atom 1592 nd1 his a 205 6.786 39.931 8.239 1.00 27.49 7 n atom 1593 cd2 his a 205 5.602 38.154 7.801 1.00 26.82 6 c atom 1594 ce1 his a 205 5.657 40.345 7.689 1.00 28.18 6 c atom 1595 ne2 his a 205 4.930 39.275 7.405 1.00 28.68 7 n atom 1596 n cys a 206 6.854 39.661 11.690 1.00 15.21 7 n atom 1597 ca cys a 206 5.769 40.001 12.592 1.00 16.62 6 c atom 1598 c cys a 206 5.895 39.280 13.947 1.00 16.65 6 c atom 1599 o cys a 206 4.902 39.159 14.669 1.00 15.00 8 o atom 1600 cb cys a 206 4.367 39.723 12.043 1.00 14.49 6 c atom 1601 sg cys a 206 3.897 40.559 10.516 1.00 14.57 16 s atom 1602 n gly a 207 7.105 38.883 14.333 1.00 16.79 7 n atom 1603 ca gly a 207 7.354 38.202 15.589 1.00 16.13 6 c atom 1604 c gly a 207 6.613 36.868 15.660 1.00 17.43 6 c atom 1605 o gly a 207 6.435 36.354 16.767 1.00 16.17 8 o atom 1606 n ile a 208 6.528 36.132 14.546 1.00 16.30 7 n atom 1607 ca ile a 208 5.765 34.883 14.596 1.00 17.45 6 c atom 1608 c ile a 208 6.371 33.839 15.527 1.00 16.64 6 c atom 1609 o ile a 208 5.608 33.151 16.238 1.00 17.08 8 o atom 1610 cb ile a 208 5.509 34.347 13.172 1.00 17.22 6 c atom 1611 cg1 ile a 208 4.710 33.042 13.262 1.00 17.93 6 c atom 1612 cg2 ile a 208 6.781 34.076 12.394 1.00 16.48 6 c atom 1613 cd1 ile a 208 3.346 33.238 13.832 1.00 19.94 6 c atom 1614 n ala a 209 7.686 33.681 15.579 1.00 13.80 7 n atom 1615 ca ala a 209 8.334 32.739 16.478 1.00 15.58 6 c atom 1616 c ^{:} ala a 209 8.931 33.442 17.694 1.00 15.72 6 c atom 1617 o ala a 209 9.696 32.868 18.476 1.00 16.75 8 o atom 1618 cb ala a 209 9.415 31.916 15.791 1.00 15.09 6 c atom 1619 n ser a 210 8.509 34.668 17.944 1.00 17.17 7 n atom 1620 ca ser a 210 8.993 35.396 19.128 1.00 17.74 6 c atom 1621 c ser a 210 8.594 34.694 20.420 1.00 18.87 6 c atom 1622 o ser a 210 9.440 34.469 21.292 1.00 19.17 8 o atom 1623 cb ser a 210 8.421 36.815 19.163 1.00 17.07 6 c atom 1624 og ser a 210 9.106 37.617 18.237 1.00 18.86 8 o atom 1625 n phe a 211 7.312 34.373 20.579 1.00 18.49 7 n atom 1626 ca phe a 211 6.816 33.808 21.830 1.00 19.86 6 c atom 1627 c phe a 211 5.921 32.601 21.639 1.00 20.65 6 c atom 1628 o phe a 211 4.708 32.656 21.886 1.00 21.46 8 o atom 1629 cb phe a 211 6.040 34.882 22.638 1.00 21.37 6 c atom 1630 cg phe a 211 6.931 35.904 23.303 1.00 22.48 6 c atom 1631 cd1 phe a 211 7.715 35.575 24.395 1.00 21.99 6 c atom 1632 cd2 phe a 211 6.998 37.200 22.815 1.00 20.63 6 c atom 1633 ce1 phe a 211 8.519 36.519 25.009 1.00 21.67 6 c atom 1634 ce2 phe a 211 7.808 38.143 23.415 1.00 22.05 6 c atom 1635 cz phe a 211 8.604 37.793 24.495 1.00 21.72 6 c atom 1636 n pro a 212 6.465 31.477 21.195 1.00 20.25 7 n atom 1637 ca pro a 212 5.724 30.266 20.917 1.00 19.53 6 c atom 1638 c pro a 212 5.624 29.275 22.066 1.00 19.38 6 c atom 1639 o pro a 212 6.577 29.099 22.821 1.00 18.42 8 o atom 1640 cb pro a 212 6.416 29.641 19.713 1.00 20.06 6 c atom 1641 cg pro a 212 7.675 30.431 19.506 1.00 20.72 6 c atom 1642 cd pro a 212 7.869 31.270 20.756 1.00 20.14 6 c atom 1643 n ser a 213 4.430 28.664 22.212 1.00 18.53 7 n atom 1644 ca ser a 213 4.278 27.636 23.233 1.00 19.58 6 c atom 1645 c ser a 213 3.214 26.607 22.853 1.00 20.54 6 c atom 1646 o ser a 213 2.270 26.913 22.129 1.00 19.38 8 o atom 1647 cb ser a 213 3.891 28.202 24.596 1.00 18.99 6 c atom 1648 og ser a 213 2.686 28.962 24.497 1.00 18.87 8 o atom 1649 n tyr a 214 3.359 25.405 23.407 1.00 20.02 7 n atom 1650 ca tyr a 214 2.357 24.372 23.216 1.00 22.71 6 c atom 1651 c tyr a 214 2.175 23.497 24.449 1.00 23.11 6 c atom 1652 o tyr a 214 3.110 23.177 25.187 1.00 21.86 8 o atom 1653 cb tyr a 214 2.707 23.551 21.969 1.00 24.35 6 c atom 1654 cg tyr a 214 3.959 22.763 22.261 1.00 26.72 6 c atom 1655 cd1 tyr a 214 5.208 23.354 22.081 1.00 27.85 6 c atom 1656 cd2 tyr a 214 3.903 21.473 22.753 1.00 27.40 6 c atom 1657 ce1 tyr a 214 6.353 22.649 22.370 1.00 28.41 6 c atom 1658 ce2 tyr a 214 5.038 20.765 23.051 1.00 29.19 6 c atom 1659 cz tyr a 214 6.277 21.359 22.849 1.00 29.82 6 c atom 1660 oh tyr a 214 7.435 20.677 23.128 1.00 31.03 8 o atom 1661 n pro a 215 0.947 23.062 24.673 1.00 23.92 7 n atom 1662 ca pro a 215 0.598 22.260 25.840 1.00 24.95 6 c atom 1663 c pro a 215 0.759 20.781 25.551 1.00 26.05 6 c atom 1664 o pro a 215 0.854 20.403 24.384 1.00 25.20 8 o atom 1665 cb pro a 215 0.876 22.591 26.044 1.00 24.66 6 c atom 1666 cg pro a 215 1.387 22.722 24.636 1.00 23.78 6 c atom 1667 cd pro a 215 0.259 23.357 23.867 1.00 24.00 6 c atom 1668 n glu a 216 0.832 19.995 26.611 1.00 28.68 7 n atom 1669 ca glu a 216 0.848 18.544 26.494 1.00 31.39 6 c atom 1670 c glu a 216 0.057 17.903 27.541 1.00 30.14 6 c atom 1671 o glu a 216 0.172 18.312 28.694 1.00 31.42 8 o atom 1672 cb glu a 216 2.259 17.965 26.543 1.00 33.58 6 c atom 1673 cg glu a 216 2.879 17.836 25.149 1.00 36.70 6 c atom 1674 cd glu a 216 4.086 16.921 25.209 1.00 39.41 6 c atom 1675 oe1 glu a 216 4.056 15.930 25.969 1.00 41.23 8 o atom 1676 oe2 glu a 216 5.064 17.209 24.501 1.00 41.73 8 o atom 1677 n ile a 217 0.679 16.795 27.170 1.00 30.29 7 n atom 1678 ca ile a 217 1.563 16.044 28.050 1.00 29.90 6 c atom 1679 c ile a 217 0.981 14.698 28.483 1.00 31.17 6 c atom 1680 o ile a 217 0.520 14.629 29.644 1.00 32.16 8 o atom 1681 cb ile a 217 2.910 15.785 27.350 1.00 28.86 6 c atom 1682 cg1 ile a 217 3.547 17.119 26.955 1.00 27.72 6 c atom 1683 cg2 ile a 217 3.852 14.953 28.209 1.00 28.09 6 c atom 1684 cd1 ile a 217 4.742 17.002 26.044 1.00 26.56 6 c atom 1685 ow0 wat w 1 0.910 21.471 19.936 1.00 12.44 8 o atom 1686 ow0 wat w 2 10.802 27.216 8.990 1.00 19.22 8 o atom 1687 ow0 wat w 3 10.377 30.344 15.881 1.00 15.32 8 o atom 1688 ow0 wat w 4 8.315 24.228 16.799 1.00 13.99 8 o atom 1689 ow0 wat w 5 10.290 34.128 11.523 1.00 19.93 8 o atom 1690 ow0 wat w 6 9.457 34.855 8.945 1.00 15.29 8 o atom 1691 ow0 wat w 7 6.530 33.715 17.567 1.00 15.58 8 o atom 1692 ow0 wat w 8 5.156 34.303 18.682 1.00 15.74 8 o atom 1693 ow0 wat w 9 13.026 27.960 21.503 1.00 18.03 8 o atom 1694 ow0 wat w 10 1.621 12.831 31.246 1.00 32.90 8 o atom 1695 ow0 wat w 11 6.079 23.010 16.980 1.00 23.03 8 o atom 1696 ow0 wat w 12 7.127 39.994 21.014 1.00 23.94 8 o atom 1697 ow0 wat w 13 0.336 43.084 10.717 1.00 23.78 8 o atom 1698 ow0 wat w 14 12.051 24.811 5.051 1.00 17.60 8 o atom 1699 ow0 wat w 15 10.134 18.120 20.608 1.00 13.60 8 o atom 1700 ow0 wat w 16 3.564 31.489 23.974 1.00 16.67 8 o atom 1701 ow0 wat w 17 1.919 33.122 25.543 1.00 19.17 8 o atom 1702 ow0 wat w 18 17.523 32.721 10.869 1.00 18.30 8 o atom 1703 ow0 wat w 19 8.645 36.781 31.864 1.00 17.00 8 o atom 1704 ow0 wat w 20 18.368 41.504 19.911 1.00 21.43 8 o atom 1705 ow0 wat w 21 1.374 43.515 23.204 1.00 17.28 8 o atom 1706 ow0 wat w 22 6.583 31.141 16.679 1.00 23.32 8 o atom 1707 ow0 wat w 23 4.936 43.220 1.608 1.00 19.07 8 o atom 1708 ow0 wat w 24 9.086 19.655 11.727 1.00 22.26 8 o atom 1709 ow0 wat w 25 9.747 28.261 17.677 1.00 14.07 8 o atom 1710 ow0 wat w 26 10.474 9.886 15.479 1.00 31.27 8 o atom 1711 ow0 wat w 27 5.019 35.857 9.836 1.00 18.07 8 o atom 1712 ow0 wat w 28 0.417 15.928 24.512 1.00 25.06 8 o atom 1713 ow0 wat w 29 14.152 33.685 11.654 1.00 26.61 8 o atom 1714 ow0 wat w 30 0.445 47.894 6.519 1.00 23.12 8 o atom 1715 ow0 wat w 31 13.212 21.438 12.066 1.00 25.71 8 o atom 1716 ow0 wat w 32 8.859 43.255 8.773 1.00 28.91 8 o atom 1717 ow0 wat w 33 8.078 28.138 4.697 1.00 27.00 8 o atom 1718 ow0 wat w 34 9.327 39.744 5.401 1.00 24.36 8 o atom 1719 ow0 wat w 35 15.238 29.329 5.938 1.00 37.48 8 o atom 1720 ow0 wat w 36 15.682 36.496 9.919 1.00 32.49 8 o atom 1721 ow0 wat w 37 20.329 31.853 29.441 1.00 18.84 8 o atom 1722 ow0 wat w 38 15.309 29.578 21.369 1.00 37.57 8 o atom 1723 ow0 wat w 39 20.112 35.889 21.955 1.00 25.41 8 o atom 1724 ow0 wat w 40 0.568 16.884 10.867 1.00 26.71 8 o atom 1725 ow0 wat w 41 11.276 27.509 37.922 1.00 24.48 8 o atom 1726 ow0 wat w 42 10.810 28.531 18.235 1.00 24.10 8 o atom 1727 ow0 wat w 43 4.428 20.883 26.323 1.00 29.31 8 o atom 1728 ow0 wat w 44 2.909 42.422 3.165 1.00 17.38 8 o atom 1729 ow0 wat w 45 15.034 33.199 9.073 1.00 38.01 8 o atom 1730 ow0 wat w 46 16.621 32.433 20.655 1.00 23.33 8 o atom 1731 ow0 wat w 47 14.849 31.179 12.633 1.00 28.83 8 o atom 1732 ow0 wat w 48 20.277 34.505 6.785 1.00 29.98 8 o atom 1733 ow0 wat w 49 20.371 36.073 9.026 1.00 57.53 8 o atom 1734 ow0 wat w 50 8.103 34.049 2.670 1.00 21.77 8 o atom 1735 ow0 wat w 51 12.130 25.137 5.917 1.00 34.30 8 o atom 1736 ow0 wat w 52 0.770 38.179 0.446 1.00 30.27 8 o atom 1737 ow0 wat w 53 11.606 27.014 19.422 1.00 17.83 8 o atom 1738 ow0 wat w 54 11.237 21.841 18.202 1.00 24.15 8 o atom 1739 ow0 wat w 55 10.850 25.169 10.852 1.00 27.41 8 o atom 1740 ow0 wat w 56 1.649 50.280 9.162 1.00 45.96 8 o atom 1741 ow0 wat w 57 2.818 22.460 3.361 1.00 30.19 8 o atom 1742 ow0 wat w 58 6.939 28.751 18.021 1.00 21.48 8 o atom 1743 ow0 wat w 59 6.711 40.295 21.129 1.00 25.28 8 o atom 1744 ow0 wat w 60 9.491 23.601 4.589 1.00 29.21 8 o atom 1745 ow0 wat w 61 4.732 22.968 32.183 1.00 25.54 8 o atom 1746 ow0 wat w 62 3.245 23.888 0.683 1.00 27.48 8 o atom 1747 ow0 wat w 63 4.549 28.827 3.443 1.00 41.84 8 o atom 1748 ow0 wat w 64 16.762 21.566 19.087 1.00 24.93 8 o atom 1749 ow0 wat w 65 16.006 29.628 25.485 1.00 23.61 8 o atom 1750 ow0 wat w 66 19.671 38.994 19.445 1.00 21.93 8 o atom 1751 ow0 wat w 67 12.770 34.587 4.211 1.00 27.77 8 o atom 1752 ow0 wat w 68 3.613 28.695 34.171 1.00 32.54 8 o atom 1753 ow0 wat w 69 2.143 46.146 22.337 1.00 21.99 8 o atom 1754 ow0 wat w 70 11.266 36.608 0.771 1.00 43.42 8 o atom 1755 ow0 wat w 71 1.389 40.584 1.897 1.00 25.69 8 o atom 1756 ow0 wat w 72 9.590 34.622 0.707 1.00 28.56 8 o atom 1757 ow0 wat w 73 15.973 28.933 11.336 1.00 29.95 8 o atom 1758 ow0 wat w 74 11.061 20.499 37.743 1.00 39.23 8 o atom 1759 ow0 wat w 75 23.739 35.262 23.970 1.00 45.10 8 o atom 1760 ow0 wat w 76 8.589 41.730 11.384 1.00 17.86 8 o atom 1761 ow0 wat w 77 17.541 31.771 17.294 1.00 34.03 8 o atom 1762 ow0 wat w 78 9.975 20.417 21.834 1.00 41.59 8 o atom 1763 ow0 wat w 79 11.434 19.893 5.251 1.00 30.44 8 o atom 1764 ow0 wat w 80 10.671 43.182 31.401 1.00 42.36 8 o atom 1765 ow0 wat w 81 15.785 42.694 28.939 1.00 43.90 8 o atom 1766 ow0 wat w 82 13.075 43.095 17.421 1.00 28.16 8 o atom 1767 ow0 wat w 83 14.757 21.720 18.178 1.00 51.85 8 o atom 1768 ow0 wat w 84 11.832 32.572 2.024 1.00 32.71 8 o atom 1769 ow0 wat w 85 2.496 45.558 19.654 1.00 24.86 8 o atom 1770 ow0 wat w 86 3.515 47.175 15.702 1.00 43.61 8 o atom 1771 ow0 wat w 87 0.695 28.516 39.132 1.00 39.24 8 o atom 1772 ow0 wat w 88 7.830 26.767 39.676 1.00 29.78 8 o atom 1773 ow0 wat w 89 0.474 41.511 32.438 1.00 23.76 8 o atom 1774 ow0 wat w 90 2.976 16.622 6.539 1.00 29.91 8 o atom 1775 ow0 wat w 91 21.948 33.748 10.159 1.00 60.45 8 o atom 1776 ow0 wat w 92 3.371 21.393 34.375 1.00 34.65 8 o atom 1777 ow0 wat w 93 22.603 33.166 31.218 1.00 32.80 8 o atom 1778 ow0 wat w 94 7.926 41.009 17.875 1.00 36.23 8 o atom 1779 ow0 wat w 95 18.439 36.474 19.412 1.00 31.61 8 o atom 1780 ow0 wat w 96 5.429 41.239 19.675 1.00 40.52 8 o atom 1781 ow0 wat w 97 20.582 37.836 35.568 1.00 30.88 8 o atom 1782 ow0 wat w 98 23.221 31.607 29.089 1.00 34.68 8 o atom 1783 ow0 wat w 99 12.146 33.846 1.004 1.00 48.25 8 o atom 1784 ow0 wat w 100 18.822 24.740 12.299 1.00 32.46 8 o atom 1785 ow0 wat w 101 1.391 41.076 1.890 1.00 24.08 8 o atom 1786 ow0 wat w 102 10.726 40.370 33.837 1.00 33.73 8 o atom 1787 ow0 wat w 103 9.632 19.629 18.745 1.00 41.29 8 o atom 1788 ow0 wat w 104 3.386 16.452 31.884 1.00 46.20 8 o atom 1789 ow0 wat w 105 12.058 13.329 24.837 1.00 33.28 8 o atom 1790 ow0 wat w 106 7.547 15.008 28.630 1.00 35.80 8 o atom 1791 ow0 wat w 107 20.373 24.734 17.211 1.00 36.71 8 o atom 1792 ow0 wat w 108 2.610 31.441 35.560 1.00 36.40 8 o atom 1793 ow0 wat w 109 9.251 25.600 28.675 1.00 32.16 8 o atom 1794 ow0 wat w 110 11.971 32.083 3.246 1.00 30.14 8 o atom 1795 ow0 wat w 111 6.002 31.109 25.234 1.00 39.01 8 o atom 1796 ow0 wat w 112 0.433 24.275 4.740 1.00 38.25 8 o atom 1797 ow0 wat w 113 18.126 28.175 19.158 1.00 36.69 8 o atom 1798 ow0 wat w 114 12.379 38.438 32.959 1.00 36.08 8 o atom 1799 ow0 wat w 115 19.054 36.626 12.854 1.00 40.25 8 o atom 1800 ow0 wat w 116 18.602 30.639 19.399 1.00 36.96 8 o atom 1801 ow0 wat w 117 10.769 44.333 16.426 1.00 48.24 8 o atom 1802 ow0 wat w 118 10.869 40.767 8.309 1.00 34.42 8 o atom 1803 ow0 wat w 119 15.068 17.935 41.396 1.00 48.39 8 o atom 1804 ow0 wat w 120 1.692 15.677 21.014 1.00 41.42 8 o atom 1805 ow0 wat w 121 2.954 23.320 36.284 1.00 31.78 8 o atom 1806 ow0 wat w 122 19.201 40.341 36.271 1.00 49.58 8 o atom 1807 ow0 wat w 123 4.898 20.057 0.086 1.00 47.55 8 o atom 1808 ow0 wat w 124 3.752 14.290 13.359 1.00 40.38 8 o atom 1809 ow0 wat w 125 11.800 44.163 24.455 1.00 39.50 8 o atom 1810 ow0 wat w 126 11.856 24.824 24.333 1.00 36.60 8 o atom 1811 ow0 wat w 127 10.353 19.516 9.105 1.00 36.56 8 o atom 1812 ow0 wat w 128 12.367 15.111 30.129 1.00 46.42 8 o atom 1813 ow0 wat w 129 5.315 20.165 33.763 1.00 30.09 8 o atom 1814 ow0 wat w 130 11.790 20.099 11.052 1.00 45.03 8 o atom 1815 ow0 wat w 131 6.630 31.565 1.492 1.00 41.58 8 o atom 1816 ow0 wat w 132 7.326 21.938 31.335 1.00 51.41 8 o atom 1817 ow0 wat w 133 2.363 35.159 23.944 1.00 44.24 8 o atom 1818 ow0 wat w 134 6.470 21.515 4.910 1.00 29.79 8 o atom 1819 ow0 wat w 135 7.467 18.227 24.247 1.00 46.37 8 o atom 1820 ow0 wat w 136 17.299 17.544 19.488 1.00 44.37 8 o atom 1821 ow0 wat w 137 17.328 14.850 19.960 1.00 54.52 8 o atom 1822 ow0 wat w 138 2.456 33.205 3.701 1.00 42.39 8 o atom 1823 ow0 wat w 139 22.647 37.826 31.682 1.00 52.60 8 o atom 1824 ow0 wat w 140 1.944 34.349 3.049 1.00 54.44 8 o atom 1825 ow0 wat w 141 9.481 19.911 41.810 1.00 38.57 8 o atom 1826 ow0 wat w 142 16.796 43.302 25.650 1.00 37.55 8 o atom 1827 ow0 wat w 143 17.581 22.451 22.538 1.00 30.74 8 o atom 1828 ow0 wat w 144 8.342 9.947 13.611 1.00 46.58 8 o atom 1829 ow0 wat w 145 13.561 26.135 8.679 1.00 40.48 8 o atom 1830 ow0 wat w 146 11.860 22.971 2.736 1.00 47.52 8 o atom 1831 ow0 wat w 147 7.907 50.707 2.759 1.00 50.48 8 o atom 1832 ow0 wat w 148 7.759 7.515 20.288 1.00 48.12 8 o atom 1833 ow0 wat w 149 10.028 32.584 1.398 1.00 48.03 8 o atom 1834 ow0 wat w 150 3.436 39.000 24.408 1.00 31.71 8 o atom 1835 ow0 wat w 151 16.914 23.112 15.212 1.00 50.74 8 o atom 1836 ow0 wat w 152 8.418 49.387 11.663 1.00 46.17 8 o atom 1837 ow0 wat w 153 15.339 36.641 26.632 1.00 50.78 8 o atom 1838 ow0 wat w 154 8.042 15.079 11.242 1.00 49.08 8 o atom 1839 ow0 wat w 155 22.392 24.495 35.273 1.00 50.96 8 o atom 1840 ow0 wat w 156 3.356 19.171 36.223 1.00 61.39 8 o atom 1841 ow0 wat w 157 3.986 34.421 26.342 1.00 43.04 8 o atom 1842 ow0 wat w 158 7.105 28.768 0.040 1.00 44.54 8 o atom 1843 ow0 wat w 159 21.138 26.977 32.703 1.00 60.31 8 o atom 1844 ow0 wat w 160 8.193 16.517 1.801 1.00 43.37 8 o atom 1845 ow0 wat w 161 2.675 46.231 24.144 1.00 46.14 8 o atom 1846 ow0 wat w 162 20.971 39.299 16.925 1.00 48.29 8 o atom 1847 ow0 wat w 163 9.185 32.433 0.852 1.00 41.71 8 o atom 1848 ow0 wat w 164 4.405 11.944 31.263 1.00 55.39 8 o atom 1849 ow0 wat w 165 4.770 27.107 0.375 1.00 54.17 8 o atom 1850 ow0 wat w 166 1.451 43.839 2.744 1.00 49.50 8 o atom 1851 ow0 wat w 167 14.061 38.714 5.956 1.00 44.09 8 o atom 1852 ow0 wat w 168 13.353 37.178 35.666 1.00 57.16 8 o atom 1853 ow0 wat w 169 1.601 14.137 24.788 1.00 47.99 8 o atom 1854 ow0 wat w 170 14.633 32.421 2.239 1.00 49.23 8 o atom 1855 ow0 wat w 171 19.385 29.831 22.003 1.00 47.08 8 o atom 1856 ow0 wat w 172 9.097 19.406 26.244 1.00 45.97 8 o atom 1857 ow0 wat w 173 13.974 18.605 8.106 1.00 55.12 8 o atom 1858 ow0 wat w 174 14.290 34.894 39.161 1.00 55.60 8 o atom 1859 ow0 wat w 175 8.495 23.075 4.682 1.00 39.35 8 o
|
088-598-494-608-093
|
IT
|
[
"WO",
"EP",
"CA",
"IT",
"US",
"AU"
] |
G16H20/17,G16H40/67,G16H40/63,A61B5/00,G06F3/048,G06F15/16
| 2008-05-09T00:00:00 |
2008
|
[
"G16",
"A61",
"G06"
] |
a medical machine for fluid treatment
|
a medical machine for fluid treatment comprises a module (400) for management and sending of signal messages containing information relating to means (3) for fluid treatment. the module (400) comprises means (401) for determining a form for sending a signal message which is selectable automatically or manually from among a plurality of predefined forms. the module further comprises means (403) for generating contents of the signal message which comprise information (404a, 404b, 404c, 404d) relating to means (3) for fluid treatment; the contents (412) are created by selecting, for example via touch buttons on a touch screen, from among a selectable plurality of types of predefined contents (404a, 404b, 404c, 404d) and associating the relative data (405a, 405b, 405c, 405d) to the selected type; the module further comprises means (406) for determining at least an addressee to whom to send the signal message.
|
1. a medical machine for extracorporeal blood treatment, comprising: means for treatment of a fluid including: a predetermined number of sensors for detecting functioning parameters of the medical machine, and a predetermined number of actuators for intervening in order to modify the functioning parameters of the medical machine; a control unit sending command signals to the actuators and receiving information from the sensors for setting and determining an operative configuration of the machine, the control unit being further configured to generate at least a local user interface; a display for viewing the local user interface and for exhibiting at least a part of the information received from the control unit and relating to the means for fluid treatment; a module for managing and sending signal messages containing information relating to the means for fluid treatment; wherein the module comprises: means for determining a sending format for sending a signal message; means for generating contents of the signal message, the contents being determined by selection from among a plurality of types having predefined contents and comprising information relating to the means for fluid treatment; means for determining at least an addressee to whom to send the signal message, and wherein the means for generating contents of the signal message are configured to complete the contents of the signal message with current data substantially at the moment when the signal message is sent. 2. the machine of claim 1 , wherein the determination of the contents of the signal message is done by a manual selection between predefined types of contents. 3. the machine of claim 1 , wherein at least a part of the predefined types of contents comprises one or more visual representations which can be viewed on the local user interface. 4. the machine of claim 1 , wherein the means for generating contents of the signal message comprise a device for entering commands for enabling a selection of one or more of the predefined types of contents and wherein the device for entering commands comprises at least a touch screen associated to the display, the touch screen enabling a selection on the local user interface of the types of contents, by a user by touching or by proximity with one or more visual representations. 5. the machine of claim 1 , wherein the plurality of types of contents comprises a type of content chosen in the group including at least a copy of the local user interface and a configuration file and diagnostic data of the medical machine. 6. the machine of claim 1 , wherein the means for determining the sending format select the sending format either automatically or manually from among a plurality of predefined sending formats, the types of contents being different according to the sending format selected from among the plurality of predefined sending formats. 7. the machine of claim 1 , wherein the local user interface comprises a graphic user interface comprising a visual representation for each type of predefined contents. 8. the machine of claim 1 , further comprising means for configuring the module for sending the signal message, the means for configuring enabling a setting-up of a list of identifying addresses of addressees who can receive the signal message. 9. the machine of claim 8 , wherein the list of identifying addresses is viewed on the local user interface. 10. the machine of claim 8 , wherein the means for configuring the module enable one or more e-mail servers to be established for sending the signal message. 11. the machine of claim 8 , wherein the means for configuring the module enable an editable common standard text to be set up to be included in a signal message. 12. the machine of claim 1 , wherein the means for determining an addressee enable one or more addressees to be selected for the signal message, from a list of identifying addresses of addressees. 13. the machine of claim 1 , wherein the plurality of sending formats for sending a signal message comprises at least an e-mail form and an sms form. 14. the machine of claim 13 , wherein when the means for determining a sending format select an e-mail form, the means for generating a content of the signal message predispose the contents in a form of one or more file enclosures with the e-mail. 15. the machine of claim 1 , wherein the local user interface comprise a predetermined number of graphic elements each relating to a sending format for sending the signal message, the means for determining the sending format enabling a manual selection of one of the graphic elements for determining the sending format to be sent. 16. the machine of claim 1 , wherein the local user interface comprise a plurality of visual representations each relating to a type of contents of the signal message, the means for generating contents enabling a manual selection of one or more of the visual representations for determining a typology of contents of the message. 17. the machine of claim 1 , wherein the local user interface comprise a predetermined number of graphic representations each relating to an identifying address of an addressee or a group of identifying addresses of a group of addressees to whom to send the message. 18. the machine of claim 1 further comprising a web server operatively cooperating with the control unit and a predetermined number of web pages publishable by the web server, the web pages being accessible from a remote position via connecting means and being consultable via a web browser, at least a web page reproducing the local user interface. 19. the machine of claim 18 , wherein at least a web page reproduces the local user interface shown on the display of the medical machine, the web pages further publishing a plurality of further data relating to the medical machine. 20. the machine of claim 18 , wherein the web server is an internet web server which is consultable from a remote position by means of a web browser. 21. the machine of claim 18 comprising remote access and control means for enabling a reproduction on the web pages of the web server of the local user interface shown on the display. 22. the machine of claim 21 , wherein the remote access and control means enable reproduction of the local user interface in the web pages, substantially in real-time. 23. the machine of claim 21 , wherein the reproduction of the local user interface is updated at an each predetermined time interval or at each predetermined change in at least a parameter represented in the user interface. 24. the machine of claim 23 , wherein the user interface is sub-divided into a plurality of regions and that the updating of the reproduction of the user interface includes the reproduction of each region of the user interface being updated at each predetermined change of at least a parameter shown in the region without updating regions where a change has not occurred. 25. the machine of claim 18 , wherein the means for generating the contents of the signal message are activated remotely, by acting on the user interface which is accessible via the web pages published by the web server, the means for determining the sending format for sending a signal message being activated remotely by acting on the user interface, selecting respective graphic elements each associated to a respective sending format, the means for determining an addressee being activated remotely by acting on the user interface to select a graphic representation corresponding to an identifying address or a group of identifying addresses. 26. the machine of claim 1 , wherein the means for generating contents of the signal message enable determining a type of contents by selection, the information present in the contents of the message being automatically inserted into the signal message by the control unit, simultaneously with selection of the type of contents. 27. the machine of claim 1 further comprising a system memory, at least the information included in the signal message being sent by the control unit to the system memory for a subsequent consultation. 28. a medical machine for extracorporeal blood treatment, comprising: means for treatment of a fluid including: a predetermined number of sensors for detecting functioning parameters of the medical machine, and a predetermined number of actuators for intervening in order to modify the functioning parameters of the medical machine; a control unit sending command signals to the actuators and/or receiving information from the sensors for setting and/or determining an operative configuration of the machine, the control unit being further destined to generate at least a local user interface; a display for viewing the local user interface and for exhibiting at least a part of the information received from the control unit and relating to the means for fluid treatment; a module for managing and sending signal messages containing information relating to the means for fluid treatment, wherein the module comprises: means for determining a sending format for sending a signal message, the local user interface comprising a predetermined number of graphic elements each relating to the sending format for sending the signal message, the means for determining the form enabling a manual selection of one of the graphic elements for determining the form to be sent; means for generating contents of the signal message, the contents being determined by selection from among a plurality of types having predefined contents and comprising information relating to the means for fluid treatment, the local user interface comprising a plurality of visual representations each relating to a type of contents of the signal message, the means for generating contents enabling a manual selection of one or more of the visual representations for determining a typology of contents of the message, the types of contents being different according to the sending format selected from among the plurality of predefined sending formats; means for determining at least an addressee to whom to send the signal message enabling one or more addressees to be selected for the signal message, from a list of identifying addresses of addressees, the types of contents of the signal message being different according to the one or more addressees selected from the list of identifying addresses of addressees. 29. the machine of claim 1 , wherein the means for generating contents of the signal message are further configured to include one or more specially-sampled machine parameters in the contents of the signal message in addition to the current data. 30. a medical machine for extracorporeal blood treatment, comprising: means for treatment of a fluid including: a predetermined number of sensors for detecting functioning parameters of the medical machine, and a predetermined number of actuators for intervening in order to modify the functioning parameters of the medical machine; a control unit sending command signals to the actuators and receiving information from the sensors for setting and determining an operative configuration of the machine, the control unit being further configured to generate at least a local user interface; a display for viewing the local user interface and for exhibiting at least a part of the information received from the control unit and relating to the means for fluid treatment; a web server operatively cooperating with the control unit and a predetermined number of web pages publishable by the web server, the web pages being accessible from a remote position via connecting means and being consultable via a web browser, at least a web page reproducing the local user interface; remote access and control means for enabling a reproduction on the web pages of the web server of the local user interface shown on the display, wherein the remote access and control means enable reproduction of the local user interface in the web pages, substantially in real-time; a module for managing and sending signal messages containing information relating to the means for fluid treatment; wherein the module comprises: means for determining a sending format for sending a signal message; means for generating contents of the signal message, the contents being determined by selection from among a plurality of types having predefined contents and comprising information relating to the means for fluid treatment; means for determining at least an addressee to whom to send the signal message.
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background of the invention the invention relates to a medical apparatus and in particular a machine for extracorporeal treatment of a fluid, i.e. a patient's blood. as is known, machines for treatment of blood, such as for example machines for treatment of kidney failure or liver insufficiency or machines for plasmapheresis, i.e. machines for other types of fluid treatment, are provided with special means for treating a fluid in general comprising appropriate sensors and actuators which enable the cited treatment to be carried out. in general all the above-mentioned machines have in common a presence of a control unit which is destined to send control signals and to receive data from the sensors and/or actuators for monitoring and controlling the treatment. obviously for interaction with the machines, the operator can provide commands to the control unit, as well as view machine data and parameters in order to monitor its functioning. to this end, usually at least a device for entering data is included which can be constituted by a keyboard, a mouse, suitable buttons and activations, or even a touch screen; there is also always a special display for visualising the data requested received from the sensors and/or relating to the actuators. as the above concerns medical machines, those briefly described above are provided with special device for generating and managing alarms and signals which relate to a plurality of levels and different types of alerts. for example, document us 2003128126 describes a medical machine in which an alarm condition detector establishes the presence of a risk situation and an alarm controller generates the alert signal. the alert signal is directly correlated to the importance of the alarm that has gone off, and can be pre-configured as an audio alarm, or a flashing or coloured light alarm, or an e-mail message alarm, a local network message or even a telephone call to a doctor/operator. document us 2002099283, also relating to a medical system for monitoring the to value of blood coagulation measured in a patient teaches notifying a technician, i.e. a doctor, etc., via various types of message such as telephone, e-mail, normal post etc., according to the urgency and type of message to be sent. devices for management and despatch of signalling messages, as briefly described above, though well achieving the aims they set for themselves, are however affected by some operating limits and/or drawbacks and have shown themselves to be susceptible to improvement under various aspects. firstly, devices for managing and sending signal messages are non-configurable (or in any case are hard to configure) if not during the stage of predisposition of the machine, and typically by a specialised technician. in general, on verifying the situation of danger the known system automatically implements the signals paired with the type of alarm. the nursing staff, doctors or patient cannot usually intervene rapidly on the medical machine to manage or configure signalling of an alarm in a way which is most suited to a particular situation that has arisen. further, known systems do not enable, if not a priori, establishing a type of despatch and the correct target (in terms of expert personnel) of a signal, nor is it usually possible to intervene in order to vary and/or implement the information sent. aim and summary of the invention the aim of the present invention is thus substantially to obviate the above-cited drawbacks. a first aim of the invention is to make available a medical machine provided with a module for managing and sending message signals which enable guaranteeing an excellent functioning reliability of the alarm signal, at the same time affording the possibility for the personnel to intervene during the sending of the signals themselves. a further aim of the present invention is to provide a medical machine which enables customisation, of the signals management, both in terms of contents and in terms of the transmission format, and also in terms of the addressees of the information. a further aim is to enable management and sending of signals at any moment without an automatic machine alarm or intervention situation necessarily having been triggered. an auxiliary aim of the invention is to enable a differentiated management of the sending of the signals according to the addressee and/or according to the type of alarm and/or signalling necessary. these and other aims, which will better emerge during the course of the following description, are substantially attained by a medical machine for fluid treatment according to the accompanying claims. further characteristics and advantages will better emerge from the detailed description that follows of a preferred though not exclusive embodiment thereof, according to the invention. brief description of the drawings the preferred embodiment will be described herein below with reference to the accompanying figures of the drawings. fig. 1 is a schematic view of an apparatus of the present invention, in which the medical machine is monitored/controlled by a remote unit; fig. 1 a schematically illustrates a medical network including machines that implement the inventive idea of the invention; figs. 2 and 3 schematically illustrate, in a first and a second embodiment, means for fluid treatment, part of the medical machines of fig. 1 ; fig. 4 is a further schematic view of a medical machine of the present invention; fig. 5 is a schematic view of a form for sending a signalling message of the machine of fig. 4 ; and figs. 6 a - 6 c are schematic views of a graphic user interface shown by the display of the medical machine of fig. 4 . detailed description of some preferred embodiments fig. 1 a is a schematic view of a medical network which incorporates the object of the present invention. the inset 310 provides an example of a first portion of the medical network, delimiting the apparatus of the network which are typically present internally of a same building, such as a hospital, a dialysis unit, or a clinic. a plurality of medical machines 2 are included in the first portion of network 310 , and in particular medical machines suitable for fluid treatment. the medical machines 2 can all be connected to one another and to a central server 309 . the central server 309 can comprise at least a computer server 311 , a database 312 , and means for access 313 to the external portion 314 of the medical network 1 . as can be seen, still schematically, there is also at least a visual access terminal (and usually a plurality) 316 in order to enable the personnel (in particular the nursing staff) an access to the data contained in the central server 309 and therefore access to the net. a plurality of desktop personal computers 317 will be connected to the network, which will have access to the central server 309 , and to the medical machines 2 as will be better clarified herein below. access can also be given to other apparatus such as hand-held computers 319 or laptops 318 , directly connectable to the server 309 and/or medical machines 2 , as shown in fig. 1 a. the external portion of the network 314 includes the presence of a plurality of remote accesses 320 which might be constituted by terminals for technicians working on the maintenance and/or control of the functionality of the medical network, terminals for doctors, terminals or even patients' medical machines, or other hospitals, clinics or medical units. access can also be given to a domiciled medical machine, not necessarily connected to a hospital network. in this case the remote access can be effected, for example, via a remote computer provided with an appropriate web browser able to communicate with a web server provided on the domiciled medical machine. in this case the network architecture will, in the most elementary form, be constituted by at least a medical machine which will be provided with its own network address and by a remote terminal which will connect to the machine via the address. obviously the use of the internet as a net infrastructure will enable creating very varied network architectures according to the needs of each individual case. in the light of the above, a medical machine 2 will now be described which is suitable for fluid treatment, which can be used in the medical network 1 as briefly described above. the machine can be, for example, a machine for blood treatment, such as a machine for treatment of kidney failure (for example a hemo(dia)filtration or dialysis machine, for chronic or intensive therapy), or liver insufficiency or a machine for plasmapheresis or in any case any other type of medical machine which is suitable for fluid treatment. in the following, reference will be made to a medical machine for extracorporeal blood treatment in its essential components of known type and therefore only partially described. the apparatus for fluid treatment comprises suitable means for blood treatment 3 . in particular the means 3 comprise a hydraulic circuit 100 . an example of a hydraulic circuit is schematically shown in fig. 2 . note that the specific structure of the hydraulic circuit 100 is irrelevant for the purposes of the present invention, so different circuits to the one specifically shown in fig. 2 can be involved, according to functional and design needs for each single medical apparatus. the hydraulic circuit 100 optionally exhibits at least a supply channel 102 , destined for the transport of a treatment liquid of at least a source 103 towards a treatment station 104 , where one or more blood treatment units 105 operate. the circuit 100 further comprises at least a discharge channel 106 destined to transport a used liquid from the treatment station 104 towards an evacuation zone, schematically denoted by 107 in fig. 2 . it should be noted that the supply channel 102 is destined to cooperate with means for moving a fluid, such as at least a pump 122 , for example a positive displacement pump, such as in particular a peristaltic pump, or a gear or diaphragm pump. a branch can be present downstream of the pump 122 and along the circulation direction, which divides the primary sterile fluid circuit into an inlet branch and an infusion branch (not illustrated but of known type). the infusion branch is connected to the blood removal line (arterial line) and/or the blood return line (venous line) of the blood circuit and enables an infusion to be obtained directly into the blood (before and/or after the blood treatment unit 105 ) using sterile fluid. the input branch brings the sterile fluid directly to the blood treatment stations 104 for exchange through the membrane 114 . obviously selector means (for example a valve element and/or means for moving, such as one or more pumps) will be present for determining the percentage quantities of fluid flow in the infusion branch and the entry branch. the sterile fluid for dialysis thus enters the discharge channel 106 of the circuit and crosses a pressure sensor 123 provided for control of the functioning of the line. there are therefore further fluid movement means present, for example a drainage pump 124 which can control the flow in the discharge channel 106 of the circuit. the drainage pump 124 can, in general, be a positive displacement pump, such as for example a peristaltic pump, or a gear pump, or a diaphragm pump. the fluid to be eliminated thus crosses a blood leak detector 125 and is conveyed towards the evacuation zone 107 . the treatment fluid (dialysis fluid or replacement fluid) can be purified before use by one or more ultrafilters 126 . the hydraulic circuit 100 cooperates with a blood circuit 108 which is also schematically represented in fig. 2 in its basic components. the specific structure of the blood circuit is also not fundamental with reference to the present invention, and thus, with reference to fig. 2 , a brief description of a possible embodiment of the circuit is provided, which should however be considered to be provided purely by way of non-limiting example. the blood circuit 108 of fig. 2 comprises an arterial line 109 for removing blood from a vascular access 110 of a patient and a venous line 111 predisposed to return the treated blood to the vascular access. the blood circuit of fig. 2 further comprises a first chamber, or blood chamber 112 , of the blood treatment unit 105 whose second chamber 113 is connected to the hydraulic circuit 100 . in greater detail, the arterial line 109 is connected to the inlet of the blood chamber 112 , while the venous line 111 is connected in outlet to the blood chamber 112 . in turn, the supply channel 102 is connected in inlet to the second chamber 113 , while the discharge channel 106 is connected in outlet to the second chamber. the blood treatment unit 105 , for example a dialyser or an ultrafilter or a plasma filter or a hemofilter or a hemodiafilter, comprises, as mentioned, the two chambers 112 and 113 , which are separated by a semi-permeable membrane 114 , for example a hollow-fibre or plate-type membrane. a blood pressure sensor 118 is located on the arterial line 109 along the circulation direction of the blood from the removal zone (vascular access) towards the blood treatment unit 105 . the arterial line 109 is further connected to a device for administering an anticoagulant 119 , for example a syringe pump for providing appropriate anticoagulant doses (heparin). the arterial line can thus be provided, optionally, with a further pressure sensor 120 (arranged between a pump 117 and the unit 105 ) for surveying the correct flow internally of the blood circuit. the blood circuit can also comprise one or more air separators 115 : the example of fig. 2 shows a separator 115 on the venous line 111 , upstream of a safety valve 116 . the treated blood, exiting from the air separator device 115 , crosses an air bubble sensor 121 , provided to check for the absence of dangerous formations internally of the treated blood which must be returned into the patient's blood circuit. in particular, should the air bubble sensor reveal the presence of faults in the blood flow, the machine, via the safety valve 116 (which might be a cock, a clamp or the like) it would be able immediately to block blood passage in order to prevent any type of consequence to the patient. the valve 116 can always be closed in the venous line should, for example for safety reasons, it become necessary to interrupt blood return to the vascular access 110 . the means 3 for fluid treatment can also comprise one or more blood pump 117 , for example positive displacement pumps such as peristaltic pumps; in the example of fig. 2 there is a pump 117 on the arterial line 109 . in general, the hydraulic circuit 100 is housed internally of a chamber in the machine body, while the blood circuit 108 is borne on a front panel of the machine body which also supports the peristaltic pump or pumps 117 . the treatment unit 105 can be removable physically supported, by rapid-attachment means (of known type) arranged, for example, on a lateral wall of the machine structure itself. the treatment unit 105 , in operating conditions of blood treatment, is connected both to the hydraulic circuit and to the blood circuit as already briefly mentioned. as is obvious and indeed known, the means 3 for fluid treatment comprise the cited sensors for detecting functioning parameters of the medical machine 2 and also the cited actuators for intervening in order to modify the functioning parameters of the machine 2 . each medical machine 2 in general comprises a control unit 4 which is programmed at least to send command signals and to receive data from the means 3 for fluid treatment. the control unit 4 is thus active at least on the blood circuit and in particular on the pressure sensor 118 , on the blood pump 117 , on the heparin infusion device 119 , on the further pressure sensor 120 as well as on the device for detecting the presence of air bubbles 121 and on the closing element 116 . the control unit 4 will be active on the pump 122 , on any selector means present, on the pressure sensor 123 , on the drainage pump 124 and will also receive information from the blood leak detector 125 . further, the control unit 4 is set up to control the hydraulic circuit 100 of the sterile fluid and in particular will receive in input the data read off by any balances present on the machine relating to the weight of the various containers which may be in use on the machine. obviously, apart from the control of the sensors and the actuators, the control unit 4 may be predisposed to receive and control further sensors and actuators present on the machine in order to guarantee and monitor the functioning thereon. the machine for extracorporeal treatment may be provided with a fluid balance system, of the type used in a machine for hemodialysis and hemo(dia)filtration, for control of the patient's weight loss during the treatment, for example a flow-meter type, or a variable-volume volumetric chambers system, or a system including balances, or other systems of known type. the machine can be provided with a system, of known type, for on-line preparation of the treatment fluid (for example dialysis fluid and/or replacement fluid) starting from water and concentrates, and/or a system (of known type) for degassing and/or heating the fluids running through the system itself, and/or a purification system having one or more treatment fluid ultrafiltration stages. the machine can be provided with a disinfection/cleaning system (of known type, for example of a chemical or thermal type, supplied by a distribution network or a batch source of disinfecting agents/cleaners) of the hydraulic circuit 100 . purely by way of example there might also be a liquid loss sensor destined to detect any eventual breakages or damage to the hydraulic circuit, which sensor will then send the data on directly to the control unit 4 for subsequent processing. the control unit 4 can, for example, comprise one or more digital microprocessing units or one or more units of an analog and/or digital type. in practice, in reference to the example of a microprocessor unit, once the unit has completed a special program (for example a program coming from outside the system or directly installed on the microprocessor), it is programmed by defining a plurality of functional modules or blocks which constitute means each predisposed to perform respective operations. the medical machine is provided with at least a display 6 for viewing at least a part of the data received from the control unit 4 relating to the means for fluid treatment. further, the medical machine will be provided with at least one and in general a plurality of devices 5 for entering the data to be supplied to the control unit 4 in order to enable a user to generate the above-mentioned command signals for the means 3 for fluid treatment. the devices for entering data can be of various natures and be constituted, even in combination, by a keyboard, a mouse, keys and buttons and activations, or even a touch screen. in particular the display or screen of the medical machine 2 displays a graphic user interface (gui) which provides an intuitively-comprehensible display of at least a part of the data received from the control unit 4 relating to the sensors and the actuators on the fluid treatment circuit. merely by way of non-limiting example, in a case in which a graphic user interface is used with a configuration of the touch screen, the display 6 itself will be divided into various areas exhibiting a plurality of touch keys and a plurality of pictograms, each for example associated to a relative touch key. the expression “touch screen” relates to a screen for data output, also used for input by means of direct selection using the fingers of parts (touch keys) of the screen display to send the commands for performing the user's requested action to the control unit 4 . the use of a touch screen might for example configure the display and the device 5 for entering the data in a single element. the main aim of a touch-screen display is that it makes the interface more intuitively simple use for the operator, and at the same time simplifies the use of the machine. the medical apparatus advantageously also exhibits remote access and control means 10 which can enable a remote unit 7 to accede to data present in the medical machine and selectively take over control of a predetermined number of functions of the medical machine itself. in general the remote access and control means 10 comprise at least a central control program 12 for enabling remote administration of the functions of the medical machine; the central control software 12 can be a vnc type program, and in particular a vnc server program. in general, vnc programs (virtual network computing) are open source with remote control and serve for remotely administrating a machine. the vnc server will cooperate with the control unit 4 which, once the program has been run, will be programmed to define the access and control functions from a remote position. purely by way of example, the vnc server can be pre-stored on a memory bank 13 of the medical machine to which the control unit 4 will be able to accede. obviously the remote access and control means 10 will also comprise client control software 14 for interacting with the central control program 12 in order to enable the mentioned data exchange between the control unit 4 and the remote unit 7 . the client control software 14 will also optionally be of the vnc type and in particular vnc client. note that while the vnc server will in general be stored internally of the medical machine, the vnc client might be differently located. the vnc client might for example be directly loaded on the remote control unit 7 which might be an electronic processor such as a computer, but also a hand-held computer or a smart-phone. alternatively the vnc client might be directly installed in an intermediate server, to which the remote unit 7 will accede and which in turn will initiate the communication with the medical machine. in a preferred embodiment it will also be possible for the vnc client to be loaded directly in the medical machine 2 such that it is possible to accede to monitoring and control functions remotely by using a remote control unit 7 without any type of dedicated software, for example a normal processor, a hand-held unit or a smart-phone, as long as it is on-line with the medical machine to be controlled and/or monitored. for this purpose the medical machine will be provided with a web server 11 operatively cooperating with the control unit 4 . in general a web server is a program which on request of a browser 18 requests one or more web pages (often written in html). a web server is also usually (though not necessarily) provided with a fixed ip address on the net such as to be able to gain remote access more simply. the data sent from the web server travel in a processor network, transported by the cited http protocol (or equivalent protocols). the web server 11 of the medical machine 2 is configured to provide a predetermined number of remotely-accessible web pages via the connecting means 16 . the web server 11 can contain the predetermined number of web pages or it can generate them at the necessary moment and send them. in particular the web server 11 can generate these web pages in real time and can therefore transmit them to a user (for example via the connecting means 16 ), particularly on request of the user him or herself. this enables system is security to be increased, especially because it prevents undesired breaches by hackers onto any pages stored in a memory. in effect the web server 11 , in order to reduce the risk of fraudulent break-ins from the outside, might not necessarily operate by storing data (web pages), but via generation on demand (in real-time) of data (i.e. web pages) requested. in detail, the medical machine is predisposed to be connected to the internet in particular with a fixed ip address such that the web pages thereof are selectively accessible. a general characteristic of a web server publishing web pages, i.e. an internet website, is that of being available on the internet with a certain degree of continuity for those who need to access the site. in this sense the connecting of the medical machine could be defined as a permanent connection which denotes the normally-active connection to the internet which characterises web-sites and distinguishes them from convention client serves which, on the contrary, must set up a new connection each time exchange of data is required, with any remote processor. it is clear that for breakdowns, maintenance or other extremely practical matters, the connection between the machine and the internet can be interrupted, without altering the characteristic of substantial temporal continuity of the connection. the connecting means 16 advantageously comprise an auxiliary memory, predisposed to contain a permanent ip address, independently associated to the medical machine; the ip address is used for the above-mentioned permanent connection to the internet. a further fundamental characteristics of an internet site is that the server which physically incorporates the contents of the site is identified by an ip address (internet protocol) so that the server can be correctly addressed by the various routers and providers constituting the internet. the ip address is basically constituted by a 32-bit number, for the sake of simplicity usually a sequence of four numbers, each comprised between 0 and 255, and separated from the others by a dot (for example 192.168.9.112). as indicated, ip addresses are used for identifying the actual physical machines in which the web pages are contained, together with the contents attached thereto, which constitute an internet site. to enable net users to record the addresses of the various sites, each ip address is usually, but not necessarily, univocally associated to a domain name, i.e. a sort of name or title given to the site and indicating the contents of the site. at the moment when a net user decides to connect to a predetermined internet site, she or he enters the name of the site or the ip address to be visited in the address bar of her or his browser. in the case in question, the remote user enters the domain name or the ip address of the machine she or he wishes to contact. the composition of the domain name constitutes the generation of the request signal; the domain name is immediately converted into the corresponding ip address, such that the request is correctly directed towards the medical machine 2 . this is made possible by the structure of the internet, internally of which the various nodes are able, via a series of pre-stored tables, to direct the signals to the pre-selected address. a first table enables the addressee's ip address to be found, if the domain name associated thereto is known; the subsequent tables set up the distance link between the remote processor 7 and the medical machine, appropriately selecting the branches of the net to be used for the transmission. finally, a last database associates the ip address to a branch which is directly connected to the addressee computer, such that the data can be sent to it. in the light of the above, it is clear how the dedicated association of a permanent ip address to the medical machine enables the machine to be visible to the users on the internet, and in particular the doctor, technician or remote user, to all effects just like a website which can be accessed independently of the physical position of the remote processor 7 . in some cases, for example, when the various servers and providers reorganise their internal databases with the aim of optimising the exploitation of the hardware and software resources and rendering net operation as efficient and possible, ip addresses associated to each site can be changed; this does not mean however that the ip address combined with a predetermined internet site cannot be defined as permanent, differently to the provisional code attributed to normal clients each time the client accesses the net via its provider. the web pages provided (contained or generated in real-time) in the web server 11 of the medical machine are consultable via a web browser 18 , i.e. a program which enables the users to view and interact with texts, images and other data contained in one or more web pages of a web server. the web browser 18 is generally able to interpret the html code and display it in the form of a hypertext, enabling surfing of the web server pages. the web server 11 in the medical machine 2 will be accessible via standard-type web browsers 18 , commonly used for surfing the internet. by way of example, the following browsers can be used: internet explorer, mozilla firefox, opera or others besides, for access to the web server of each of the medical machines. usually, and advantageously, web pages of the web server comprise the client control software 14 such that it does not necessary have to be resident or have been downloaded previously on the remote processor for access to the medical machine. obviously the control software could be a compiled program, resident on the web page of the web server of the medical machine, for downloading, installing on the remote unit and thereafter being usable; however it has been found to be particularly advantageous to upload the program to the web page in the form of a specific language, for example a scripting language or an interpreted programming language (i.e. which is not compiled)—destined in general for use in system automation (batch) or applications (macros), or for use in the web pages. examples of scripting languages are javascript, vbscript, shell scripting (unix), perl, php, python e ruby. an example of an interpreted language is javaapplets. all of the above means that the client program 14 , in scripting language or interpreted language, is directly and automatically executed (interpreted) by the web browser 18 without any need for intervention on the part of the user. having directly provided the web server 11 with the vnc client software 14 constitutes a considerable simplification of the monitoring and control procedures. it should be noted that at least one of the web pages of the medical machine 2 reproduces the graphic user interface shown on the display 6 of the machine itself, apart from a plurality of further data and information relating to the medical machine. in more detail, thanks to the remote access and control means 10 (which comprise the vnc server and the vnc client), the graphic user interface shown on the display 6 is reproduced in the web pages of the web server 11 and the reproduction is done practically in real-time. in other words, the reproduction of the graphic user interface is updated at each predetermined time interval and/or at each predetermined change of at least a parameter represented in the graphic user interface itself. the above-mentioned update of the graphic user interface can also be done as follows, with the aim of reducing the amount of work done by the controller. the display is subdivided into a plurality of regions (distinct monitoring regions) in which each region of the display is subjected to a monitoring; each time a change in the information reproduced in a certain region of the screen occurs, the update only for that region is sent. the user can therefore, for example by means of an authentication with a password or similar authentication systems, access the web pages of the medical machine, receive a graphic representation which substantially coincides and is in real-time with the graphic representation of the user interface or gui, and can also surf between the cited plurality of further data published in the web pages of the web server 11 , such as for example information relating to the configuration of the machine (version of the programs loaded, cards installed on-board, etc.). the user can also access the pages for data relating to maintenance (days since last check, or until next maintenance operation). the user can receive information relating to the replacement of the ultrafilter (days since the last or before the next replacement of the ultrafilter, number of disinfection operations carried out since the last replacement, etc.). time/variation graphs can be viewed for some predetermined parameters, so that their progress can be monitored. access might be given to the alarm record of the machine (for example the last n alarms, the most frequent alarms, etc.). access can be given to data relating to the dates of disinfections performed on the machine, as well as to the history of control tests done by the machine in the context of preventive maintenance, as will be more fully described herein below. as however previously mentioned, the remote access and control means 10 are not exclusively dedicated to enabling secure access to a plurality of data relating to the medical machine, but have also the function of enabling selective control of at least a predetermined number of functions of the machine itself. the controllable functions of the medical machine are multiple and can comprise, purely by way of example, pump velocity, heparin doses (or other substances), treatment operating parameters, such as the treatment times of the rate of ultrafiltration; further, among the controllable functions are the internal check or diagnostic check procedures, as are the updating or downloading of programs onto the machine. in a non-exclusive preferred embodiment, the remote access and control means 10 enable the remote control unit 7 to take over complete control of the medical fluid treatment machine 2 such that a remote user can interact with the machine as if she or her were actually standing in front of the machine 2 controls. generally, for each remote connection, the user will have to be identified and the authentication will be done for example by means of entering the identification and corresponding password. in any case remote identification might be done in different ways, possibly even in combination, and according to the required level of security. identification systems can be used such as cards with chips, or contactless, means for biometric recognition (fingerprints, iris recognition or the like), or others besides. in any case, at least an id datum must be included among the data exchanged by the medical machine 2 with the remote unit, perhaps for example by the control unit 4 (but also from the web server 11 or even from the central control program 12 ). the machine 2 will include a list of predefined identification data, to each item of which a respective access authorisation to the medical machine will be associated. the access authorisations define the remote interventions the user can make on the medical machine. they comprise at least the authorisation to passive access to vision, i.e. to be allowed to view the web pages of the web server 11 without however being able to control any machine 2 functions, and at least permission to actively access in order to control, i.e. to actively control (i.e. change or set machine operating parameters or activate/deactivate functions) from a remote location. in reality the access levels can be many, and can be easily customised such that each user can only view and/or intervene on the machines 2 to pre-decided extents. some users might only be authorised to view the gui, while others might be authorised to view all machine data but without any authority to intervene. others besides might have active control access only to some machine functions and not others, while still others might have total access to all machine functions both passively (viewing) and actively (controlling). thus levels of access can be defined, for example for medical personnel, nurses, technical staff controlling and maintaining the machine, or net system administrators. on each connection, after the id procedure, the control unit 4 (or as mentioned the web server 11 or the central control program 12 ) will verify access authorisation and will assign the user the level of access afforded to him or her. in other words, according to the type of protected access afforded, the remote user will be able to operate at least in a solely monitoring mode (having access to all the above-mentioned data without any power to interact actively with the medical machine) and a full machine control mode (where she or he will be able to interact and command the medial machine as if standing right before it). obviously situations can be set up in which there is only a partial control modality, i.e. only some of the functions normally controlled by acting directly on the machine. note however that the control unit 4 of the medical machine is predisposed to selectively inhibit the remote access and control means 10 from taking and/or maintaining control of at least some of the predetermined number of medical machine functions in particular not only according to the id of the user, but also (or even only) according to the operating configuration (or modality) of the machine itself. in other words the medical machine 2 will operate in a plurality of different operating configurations (or modes), some of which will be more or less critical for security. with reference to known-type medical machines for extracorporeal blood treatment, some of the above-mentioned various operating configurations can be described: at least a first operating configuration for machine start-up and automatic check of its operability; a priming operating configuration of the hydraulic circuit, which consists in the preparatory stage of the machine before treatment in which air is removed from the piping; a disinfecting/cleaning operating configuration (for example chemical and/or thermal) of the hydraulic circuit; a rinsing operating configuration of the hydraulic circuit; an operating configuration in which treatment fluid is prepared (for example a dialysis fluid) up to reaching the desired characteristics of the fluid, etc. there is also an operating configuration in which the medical machine is set up for use, i.e. all single-use disposable components are applied, such as the filter and the blood circuit. there is also a blood circuit priming operating configuration, and configurations for other disposable circuits too. there is also an operating configuration of connecting the patient to the machine and a treatment configuration followed by the patient blood return operating configuration (rinse-back) after finishing the treatment, and finally the disconnection of the patient. further machine configurations can be identified, i.e. a configuration in which the disposable components are removed, or one in which the liquids still present in the circuits are eliminated, as well as other operating configurations connected with various further procedures such as calibrations, maintenance or more besides. merely by way of example the critical operating configurations for questions of security are the stage of connecting and the stage of disconnecting the patient to and from the machine before and after treatment, as well as the stage of treatment true and proper and the stage of rinse-back, in which the residual blood is returned to the patient. should the control unit 4 detect that the machine is in one of the operating configurations defined as critical for security, the control unit itself would be empowered to prevent the remote means for access and control 10 to take control of the medical machine or, in a case in which a remote unit 7 is controlling, the control unit 4 would exclude any possibility of proceeding with said control/intervention from remote. all of the above is true whatever the type of the individual in remote connection (doctor, technician, etc. . . . ) thus according to the operative configuration, the control unit 4 is automatically able to detect a situation of potential danger and will prevent access by a remote user whatever her or his authorisation level. this mode of operation thus enables potentially dangerous situations to be accounted for, in which sending commands to the machine would be preferable or it would be physically necessary to be present in the place where the medical machine is located in order to take account of situations which cannot be perceived from a remote position (interactions with the patient such as disconnection or connection, or the state of the patient during treatment etc.). it should be noticed that in general, in order to be able fully to exploit the above-described functionalities, the remote unit 7 will be provided with a respective device 8 for entering at least command data (in this case too it might be a keyboard, a mouse or a touch screen or another suitable system) and also a display screen 9 for viewing at least a part of the information relating to the fluid treatment means 3 and in general the graphic user interface substantially in real-time (i.e. with transmission delays of a few seconds). obviously there will be connecting means 16 present for setting the remote unit 7 in communication with the medical machine 2 for fluid treatment for exchange of data. in general the connecting means 16 are of known type and comprise a computer network, for example an internet network and/or an ethernet and/or a wireless network, for setting the remote unit 7 (any unit 7 connected to the network) in communication with a the means for fluid treatment 2 (i.e. the desired machine from among all the machines connected up to the network and therefore accessible). the means 16 shall be provided with receiving and transmitting modules able to receive a request signal coming from the remote unit 7 and transmitting, following the reception, a transmission signal destined for the remote processor and incorporating the data and/or one or more of the web pages present on the web server 11 managed by the processing unit 4 . to this end there will also be special communication ports, network cards and/or modems not further described herein inasmuch as they are of absolutely known type in the sector. the medical machine 2 will advantageously be provided with at least a module 400 for the management and despatch of a signal message containing data relating to means for fluid treatment. this module, which can for example be a software program stored in the memory and run by the control unit 4 , is schematically illustrated in fig. 5 . means 401 for selecting a format 402 a , 402 b are present for sending a signal message. in general the means 401 select the format from among a plurality of predefined formats 402 a , 402 b , 402 c , 402 d either automatically or manually. purely by way of example, possible formats (which can be of many types) comprise e-mail messages, sms text messages, mms or others besides. the selection of the format can be automatic and obviously predefined, in which an alarm (for example a pump failure), or a notification (for example n days since a maintenance intervention) have been configured such that the control unit 4 uses the format without any need for the intervention of an operator, thus guaranteeing top-level reliability of notification in predetermined situations. in the case of a manual selection (the operator can decide at any moment), the user interface 300 will comprise a window exhibiting a predetermined number of graphic elements 413 , such as pictograms and/or logograms (for example in the form of touch buttons), each relating to a format for sending a signalling message. the user interface, which in the specific case comprises the display of the graphic user interface (i.e. associated to the medical machine), can comprise, in other embodiments, a remote device, either additionally or alternatively to the local display. it is thus possible to include both the use of a local graphic user interface and the use of a remote graphic user interface (for example such as the one described herein above). the remote user interface might be able to is reproduce another user interface, different from the one viewed on the local display, for example a further interface which can be generated by the control unit of the medical machine 2 . in other terms, the control unit 4 will predispose a predetermined number of pages (for example web pages) corresponding to different user interfaces and the user can shift among the pages either directly on the medical machine 2 in question, or remotely with a common terminal and further the pages viewed on the machine and on one or more of the connected remote terminals can be different from one another (i.e. each user can view the page of interest to him or her). looking at fig. 6 a , a plurality of touch buttons 413 can be seen, each of which relates to a different format. the nurse, doctor or maintenance technician alike can decide at any moment during operation (even not in the presence of alarms or specific predefined situations) to generate a particular message, by sending a predetermined number of data to predefined addressees (as will better emerge in the following description). the manual selection can be done differently, for example by using a keyboard or a mouse and clicking on the respective touch button. alternatively and advantageously a touch screen can be used by directly pressing the corresponding touch button such as to make the operation more intuitive, rapid and simple. the module 400 further comprises means 403 for generating contents for the signal message. the contents 412 are usually constituted by the type of contents 404 a , 404 b , 404 c , 404 d and by the actual information 405 a , 405 b , 405 c , 405 d relating to the medical machine in general and specifically to the means 3 for fluid treatment. the contents 412 are principally determined by means of selection from among a plurality of types of predefined contents 404 a , 404 b , 404 c , 404 d. in general, following each selection relating to the format 402 a , 402 b , 402 c , 402 d of the signalling message, the user interface 300 will present a plurality of visual representations 410 , for example pictograms or logograms (optionally, as in this case, in the form of touch buttons), each relating to a type of contents 404 a , 404 b , 404 c , 404 d of the signal message (see fig. 6 b ). in general, though not necessarily, the visual representations 410 will be different according to the format 413 of the message selected. it is clear that an e-mail has a different capacity of information in comparison with an sms or an mms message. in particular, the means 403 for generating the contents enable a selection to be made from among one or more visual representations 410 in order to determine the type of contents of the message. as in the preceding situation, the means 403 for generating contents of the signalling message comprise a device 5 for entering commands with the aim of enabling selection of one or more types of predefined contents 404 a , 404 b , 404 c , 404 d. the device for entering commands 5 will advantageously comprise at least a touch screen associated to the display 6 ; the touch screen enables the user to select the types of contents 404 a , 404 b , 404 c , 404 d from the user interface 300 , selecting by contact with or proximity to the respective visual representations 410 . it is stressed that several types of predefined contents can be associated to each format of the signalling message. when, for example, the means 401 for determining a format select an e-mail format 402 a , the means 403 for generating signal message contents predispose the contents 412 in the form of one or more attached files to the e-mail message. the plurality of types of contents 404 a , 404 b , 404 c , 404 d comprise, for example, a copy (screenshot) of the current graphic user interface 300 , as visualised by the machine 2 at the moment when the selection of the type of attached file was sent, and its time of despatch. other types of contents (enclosed with the e-mail) can be files or models containing specially-sampled n machine parameters, which can be preconfigured and completed with the current data at the moment of selection of the type or at the moment the message is sent; alternatively, or in addition, files or blocks relating to the configuration of the medical machine itself (data relating to the cards mounted on the machine, the release of the various programs etc) can be sent, and/or the diagnostic data (alarms set off during the time period, tables summarising the machine status, etc) or apparatus check-ups. it will be understood that the types of contents will be different and will be sent according to the needs of the moment. it is also clear that a maintenance technician will wish to see the machine check-up data or configuration information; the doctor will want to check the medical machine parameters during its functioning, i.e. the graphic user interface when a problem crops up during treatment. note that at the moment when the means 403 generating the contents of the signal message determine the type of contents, the information 405 in the contents of the message will optionally be automatically uploaded to the signal message at the same time as the selection of the type of contents of the control unit. in other words, when the operator decides to send, for example the graphic user interface by e-mail, the medical machine, i.e. the control unit 4 , can automatically load the data relating to the moment it was decided to send the e-mail. equally, at the moment that the operative machine parameters are selected for mailing, the machine automatically acquires the parameters and enters them into the format, completing the contents 412 of the signal message. it is therefore evident that, selected by one of the predefined formats, the contents which are associated to the format for completing the contents 412 of the signal message will vary from moment to moment, thus enabling a photograph of a topical moment to be made at any time for future analysis. finally, the form 400 comprises means 406 for selecting at least an addressee to whom to send the message. the user interface 300 exhibits, usually, a predetermined number of graphical representations 414 , 415 , for example pictograms and/or logograms (in this case too they can be touch buttons), each of which relates to an addressee's identification address, or relative to a group of identifying addresses of a list of addressees. in other words the means for selecting an addressee 406 enable one or more addressees of the signal message to be chosen from a list of identifying addresses 407 a , 407 b , 407 c , 408 a , 408 b , 408 c. as can be seen in fig. 5 , single addressee-identifying addresses (e-mail addresses, cell-phone numbers, etc.) can be created, i.e. lists of addressees a same message can be contemporaneously sent (doctors, technicians etc.). this operation too, like the preceding ones, can be done manually by an operator, i.e. automatically when the predetermined conditions occur. selection can be done via a keyboard, mouse or even a touch-screen, as mentioned herein above. selection can be done via the local user interface or the remote user interface. note that the medical machine is further provided with means 411 for configuring the form 400 . the means 411 for configuring enable the list of identifying addresses to be notified via the signal message to be set up; otherwise the means 411 for configuring enable one or more e-mail servers to be established for sending the signal message and also to predispose a common standard text, possibly editable, to be inserted as the text of the signal message in addition to the above-mentioned further data and information. the means 411 for configuring (for example a program code) can be graphically represented in a window of the user interface 300 such as to be able to intervene with the aim of predisposing the configuration modifications of the module 400 with the above-mentioned data entering device 5 (mouse, touch screen, etc.). the machine further comprises a system memory 416 ; at least the data 405 a , 405 b , 405 c , 405 d included in the signal message are sent from the control unit 4 to the system memory 416 for conserving the data and possibly for consulting it later on. also to be noted is the fact that the means 401 for selecting the format, the means 403 for generating the contents of the signal message, the means 406 for selecting the addressee (but possibly also the means 411 for configuring the form 400 ) are remotely activatable via the graphic user interface 300 accessible through the web pages published by the web server 11 . it is further possible to activate the means 401 , 403 , 406 , 411 via a web page published by the web server on the remote display and different to the graphic representation on the local interface user 300 . by doing this, the functions of the module 400 are also remotely usable without any need for the operator to be present in the place where the medical machine 2 is actually working. in this way a technician, or any other authorised person, can send messages containing the most relevant or significant or interesting information to any of the personnel whose addresses are stored on the user interface 300 (for example to him- or herself and to other operators), including directly from a remote position without there being any need to be present in the machine locus. sending the message (especially the e-mail message) might for example be generated by the following situations: pressing the button (i.e. e-mail 402 a ) present on the graphic user interface 300 (a nurse, seeing the moment of difficulty, can be assured that the information relating to the problem will not be lost but will be received by a technician; a maintenance technician can send some data of interest to the machine or send it to another technician for consultation purposes);pressing the button from a remote location (i.e. e-mail 402 a ) present on the graphic user interface 300 published on the web pages of the web server 11 (with the graphic user interface published on the web pages of the web server being possibly different from the graphic user interface 300 shown on the local display);on one or the predetermined events occurring with automatic sending of the message (serious alarms or malfunctioning will lead to a message being sent bearing information which will be automatically stored in the system memory);when the predetermined deadline has passed (for example every n days, or every n hours of use of the medical machine, or even every n treatments performed by the medical machine);fewer than n days until the next maintenance check. the invention leads to important advantages. primarily, the proposed system and methodology for the management of signals enables message to be sent which are of a different nature, at any moment of operation of the machine. in other words, the machine is configurable for automatic sending of certain types of pre-organised messages when certain special events occur, but it can be used at any time for sending messages of a different nature (e-mails, sms messages, local network messages . . . ) according to the needs of the operator, nurse or technician. it is extremely simple to send a plurality of messages of a different nature to different addressees, by a touch-screen manual selection, very simple to understand and use. for example, when a dangerous situation for the patient arises, a nurse can send messages with certain contents to a doctor and, at the same time, send different messages with contents of a different nature to a technician such that the technician can receive instructions relating both to the treatment and to the technical interventions on the machine. further, the form 400 is also remotely accessible such that the implemented system can be exploited without having necessarily to be present in the machine locus. worthy of note is the fact that all the information sent are stored in the central server such that a situation of danger/warning/interest is subject to a snapshot and the relative data are accessible at any moment thereafter. the follow are the numerical references in fig. 3 . 201 hemodiafiltration apparatus202 water inlet203 inlet pressure sensor204 inlet pressure regulator205 inlet check valve206 ultrafilter for water at inlet207 first heat exchanger208 second heat exchanger209 pressure sensor at inlet of the heating and degassing circuit210 heater211 temperature sensor in the heating and degassing circuit212 degassing choke213 bypass valve of degassing choke214 pressure sensor for control of degassing pump215 degassing pump216 first gas-liquid separator in heating and degassing circuit217 first degassing valve218 check valve for the heating and degassing circuit19 pressure regulator at outlet of heating and degassing circuit20 on-line preparation device for dialysate with water and concentrates21 fresh dialysate movement pump22 second gas-liquid separator for the fresh dialysate23 second degassing valve24 sensor system for measuring some parameters (in particular temperature, conductivity and ph) of the fresh dialysate25 protection system for fluid balance in excess in control system26 fluid balance control system27 pressure sensor at inlet of dialysate ultrafilter28 first bypass valve for bypass of dialysate ultrafilter29 dialysate ultrafilter30 connection for a disposable line for replacement fluid31 second bypass valve for dialyser bypass32 pressure sensor at dialyser inlet33 dialyser34 check valve at dialyser outlet35 pressure sensor at dialyser outlet36 used dialysate movement pump37 third gas/liquid separator for used dialysate38 third degassing valve39 sensor system for measuring some parameters (in particular temperature, conductivity, pressure and presence of blood loss) of the used dialysate40 aspiration pump for stabilising pressure downstream of the fluid balance control system41 normally-open check valve at outlet42 outlet pressure sensor43 outlet check valve44 outlet end connected to a drainage45 water ultrafilter flushing line46 flushing line choke47 check valve on flushing line48 breather valve connected to the breathers of the various gas-liquid separators49 choke connected to the breathers of the various gas-liquid separators50 check valve operating on a tract of line in common with the flushing line and the breather circuit51 recycling circuit for complete thermal or chemical disinfection circuit52 source of a chemical disinfectant including the means for supplying the disinfectant53 first check valve for enabling recycling during thermal or chemical disinfection54 pair of connectors for dialyser bypass during thermal or chemical disinfection55 dialyser bypass flow sensor56 second check valve to enable recycling during thermal or chemical disinfection57 first check valve for enabling supply of disinfectant to the first discharge port of the priming fluid58 second check valve for enabling supply of disinfectant to the second discharge port of the priming fluid59 first branch for disinfection of the first discharge port of the priming fluid60 second branch for disinfection of the first discharge port of the priming fluid61 first discharge port of the priming fluid62 second discharge port of the priming fluid63 first discharge line of priming fluid64 second discharge line of priming fluid65 first check valve66 second check valve67 line conjoining the first and second priming fluid discharge lines with the used dialysate line68 line connecting with the atmosphere upstream of the heating and degassing circuit69 check valve of the connecting line with the atmosphere70 air filter71 first bypass line (dialysate ultrafilter bypass)72 second bypass line (dialyser bypass)73 flushing line of the dialysate ultrafilter74 check valve of the dialysate ultrafilter flushing line75 replacement fluid supply line76 replacement fluid movement pump77 replacement fluid pump ultrafilter78 replacement fluid breather system79 arterial line80 blood pump81 arterial chamber82 arterial chamber service line83 arterial clamp84 arterial line access site85 anticoagulant supply line86 anticoagulant source87 venous line88 venous chamber89 venous chamber service line90 venous clamp91 venous line access site92 air bubble sensor93 blood presence sensor (patient sensor)94 hemoglobin or hematocrit sensor, or blood volume sensor.
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090-329-727-115-81X
|
PL
|
[
"PL",
"EP"
] |
E01F9/524,C09K11/00,G09F13/20,E01C5/22,E01F9/559
| 2015-07-22T00:00:00 |
2015
|
[
"E01",
"C09",
"G09"
] |
prefabricated element containing permanently inbuilt mark and method for making the prefabricated element
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prefabricated element (12) containing a permanently embedded sign or its part (14), characterized by the fact that at least one surface of the element (12) has a cut (20) in the shape of the sign or its part (14), whereas inside the cut (20) is permanently embedded photoluminescent mass (22) which is flush with the external surface of the element (12). production method of the element, according to which, in the first place the element (12) with the cut (20) is prepared and later the cut (20) is cleaned and dried. next, it is primed and painted with reflective paint suitable for the photoluminescent mass (22) and into the cut (20) the fresh photoluminescent mass (22) is placed and left until it hardens.
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prefabricated element containing a permanently embedded sign or its part, characterized in that at least one of the surfaces of prefabricated element (12) has a cut (20) in the shape of the sign or its part (14), whereas in the cut (20) photoluminescent mass (22) is permanently embedded and it is flush with the external surface of the element (12). prefabricated element according to claim 1 characterized in that , the cut (20) in the element (12) has depth ranging from 1 to 5 mm and the width from 5 to 100 mm, whereas the internal surface of the cut (20) is coated with reflective paint (210), on the surface of which a lightning system is placed, while the element (14) has at least one opening for providing power supply to the light system. prefabricated element according to claim 1 or 2 characterized in that , the photoluminescent mass (22) consists of synthetic mass resistant to uv rays (214) mixed with a photoluminescent component (216). prefabricated element according to claim 1, 2 or 3 characterized in that , the photoluminescent component (216) comprises of the compounds of rare earth elements with photoluminescent properties in light yellow, light green or light blue colour, the granularity of 40-50 µm compliant with norm din67510. prefabricated element according to claim 1, 2, 3 or 4 characterized in that , the photoluminescent mass (22) contains quartz sand or powdered white glass (212) with the fraction of 0,05 - 0,3 mm or glass microspheres with the diameter from 125 to 850 µm or components with antifungal and antibacterial properties or components acting as filters changing the glow colour of a given sign or hardening components. production method of prefabricated element characterized in that , the element (12) with the cut (12) is prepared and later the cut (20) is cleaned and dried, in next step it is coated with reflective paint suitable for the photoluminescent mass (22) and into the cut (20) the fresh photoluminescent mass (22) is placed permanently and is left till it gets hardened. the method according to claim 6 characterized in that , at the stage of preparing the element (12) with the cut (20), the element is cast in a formwork mould (50), at the bottom of which the mould of the mirror image of the sign, or its part, is placed and then after setting reinforcement mesh, the mould is filled in or poured with a plastic material mix, preferably concrete, then the material is thickened during the vibration process and is left until it gets hardened. the method according to claim 7 characterized in that , both of the moulds are made of a non-porous material, resistant to vibrations, and the moulds are cleaned and spray-coated with an anti-adhesive oil. the method according to claim 6 characterized in that , at the stage of preparing the element (12) with the cut (20), the cut (20) is made by mechanical processing of the element (12) with the use of a milling machine or an engraving machine. the method according to claim 9 characterized in that , a milling machine or an engraving machine receives data from a computer which controls the process of milling or engraving based on a programmed project of a given sign or its part (14). the method according to claim 6, 7, 8 or 9 characterized in that , the surface of the photoluminescent mass (22) is flush with the external surface of the element (12). the method according to claim 6, 7, 8, 9, 10 or 11 is characterized in that , a transparent synthetic mass resistant to uv rays (214) and the photoluminescent component (216) are used as the photoluminescent mass (22), whereas the photoluminescent component (216) is comprised of the compounds of rare earth elements with photoluminescent properties. the method according to claim 6, 7, 8, 9, 10, 11 or 12, characterized in that quartz sand or powdered glass (212) with the fraction of 0,05 - 0,3 mm or glass microspheres with the diameter from 125 to 850 µm or components with antifungal and antibacterial properties or components acting as filters changing the glow colour of a given sign or hardening components.
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the invention relates to a prefabricated element in the form of a complete element which contains a permanently embedded, photoluminescent sign of any shape - be it a pictogram, a geometric figure, a line, a digit or a sequence of them, as well as the production method of the element in question. the solution provided by the invention can have its application as a energy-saving information sign, a mandatory sign, a prohibitory traffic sign or a warning sign, signs increasing safety and facilitating transport, especially after dark, on all kinds of hardened surfaces i.e. traffic and transport routes, bike paths, alleys, on parking lots, pavements, quays, railway platforms, swimming pools' edges, stairs, stairwells as well as in other applications tailored to meet specific needs. the prefabricated element can also serve as a decorative or identification element in gardens, parks, public spaces, cemeteries, in front of the main entries to buildings and it can also be a marketing tool when it contains a logo or a slogan. the surrounding space contains a lot of signs and elements aimed at ensuring safety, facilitating transport, transmitting information and making our surroundings functional and friendly. all those signs and elements are installed out of concern for all of us: drivers, cyclists, motorcyclists, pedestrians, the disabled, children and elderly people, tourists, foreigners and others. most of those signs and elements are based on visual communication. after dark, however, its effectiveness decreases unless it is supported by electrical systems generating light which can illuminate given elements of visual communication. the cost of an electrical installation and energy consumption can be eliminated or limited due to the use of a photoluminescent pigment in the material which a sign is made of. then, after exposing to light, signs will emit their own light thanks to which they will be visible after dark. thus in some places it could be possible to get rid of electrical systems and, as a result, save significant amounts of money. the state of the art includes combinations of photoluminescent materials with building materials. such a solution is described by a belgian patent description be822626 . according to it, a photoluminescent component is combined with building materials e.g. concrete in order to create a homogenous building material with photoluminescent properties. a chinese utility model in protective specification cn2718049 sets forth a prefabricated, glowing curb with a cable duct. the top outer part of the curb contains a concrete binder with a photoluminescent component. patent specification wo2010134805 presents the production method of concrete products whose surface is covered with a coating containing small, glowing pieces of glass. the glass contains a photoluminescent pigment and adheres to the concrete due to resin, glue or plastic. patent specification wo2014175732 provides the method of a photoluminescent marking of road lanes and lines. a cut is made in the surface of a road. then an elastic section, which contains a photoluminescent material (with a source of light, too, if necessary), is placed inside the cut. patent specification ep2531655 shows markings placed on hardened surfaces by painting them with paint or by sticking on them tapes with a photoluminescent component. similarly, patent specification gb2224296 describes an invention in the form of a line made of plastic and epoxy paint stuck on road surfaces. patent specification jp4066051 presents an invention where concrete elements and photoluminescent markings are heat-sealed using a burner. the efficiency and durability of the above described methods of installation, sticking, painting or heat-sealing of photoluminescent materials outdoors are dependent upon given weather conditions. the durability of markings is lowered due to the effect of humidity, frost or dirt during installation and painting works. the use of paints in outdoor conditions increases the risk of a leak into the natural environment and the contamination of soil and groundwater. additionally, even a slight protrusion (0,3mm - 0,8mm) of markings above the road surface they are placed on, exposes them to abrasion. consequently, markings need to be renewed even every six months. the comparison between the solution belonging to the state of the art and the concept developed by the invention is presented by fig.4 and fig. 4a respectively. the subject of the invention solves the above mentioned problems: it eliminates the problem of marking abrasion and the dependency on favorable weather conditions during the installation process. the production of the invention takes place in an industrial plant, which facilitates the quality control of production processes and decreases the risk of environmental contamination. the technology of the invention provides unlimited possibilities of shaping photoluminescent signs on prefabricated elements. the solution set forth by the invention, by embedding a marking made of photoluminescent mass in a properly shaped element, provides a durable prefabricated element performing the function of information, warning, prohibition, order or decoration. due to their embedding in a properly prepared cut, photoluminescent markings gain a side construction protection, which increases their resistance to abrasion significantly in comparison with photoluminescent layers used on non-cut surfaces. careful priming of the surface of a cut and covering it with reflective paint increases its intensity of reflecting light energy from the marking embedded in the cut, thus its functional efficiency is also increased. the production of prefabricated elements with photoluminescent markings in factory conditions, in a stable environment, makes the pace and the quality of production independent from weather conditions and it enables, to a greater degree, to prevent uncontrolled leaks of chemical substances into the natural environment. the invention is characterized by energy efficiency as it limits or eliminates the use of electrical energy which is necessary for it to perform its function after dark. the operational-functional readiness of prefabricated elements in a designated place depends only on the length of time of their installation, and not on the time of drying of photoluminescent material creating markings. the controlled conditions in the factory allow for the use of a wider spectrum of milling technologies to make cuts in the finished elements and for modeling formwork molds, as a result of which the choice of the shapes of photoluminescent signs is virtually unlimited. the factory conditions allow for producing repeatable elements distinguished by the best possible properties. the simplicity of the production technology makes it easier to ensure products' durability and is relatively inexpensive. the technology's durability contributes to the reduction of maintenance costs (i.e. renewal) of hardened surfaces, which should, in turn, contribute to the improvement of the safety of users of public spaces, in particular after dark. the subject of the invention is characterized by the fact that a photoluminescent sign (or its part, if a given sign is bigger than a single prefabricated element) is permanently embedded in the element. the prefabricated element has a cut in the shape of a marking or its part in which photoluminescent mass is embedded. during the production phase it is preferable, once a fresh photoluminescent mass is hardened, for a sign to be flush with the external surface of the element. it is preferable when the depth of a cut in the element is from 1 to 5 mm and the width from 5 to 100 mm and when the external surface of a cut is covered with reflective paint. preferably, a lightning system should be installed on the surface of a cut. the use of a lightning system, e.g.in the form of leds embedded in the mass, additionally illuminates a photoluminescent sign from underneath. any lightning system requires power supply, therefore the element should contain at least one opening for providing power supply. the cut of the said depth and width prevents spillages, dispersals and smears of a fresh photoluminescent mass during forming it into the shape of a given marking in the element and during transporting it within the premises of an industrial plant. thus, during the production of prefabricated elements any potential loss of photoluminescent mass is minimized. the precision of making the edge of a cut and filling it up with photoluminescent mass translates directly into increased visibility of a sign in prefabricated elements, which consequently translates into its clearness and effectiveness. the required precision depends on the distance from which a marking is supposed to be visible - it will be different for a prefabricated element placed in a pavement than for the one placed high in the elevation of a building. in every instance, the precision should very from 0,1 to 5 mm. the edges of a cut and the marking protect one another from abrasive horizontal forces, which is presented by fig.4a and fig. 4b comparing the solution delivered by this invention with the solutions belonging to the state of the art. abrasive forces exists in the city traffic e.g. vehicles' wheels running onto markings or shoe soles rubbing them off. in places of particularly increased pedestrian traffic e.g. stairs at railway stations, the cut provides a long-lasting protection of signs and they comfortable in daily use (signs are imperceptible under feet) and financial savings due to the fact that regular renewing of signs is unnecessary. in a preferable variant, photoluminescent mass consists of a transparent synthetic mass resistant to uv rays mixed with a photoluminescent component. the synthetic mass performs the role of a binding agent. additionally, it is preferable when a photoluminescent component is in the form of compounds of rare earth elements with photoluminescent properties in light yellow, light green or light blue color and the granularity of 40-50 µm. in the daytime these compounds absorb light energy (by exposition to sunlight) and after dark they release it into the surrounding environment as a part of the visible spectrum. as the result of their absorption of light energy from any portion of the visible spectrum, ultraviolet or infrared, the photoluminescent component can glow even up to 12 hours, although the intensity of light weakens with time. it is preferable when the photoluminescent component added to the synthetic mass is compliant with norm din67510. photoluminescent mass can also contain quartz sand, powdered white glass of 0,05 - 0,3 mm fraction or additions in the form of glass microspheres from 125 to 850 µm in diameter. the higher the ratio of the amount of the synthetic mass to quartz sand, powdered glass, glass microspheres in the upper part of a given marking, the smoother and softer its surface becomes. quartz sand (alternatively, powdered glass or glass microspheres) gives constructional strength to the mass - i.e. it constitutes its building material. in order to achieve a better exchange of light energy between the photoluminescent element and the environment, the building material should be transparently white. the more grains of quartz sand, powdered glass, glass microspheres in the upper part of a given marking, the rougher its texture becomes. it is also possible for photoluminescent mass to contain components with antifungal or antibacterial properties or components acting as filters changing the glow colour of markings or hardening components. the subject of the invention also includes the method of producing prefabricated elements. the method is characterized by the fact that, in the first place, an element with a cut is prepared, and then the cut is cleaned and dried to be primed and painted with reflective paint suitable for the mass. subsequently, the photoluminescent mass is placed permanently inside the cut and after hardening, it constitutes a embedded photoluminescent sign. in a preferable variant of the method, an element is casted in a formwork mold, at the bottom of which a mold of the mirror image of the marking, or its part, is placed. later, after a reinforcing mesh is placed, the mould is filled in or poured with a material mixture, preferably concrete. the material is condensed by vibrations and later left to harden. it is preferable when both of the moulds are made of a non-porous and resistant to vibrations material. it is also preferable when the moulds are cleaned and spray-coated with an anti-adhesive oil in order to prevent the material mixture from sticking to them. another preferable variant of producing the prefabricated element according to the method is when a cut is made by mechanical processing with the use of a milling machine or an engraving machine. these machines receive data from a process-controlling computer based on a programmed project. this variant of the production method is intended for the materials not subject to plastic forming e.g. paving slabs. it is preferable when photoluminescent mass, after being placed in a cut and hardening, is flush with the external surface of the element. in the production method, it is also possible to use, as photoluminescent mass, a transparent synthetic mass resistant to uv rays and a photoluminescent component. the photoluminescent component can come in the form of rare earth elements with photoluminescent properties. optionally, what can be added to photoluminescent mass is quartz sand or powdered glass of 0,05 - 0,3 mm fraction or additions in the form of glass microspheres from 125 to 850 µm in diameter, or components with antifungal or antibacterial properties or components acting as filters changing the glow colour of markings or hardening components. the additions to photoluminescent mass are aimed at providing durability of a sign, roughness of its surface, its reflectiveness or other properties depending on specified requirements. the subject of the invention and its production method are presented in the following figures: fig.1 shows an axonometric view of the prefabricated element with a photoluminescent sign as an example; fig.2a - a cross-section of the cut with photoluminescent mass in the element; fig.2b - a cross-section of the cut with photoluminescent mass in the element with a duct for an additional light source system; fig.3a - a projection of the prefabricated element in the form of a concrete slab with a photoluminescent pictogram in the shape of a bike; fig.3b - a projection of the prefabricated element in the form of two adjoining concrete slabs, which, as a result, creates a bigger photoluminescent sign in the shape of a bike; fig.4a - a side view of a wheel running over the sign in the cut; fig.4b - a side view of a wheel running over the sign placed on the surface and a distribution of forces; fig.5 - a cross-section of the moulds prepared for casting an prefabricated element; fig.6a - a cross-section of the cut with a fresh photoluminescent mass before the vibration process; fig.6b - a cross-section of the cut with a fresh photoluminescent mass after the vibration process. prefabricated element 10 consisting of element 12 with photoluminescent sign 14 whose example is shown in fig.1 , constitutes a fragment of a horizontal hardened surface - for example, prefabricated element 10 can be embedded in the surface of a bike path. prefabricated element 10 consists of element 12 in the form of a slab and sign 14 made of photoluminescent mass 22 permanently embedded in cut 20 in element 12. model sign14 is in the shape of a bike pictogram. fig.3a shows a projection of the prefabricated element according to fig.1 , whereas fig.3b presents a projection of prefabricated elements placed side by side, as a result of which one photoluminescent sign 14 is obtained in the shape of a bike. the use of cut 20 has two advantages: it gives fresh photoluminescent mass 22 the form of sign 14, it protects sign 14 from destructive horizontal forces 40 shown in fig.4a , b. cut 20, in the example of embodiment, has the depth of 5 mm and the width of 70 mm, while the inner surface of cut 20 is coated with reflective paint 210. photoluminescent mass 22 consists of synthetic mass 214 resistant to uv rays mixed with photoluminescent component 216. photoluminescent component 216 contains a compound of rare earth elements with the granularity of 50 µm. moreover, photoluminescent mass 22 contains quartz sand, powdered white glass 212 with the fraction of 0,3 mm and glass microspheres of 125 µm in diameter. additionally, photoluminescent mass 22 contains components with antifungal or antibacterial properties, hardening agents as well as a component acting as the filter changing the glow colour of a marking. in a different version of cut 20, inner surface of cut 20 is coated with reflective paint 210, and on the surface of reflective paint 219 a lightning system is placed in the form of leds 218 together with power cord 220 through an opening in element 12. the example of a patent application method no. 1 in the first place, element 12 with cut 20 is prepared. in elements 12 formed in a plastic way, e.g. from reinforced concrete, element 12 is prepared using moulds and casting techniques. first, the formwork mould of element 50 is made separately and the formwork mould of the mirror image of sign 52 is prepared, as shown in fig.5 . both of the moulds are made of a non-porous material, resistant to vibrations. the mould of the mirror image of sign 52 is made from an acrylic plate, 3 mm thick, stabilized to avoid any movement during making a cast and later, during the vibration process. the stability is achieved by sticking the plate to the bottom of the mould. before the material mixture is placed in the mould of element 50 and reinforcement is set in mould 50, the mould are cleaned and coated with an anti-adhesive oil 54. later, when the reinforcement is set and immobilized in mould 50, an earlier prepared material e.g. concrete is placed inside the mould of element 50. at this stage, the mould of element 50 is vibrated for a short time in order to thicken the inserted material, to obtain level edges 24 and a level shape of cut 20 and to remove air gaps, as shown in fig.6a and 6b . air gaps are highly undesirable as they weaken the construction of element 12, make it possible for moisture to build up, create the risk of reinforcement corrosion. moreover, water frozen inside air gaps can burst sign 14 and element 12. the vibration process should not take too long as it can delaminate the material element 12 is made of. next, the filled-up mould is left for the time necessary for the material to harden. once the material is hard, element 12 with a prepared cut 20 is taken out of the mould and it goes through quality control and, if necessary, correction are made. after element 12 with cut 20 is made, element 12 undergoes a further processing. before cut 20 is filled up with fresh photoluminescent mass 22, it should properly be prepared. first, cut 20 is cleaned of dust and degreased. next, cut 20 is primed with colourless priming agent 28. when priming agent 28 is dried, a single layer of white reflective chemically-resistant priming paint 210 for concrete is applied on it. sign 14 is made of fresh photoluminescent mass 22 inserted into cut 20. for the comfort of end users, it is preferable when vehicles running over horizontal signs 14 and pedestrians walking over them cannot sense any irregularities at the junction of sign 14 with element 12 or any difference in texture between them. in particular cases, the protuberance of sign 14 over element 12 can be justified e.g. in order to draw special attention to a given sign. nevertheless, in the example of a patent application, photoluminescent mass 22 in cut 20 is flush with the surface of element 12. the surface of element 12 and sign 14, in the example of a patent application, were given an anti-slip texture. optionally, element 12 or sign 14 can be smooth. photoluminescent mass 22 consists mainly of synthetic mass 214 and photoluminescent component 216, whereas photoluminescent component 216 is comprised a compound of rare earth elements. quarts sand and powdered glass 212 of 0,05 mm fraction and glass microspheres of 850µm in diameter, hardening and antifungal substances were also added to photoluminescent mass 22. fresh photoluminescent mass 22 is poured into cut 20 in such a way that: the mass is evenly distributed, there are no air gaps, the surface is level, material waste is minimal, no external surfaces of element 12 gets stained in the process. after inserting fresh photoluminescent mass 22 into cut 20, prefabricated element 10 should be left until sign 14 gets hardened, it should stay in a stable and clean environment. after hardening, prefabricated element 10 is ready for its installation in a designated place. the example of a patent application method no. 2 in the first place, element 12 with cut 20 is prepared. in case of element 12 being made of stone, cut 20 is made by mechanical processing using e.g. a milling machine. the milling machine receives data from a computer which is equipped with software for designing signs 14 and the one for controlling the milling process. a designer uses the software to determine, among others, the location and dimensions and shape of cut 20 on a computer model of element 12. after cut 20 is milled, it is cleaned and dried and then it is coated with reflective priming paint. once the paint is hardened, but still before it is completely dried, fresh photoluminescent mass 22 is inserted in cut 20 and when the mass is hard, it constitutes sign 14 embedded in cut 20. the advantage of the prefabricated element is: the darker it gets, the brighter the sign glows. thus, as people's alertness weakens, the visual message, which is the function of the element, directed to them gets stronger. it translated positively into safety and lives of people who are in the vicinity of signs e.g. pedestrians, cyclists, the disabled, drivers. thanks to that, everyone feels safer in the space they happen to be. for 6 hours after dark, signs glow very intensively e.g. a pedestrian crossing marked with them can be visible even from the distance of a few hundred meters. additionally, late at night on the road, the photoluminescent component is illuminated temporarily by the lights of passing vehicles and gives out light for a short time afterwards. another advantage of the prefabricated element being the subject of the invention is the fact that it performs its informative, warning, mandatory, prohibitive, or decorative function without electricity consumption. what it means is huge savings at the investment stage because the owner does not have to incur the costs of arranging, designing and building additional electrical installations and protecting them from being accessed by unauthorized persons e.g. thieves. during daily use, the owner of prefabricated elements does not incur the cost of electricity, for which he would need to pay in case of standard illuminated signs. moreover, photoluminescent signs are unfailing - they never stop working during a power cut, or when a short-circuit occurs, or when cables are cut. the key to their reliability is in the laws of physics, chemistry and in their durable construction - hence the idea to produce prefabricated elements in an industrial plant, in stable and controlled conditions. another advantage of the invention is its pro-ecological nature which also includes, mentioned earlier, energy efficiency. moreover, the use of prefabricated elements instead of paints applied on site eliminates the emission of paints' ingredients into the environment and also eliminates the risk of an uncontrolled spillage of paints and their penetration into groundwater. the durability of prefabricated elements, higher than the durability of paints, enhances these advantages as paints need to renewed, on average, every six months. as a result, every six months thinners are emitted, which creates the risk of their penetration into the environment. another advantage of the invention is time savings during construction of hardened surfaces such as roads, pavements, parking lots or stairs. in case of the necessity to paint or stick signs on these surfaces, a contractor would have to devote time at least for preparing the surface (cleaning, degreasing), painting or sticking, securing it for the time necessary for markings to dry. in addition, these actions may be extended due to unfavourable weather conditions e.g. rain or frost. prefabricated elements are ready to be used immediately after installation and it takes the same amount of time as installing elements without markings. thus, it is safe to assume that, in case of marking the surface only with prefabricated elements, the time of making markings equals zero. it is of great importance in case of major traffic routes which are vital for an uninterrupted functioning of cities. the solution according to the invention has a wide range of applications in marking and securing spaces. additionally, the solution can be used for decorating and for marketing purposes. moreover, prefabricated elements can be divided into the following groups: information signs; e.g..: p - a parking lot, bike sign - a bike path, number - a distance, zebra - a pedestrian crossing, etc. warning, prohibitive or mandatory signs; e.g..: line - a change of the surface's purpose, a change of height e.g. prefabricated stairs, stop sign - an order to stop, inscription "attention!" - a warning, etc. decorative elements; e.g.: elevation panels with a embedded sign in the shape of a line as an ornament of the building's edge, parking posts with embedded signs - patterns of any shape, etc. special signs; np.: logo - the marking of a company's headquarters, etc. the above description of the invention presents the best possible and the most up-to-date, as of the moment of preparing the description, methods of production and applications, which does not exclude other variants, combinations and equivalents of the productions methods and applications of the invention. therefore, the invention is not restricted to the above described production methods and examples of application, but to all the possible production methods and applications within the nature of the invention.
|
090-693-181-113-775
|
JP
|
[
"US",
"CA"
] |
E02F3/43
| 1987-08-12T00:00:00 |
1987
|
[
"E02"
] |
apparatus for controlling posture of work implement of loader
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an apparatus for controlling the posture of the work implement of a loader comprises a boom supported by a boom pivot on a mast secured to a vehicle body and movable upward and downward by a boom cylinder, first and second arms supported by an intermediate portion of the boom and pivotally movable relative to each other, a pivotal member pivoted to the boom by the boom pivot, a first connecting member operatively connecting a point on the pivotal member away from the pivoted point thereof to the first arm, a second connecting member connecting the second arm to the work implement at the forward boom end, an engaging portion for engaging the second arm with the first arm when the implement is moved by an implement cylinder in the scooping direction approximately into a specified posture, and an interlocking member operatively connecting the pivotal member to an implement control valve for the implement cylinder so that the valve is operated in the dumping direction by the movement of the pivotal member with the rise of the boom after the second arm is engaged with the first arm by the engaging portion. the implement can be maintained in the specified posture when the boom is raised, preventing earth from spilling from the implement.
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1. an apparatus for controlling the posture of the work implement of a loader having a pair of masts secured to a vehicle body, a boom supported by a boom pivot on each of the masts and movable upward and downward by a boom cylinder, the work implement being pivotally movably supported by the forward end of the boom and movable by an implement cylinder for scooping and dumping, and a control unit for controlling the boom cylinder and the implement cylinder, the control unit having a boom control valve for operating the boom cylinder, an implement control valve for operating the implement cylinder, and control lever means for operating the two control valves, the apparatus being characterized in that the apparatus comprises first and second two arms supported by an intermediate portion of the boom and pivotally movable relative to each other, a pivotal member pivoted to the boom coaxially with the boom pivot, a first connecting member operatively connecting a point on the pivotal member away from the pivoted point thereof to the first arm, a second connecting member connecting the second arm to the work implement, engaging means for engaging the second arm with the first arm when the work implement is pivotally moved toward the scooping direction approximately into a specified posture, and interlocking means operatively connecting the pivotal member to the implement control valve so that the implement control valve is operated for dumping by the movement of the pivotal member with the rise of the boom after the second arm is engaged with the first arm by the engaging means. 2. the apparatus as defined in claim 1 wherein the boom is bent at the intermediate portion, and the rear portion of the boom from the bent portion to the mast and the front portion thereof from the bent portion to the work implement are substantially straight, the bent portion being provided with a lateral pin for supporting the boom cylinder and a lateral pin for supporting the two arms, the first connecting member extending substantially alongside the boom rear portion, the second connecting member extending substantially alongside the boom front portion. 3. the apparatus as defined in claim 2 wherein the lateral pin for supporting the boom cylinder and the arm supporting lateral pin are combined together in the form of a single pin, and the arm supporting lateral pin extends laterally from the bent portion. 4. the apparatus as defined in claim 2 wherein the bent portion has a support plate secured to the boom, and the support plate carries the boom cylinder supporting lateral pin and the arm supporting lateral pin and is provided with a horizontal indicating panel, the second arm having a pointer opposed to the indicating panel. 5. the apparatus as defined in claim 2 wherein the first connecting member and the second connecting member are each in the form of a rod, and at least one of the connecting members is adjustable in length. 6. the apparatus as defined in claim 1 wherein the work implement is connected at its rear lower portion to the forward end of the boom and has first and second two links flexibly connected together end-to-end by a connecting pin, the first link being connected at the other end thereof to the boom in the vicinity of its forward end, the second link being connected at the other end thereof to the rear upper portion of the work implement, the implement cylinder being connected to the connecting pin, the second connecting member being connected to an intermediate portion of the first link. 7. the apparatus as defined in claim 1 wherein the work implement is connected at its rear lower portion to the forward end of the boom, at its rear upper portion to the implement cylinder and at a rear intermediate portion to the second connecting member. 8. the apparatus as defined in claim 1 wherein the work implement is a bucket having at its front an opening holdable approximately in an absolutely horizontal specified position. 9. the apparatus as defined in claim 1 wherein the engaging means is an engaging portion projecting from one of the first and second arms toward the other arm and adapted to contact the other arm when the work implement is pivotally moved for scooping into the specified posture with the boom in its lowered position, permitting the second arm to pivotally move toward the first arm substantially into a lapping relation therewith. 10. the apparatus as defined in claim 9 wherein the engaging portion comes into contact with the other arm when the work implement is moved toward the scooping direction slightly beyond the specified posture. 11. the apparatus as defined in claim 9 wherein the engaging portion comes into contact with the other arm when the working implement is brought into the specified posture. 12. the apparatus as defined in claim 1 wherein the pivotal member comprises a bell crank, and the boom pivot is projected laterally from the mast, the bell crank being supported by the projected pivot portion and having one end connected to the first connecting member and the other end connected to the interlocking means. 13. the apparatus as defined in claim 1 wherein the control lever means is in the form of a single control lever, and a control box having a lever guide portion for guiding the control lever is disposed above the boom control valve and the implement control valve, the control box being provided with a first pivotal element movable about a first pivot for operating the boom control valve, and a second pivotal element movable about a second pivot for operating the implement control valve, the second pivot having an axis intersecting the axis of the first pivot at right angles therewith, the control lever being attached to the second pivotal element, the interlocking means being provided between the second pivotal element and the pivotal member. 14. the apparatus as defined in claim 13 wherein the interlocking means comprises a ball joint fitted to a pin portion projecting from the second pivotal element and a rod having one end screwed in the ball joint adjustably in its length and the other end connected to the pivotal member. 15. the apparatus as defined in claim 13 wherein the interlocking means comprises a bowden cable having one end connected to the second pivotal element and the other end connected to the pivotal member. 16. the apparatus as defined in claim 1 wherein the control lever means comprises a control lever for operating the boom control valve and a control lever for operating the implement control valve, and the interlocking means is provided between the control lever for the implement control valve and the pivotal member. 17. an apparatus for controlling the posture of the work implement of a loader comprising a pair of mounts provided at the lower portion of a vehicle body on the respective opposite sides thereof, an upright mast removably attached to each of the masts, a boom bent at an intermediate portion thereof and supported at its base end by a boom pivot on the upper portion of the mast, a boom cylinder connected between the lower portion of the mast and the intermediate portion of the boom for moving the boom upward and downward, a bucket having an opening at its front and pivoted at its rear lower portion to the forward end of the boom, a first link connected at its one end to the boom in the vicinity of the forward end thereof, a second link connected at its one end to the rear upper portion of the bucket, the two links being flexibly connected together at the other ends thereof by a connecting pin, a support plate attached to the intermediate portion of the boom and having a lateral pin, a bucket cylinder connected between the lateral pin and the connecting pin for causing the bucket to perform a scooping movement and a dumping movement, a first arm and a second arm both supported by the outer end of the lateral pin projecting laterally from the support plate, the first and second arms being pivotally movable relative to each other, the second arm being connected to an intermediate portion of the first link by a second rod, one of the two arms being provided with an engaging portion adapted to contact the other arm when the bucket is brought into a specified posture with its opening approximately in an absolutely horizontal position while the boom is in its lowered position, a bell crank supported by the outer end of the boom pivot projected laterally from the mast, the bell crank having one end connected to the first arm by a first rod, a boom control valve having a spool and connected to the boom cylinder, a bucket control valve having a spool and connected to the bucket cylinder, a control box disposed above the two control valves, the two control valves and the control box being mounted on the rear upper portion of the mast, a first pivotal element movably supported by a first pivot on the control box and connected to the spool of the boom control valve, a second pivotal element movably supported by a second pivot on the first pivotal element, the second pivot having an axis intersecting the axis of the first pivot at right angles therewith, the second pivotal element being connected to the spool of the bucket cylinder and being connected to the other end of the bell crank by interlocking means, and a single control lever attached to the second pivotal element, the control box having a lever guide portion for the control lever, the control valves being each provided with spring means for returning the spool to its neutral position, whereby as the boom is raised by the boom cylinder after the engaging portion has come into contact with the other arm with the bucket opening brought to the absolutely horizontal position by the scooping movement of the bucket, the bell crank is pivotally moved to cause the second pivotal element to operate the bucket control valve for. dumping through the interlocking means and thereby hold the bucket opening in the absolutely horizontal position. 18. the apparatus as defined in claim 17 wherein the second pivotal element is provided with first and second two pin portions coaxial with each other and having an axis intersecting the axis of the second pivot at right angles therewith, a ball joint being connected to each of the pin portions, a rod being screwed in the ball joint of the first pin portion adjustably in its length and connected to the spool of the bucket control valve, another rod being screwed to the ball joint of the second pin portion adjustably in its length and connected to the pivotal member.
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field of the invention and prior art statement the present invention relates to an apparatus for controlling the posture of work implements of loaders such as front loaders. front loaders are used as attached to tractors with their booms equipped with a bucket serving as a work implement. when sand or earth is scooped up with the bucket, the booms are raised with the opening of the bucket held in a horizontal posture. as the booms are raised at an increasing angle, the opening of the bucket tilts rearwardly downward even if horizontal at a low level, permitting the scooped earth to spill toward the tractor. to prevent the spillage of earth, there is a need to alter the posture of the bucket toward the dumping direction with the rise of the booms so as to maintain the bucket opening in a horizontal position at all times. however, it is not easy for the operator to maintain the bucket in the horizontal position manually. accordingly, conventional front loaders have a sensor for detecting the posture of the bucket and a sensor for detecting the angle of rise of the booms and are thereby adapted to electrically detect the posture of the bucket with the rise of the booms and control the bucket cylinder control valve through an electromagnetic valve so that the bucket is corrected to a horizontal posture not permitting spillage of earth by the dumping operation of the bucket cylinders. nevertheless, the prior art described requires the two sensors, electromagnetic valve or like expensive electric components and involves difficulties in assuring improved reliability. objects and summary of the invention the main object of the present invention is to overcome the foregoing problem heretofore encountered. an important object of the present invention is to convert the rising movement of the booms from a position at which the work implement is brought into a specified posture to an action to operate an implement control valve in the dumping direction, through a link mechanism provided between the implement and the control valve so as to maintain the implement in the specified posture when the booms are raised. another important object of the invention is to provide the link mechanism for entirely mechanically controlling the implement control valve, the link mechanism comprising a pivotal member connected to the implement control valve by interlocking means, a first arm connected by a first connecting member to the pivotal member at a point away from the point where the pivotal member is supported, a second arm connected to the work implement by a second connecting member, and means for engaging the first arm with the second arm to make the first and second arms, and the first and second connecting members immovable relative to the boom when the implement is brought into the specified posture. another object of the invention is to render the work implement movable through an increased angle by a flexible link connected between the rear upper portion of the implement and each beam and connected to each implement cylinder. another object of the invention is to provide on one of the first and second arms an engaging portion engageable with the other arm for detecting that the opening has become horizontal or slightly tilted rearward from the horizontal position. another object of the invention is to make the pivotal member movable to cause the implement control valve to perform a dumping action with the rise of the boom by supporting the pivotal member by the pivot of the boom and connecting a portion of the pivotal member away from the pivoted portion thereof to the first arm by the first connecting member. another object of the invention is to provide an arrangement comprising a first pivotal element for operating a boom control valve, a second pivotal element supported on the first pivotal element for operating the implement control valve, and a control lever attached to the second pivotal element to make the two control valves operable with the single control lever, the second pivotal element being connected to the pivotal member by the interlocking means, whereby the implement control valve is caused to effect a dumping action with the rise of the boom. another object of the invention is to make the connecting member or the interlocking means of the link mechanism adjustable in length so as to render the specified posture of the work implement adjustable in accordance with the slope of the ground. further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. however, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. brief description of the drawings the present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitative of the present invention, and wherein: figs. 1 to 7 show an embodiment of the present invention; fig. 1 is a side elevation showing the overall construction and the movement of the embodiment; figs. 2 and 3 are an enlarged side elevation and a perspective view of an intermediate portion of a boom; fig. 4 is an enlarged perspective view of a control unit; fig. 5 is a plan view in section of the control unit; fig. 6 is a view in section taken along the line e--e in fig. 5; fig. 7 is a view in section taken along the line f--f in fig. 5; figs. 8 and 9 show a modified embodiment of the invention; fig. 8 is an overall side elevation of the same; fig. 9 is an enlarged perspective view of a control unit; and fig. 10 is a sectional view showing modified control lever means. description of the preferred embodiments embodiments of the invention will be described below with reference to the drawings. referring to figs. 1 to 7, a front loader 1 of the bucket type is attached to the front portion of a tractor 2. the tractor body 3 has a pair of mounts 4 on its opposite sides. a pair of masts 5 are removably fixed to the upper portions of the mounts. a pair of booms 7 are supported by a pivot 6 on the upper portions of the respective masts 5 and are movable upward and downward. a bucket (work implement) 9 is supported by a pivot 8 on the forward ends of the booms 7. each of the booms 7 is bent at an intermediate portion thereof, and the rear portion from the bent portion to the mast 5 and the front portion from the bent portion to the bucket 9 are approximately straight. the bucket 9 has an opening 9a at its front as positioned as indicated in solid line in fig. 1. besides the bucket, a fork, a grader, a bucket of a backhoe or the like can be used as the work implement. provided between the intermediate portion of each boom 7 and a lower portion of the mast 5 is a boom cylinder 11 for raising and lowering the boom. a bucket cylinder 12 is provided between the boom intermediate portion and the bucket 9 for causing the bucket to perform a scooping movement and a dumping movement. the bucket 9 has a pair of brackets 13 secured to its rear side, and the lower portion of each bracket 13 is connected to the boom 7. two links 15, 16 are connected at their outer ends between the bracket upper portion and the boom 7 for forming a four-point link assembly 14. the other ends of the two links 15, 16 are connected together by a pin 17 having the rod of the bucket cylinder 12 connected thereto. the four-point link assembly 14 is provided to make the bucket 9 movable through an increased angle. a sectorial support plate 18 is secured to the lengthwise intermediate portion of one of the opposed booms 7. the support plate 18 has a lateral pin 19 for supporting the bucket cylinder 12. the pin 19 is projected laterally from the plate 18 for supporting on its outer end two arms 21 and 22 movably relative to each other. a horizontal indicating panel 23 is secured to the support plate 18, and a pointer 24 opposed to the panel 18 is provided on the second arm 22. although the lateral pin 19 for the cylinder 12 also serves to support the arms 21, 22, another laterally projecting pin may be provided on the support plate 18 or on the boom intermediate portion. the second arm 22, which is positioned closer to the support plate 18 than the first arm 21, has fixed to its front side edge a contact plate providing an engaging portion 25 which is adapted to contact the first arm 21. a rod (second connecting member) 26 has one end connected to the free end of the second arm 22 and the other end connected to an intermediate portion of the link 15 pivoted to the boom 7. through the links 15, 16 and the rod 26, the second arm 22 is pivotally movable with the scooping movement and dumping movement of the bucket 9 to detect the posture of the bucket 9. the rod 26 extends approximately alongside the front portion of the boom 7. a rod 29 extends generally alongside the rear portion of the boom 7. thus, the two rods 26 and 29 are protected by the boom 7. the rod 29 (first connecting member) has a front end connected to the free end of the first arm 21 and a rear end screwed on a screw portion 62 of a connector 61. the connector 61 is connected to a pivotal member 28. the distance between the first arm 21 and the pivotal member 28 is therefore adjustable. such a means for adjusting the length of the rod 29 can also be used for the rod 26. the horizontal indicating panel 23 bears a mark 23a which is positioned opposite the pointer 24 when the opening 9a of the bucket 9 is positioned substantially horizontally. the mark is so positioned as to be readily observable by the operator on the tractor 2. the pivot 6 on the mast 5 has one end projecting laterally therefrom. the pivotal member (bell crank) 28, which is l-shaped when seen from one side, is supported by the projected end. a pin 30 connecting one end of the pivotal member 28 to the rear end of the rod 29, i.e. to the connector 61, is positioned above the pivot 6 away therefrom. with reference to fig. 1, the upward or downward movement of the boom 7 therefore varies the distance from the lateral pin 19 to the connecting pin 30. clockwise movement of the first arm 21 moves the pivotal member 28 counterclockwise. a mount plate 33 for a control unit 32 is attached to the rear side of the mast 5 at its upper portion. with reference to figs. 1 and 4 to 7, indicated at 34 is a boom control valve for controlling the boom cylinders 11, and at 35 a bucket control valve for controlling the bucket cylinders 12. these control valves 34, 35, each of which is a three-way valve of the spool type, are fixed to the mount plate 33 with spools 34a, 35a positioned vertically. the spools 34a, 35a of the control valves 34, 35 are returned to the neutral position by return springs 34b, 35b, respectively. the return spring may be provided on a control lever 37. a control box 36 above the control valves 34, 35 is fixed to the mount plate 33, supports the control lever 37 and has a lever guide portion 38. fixedly provided inside the box 36 is a bracket 39 which is channel-shaped when seen from above. a lateral first pivot 41 secured to a first pivotal element 40 is rotatably supported by the bracket 39. a second pivotal element 42 is disposed in a u-shaped portion of the first pivotal element 40 and supported by a second pivot 43 extending in the front-to-rear direction. the axes of the first pivot 41 and the second pivot 43 intersect each other at right angles. the control lever 37 has its base end secured to the second pivotal element 42, which has two pin portions 44 and 45 projecting therefrom leftward and rightward and having an axis intersecting the axis of the second pivot 43. the pin portions can be coaxial with the first pivot 41. the first pin portion 44 is connected to the spool 35a of the bucket control valve 35 by a ball joint 46 and a rod 47. the second pin portion 45 is connected to the rear end of the pivotal member 28 by a ball joint 48, rod 49 and pin 57. the ball joint 48 and the rod 49 provide interlocking means 52 for transmitting the movement of the pivotal member 28 to the second pivotal element 42. the rods 47, 49 are screwed in the ball joints 46, 48, respectively, and are adjustable in length by varying the amount of screw-thread engagement to adjust the distance from the first pin portion 44 to the spool 35a and the distance from the second pin portion 45 to the pivotal member 28, whereby the control operation of the control valve 35 is adjustable. the first pivotal element 40 has a forwardly projecting arm portion 40a, which is connected to the spool 34a of the boom control valve 34 by a joint 51 and a rod 50. the rod 50 is screwed in the joint 51 and is adjustable in length. the control unit 32 operates as follows. the single control lever 37, when shifted upward or downward in fig. 5, moves the first pivotal element 40 about the first pivot 41, pushing the spool 34a of the boom control valve 34 downward or upward and causing the boom cylinders 11 to lower or raise the booms 7. when the control lever 37 is shifted leftward or rightward in fig. 5, the second pivotal element 42 is moved about the second pivot 43 to push the spool 35a of the bucket control valve 35 downward or upward, causing the bucket cylinders 12 to pivotally move the bucket upward or downward. further when the lever 37 is shifted obliquely, the control valves 34, 35 operate at the same time, whereby the booms 7 and the bucket 9 can be moved at the same time. the control valves 34 and 35 can be moved independently of each other and also at the same time by the control lever 37. when the control lever 37 is moved laterally, the movement of the second pivotal element 42 moves the pivotal member 28 through the rod 49, causing the rod 29 to pivotally move the first arm 21. thus according to the present embodiment, the depression of the spool 35a of the bucket control valve 35 pivotally moves the bucket 9 upward for scooping, while the spool 35a, when pulled up, causes the bucket 9 to perform a dumping action. alternatively, the control unit can be so adapted that the depression of the bucket control valve spool 35a effects the dumping movement and that the spool 35a is pulled up for the scooping movement. the pivotal member 28 can then be connected directly to the rod 47 or the spool 35a for the rod 47 and the like to serve as the interlocking means 52 for transmitting the movement of the pivotal member 28 to the bucket control valve 35. on flat ground, the bucket 9 can be made to scoop up or dump earth from a scooping posture a, shown in solid line in fig. 1, wherein the bottom of the bucket is positioned horizontally. after scooping earth up, the bucket cylinders 12 are contracted to continue the scooping movement until the opening 9a is brought to a horizontal position to prevent the earth from spilling. when the bucket 9 is on the ground with the booms 7 lowered, the bucket 9 can be moved upward to a position in which the opening 9a is tilted slightly rearward, but when raising the earth, the bucket is set in a specified posture b wherein the opening 9a is approximately horizontal. this specified posture b can be visually recognized with reference to the pointer 24 which is caused to point to the mark 32a by the link 15, rod 26 and second arm 22. when the bucket 9 is brought approximately to the specified posture b in contact with the ground, the second arm 22 is pivotally moved toward the first arm 21, bringing the engaging portion 25 closer to the first arm 21. when the boom cylinders 11 are extended in this state, raising the booms 7 about the pivot 16 to lift the bucket 9 to the dot-and-dash line position of fig. 1, the lateral pin 19 is moved upward about the pivot 6, with the rod 29 moved upward about the pin 30, decreasing the distance from the lateral pin 19 to the pin 30 and relatively moving the first arm 21 about the lateral pin 19 counterclockwise in fig. 1, whereby the first arm 21 is brought into contact with the engaging portion 25 of the second arm 22 in an initial stage of rise of the booms. in this state, the first arm 21 is restrained by the second arm 22 from counterclockwise movement in fig. 1 and made immovable relative to the arm 22 unless the bucket cylinders 12 are operated, with the result that the link mechanism comprising the first and second arms 21, 22 and rods 26, 29 remains stationary relative to the booms 7. while the booms 7 further rise to a lifted position c indicated in dotted line in fig. 1, the distance from the lateral pin 19 to the pin 30 further decreases. however, the first arm 21 is in contact with the engaging portion 25 and therefore remains stationary relative to the second arm 22. consequently, the pivotal member 28 relatively moves counterclockwise in fig. 1 to move the second pivotal element 42 through the rod 49 and the ball joint 48, thereby pulling up the spool 35a and causing the bucket control valve 35 to effect a dumping movement. this dumping movement continues during the rise of the booms 7, finely moving the bucket 9 toward the dumping direction, so that the second arm 22 is moved counterclockwise in fig. 1. when the booms 7 stop rising, the first arm 21 remains in engagement with the engaging portion 25, but the pivotal member 28 is so positioned as to position the bucket control valve 35 in its neutral position. this position is maintained by the return spring 35b of the spool 35a. thus, the bucket 9 moves in the dumping direction as the booms 7 rises to hold the opening 9a horizontal, thereby preventing the earth from spilling toward the tractor 2. the posture of the bucket is automatically, mechanically controllable and therefore very reliably without necessitating manipulation therefor. with the booms 7 in its lifted position c, the bucket 9 is moved for dumping by pulling up the spool 35a by the control lever 37. at this time, the first arm 21 moves away from the engaging portion 25. the adjustment of the length of the rod 26, 29 or 49 results in the adjustment of the time when the engaging portion 25 engages with the first arm 21 to forcibly operate the bucket control valve 35. this adjustment is made to determine the specified posture of the bucket 9 or alter the specified posture and accomplished chiefly by adjusting the length of the rod 49. the specified posture of the work implement is such that when it is the bucket 9, the opening 9a is horizontal. when the implement is a fork, the posture is the position in which grass or the like will not fall off. when the bucket 9 is in the specified posture on flat ground, the opening 9a is parallel to the ground and the tractor. on an upward or downward slope, the opening is in an absolutely horizontal position inclined with respect to the ground and the tractor. to assure such absolutely horizontal position, the length of the rod 26, 29 or 49 is adjusted according to the slope of the ground. the specified posture of the work implement has a small allowance range in the scooping and dumping directions, such that with the booms 7 in the lowermost position, the bucket control valve 35 may start operating when the bucket opening 9a is brought to the absolutely horizontal position or to a position slightly tilted forward or rearward from this position. figs. 8 and 9 show a modified embodiment. the bracket 13 on the rear side of the bucket 9 is not provided with any flexible link but is directly connected at its upper portion to the bucket cylinder 12 and at an intermediate portion thereof to the rod 26. the engaging portion 25 is provided on the first arm 21 and adapted to contact with the second arm 22. the pivotal member 28 of the embodiment is in the form of an l-shaped bell crank having two short arms. interlocking means 52 for operatively connecting one of the arms to the second pivotal element 42 comprises a bowden cable 53, which comprises an outer wire 53a connected at its respective ends to a bracket 54 secured to the mast 5 and to a bracket 55 secured to the mount plate 33, and an inner wire 53b. the inner wire 53b has one end connected to the above-mentioned arm of the pivotal member 28 by a pin 57 and the other end connected to the second pin portion 45 directly, or through the ball joint 48 or through the ball joint 48 and the rod 49. with the modified embodiment, the bowden cable 53 can be of a large length, so that the control unit 32 need not be attached to the mast 5 but can be disposed, for example, in the vicinity of the seat of the tractor 2. this makes it possible to position the control unit 32 as desired relative to the pivotal member 28. however, since the bowden cable 53 has some elongation and attachment errors, the control unit is operable with higher accuracy when an interlocking means 52' comprising the ball joint 48 and rod 49 is used in combination with a pivotal member 28 having an elongated arm and connected directly to the rod 49 as in the foregoing embodiment. fig. 10 shows modified control lever means. the boom control valve 34 and the bucket control valve 35 have their own control levers 59, 37. pivotal elements 60, 42 for the control levers 59, 37 are rotatably supported on a single pivot 61 supported by the control box 36. a rod 50 is connected to a pin portion 62 projecting from the pivotal element 60, and a rod 47 to a pin portion 44 projecting from the pivotal element 42. the pivotal element 42 or the control lever 37 has a pin portion for connection to the interlocking means. the invention being thus described, it will be obvious that the same may be varied in many ways. such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
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092-355-861-647-27X
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US
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[
"US"
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H01M10/0585,H01M6/18,H01M10/04,H01M10/0562,H01M10/28,H01M50/54,H01M6/46,H01M10/052,H01M10/42
| 2012-10-16T00:00:00 |
2012
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[
"H01"
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embedded solid-state battery
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elements of an electrochemical cell using an end to end process. the method includes depositing a planarization layer, which manufactures embedded conductors of said cell, allowing a deposited termination of optimized electrical performance and energy density. the present invention covers the technique of embedding the conductors and active layers in a planarized matrix of pml or other material, cutting them into discrete batteries, etching the planarization material to expose the current collectors and terminating them in a post vacuum deposition step.
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1. a method for manufacturing of a solid-state electrochemical device, the method comprising: forming, using at least a process chamber, a plurality of first strip regions overlying a surface region of a substrate member coupled to a transfer device, the transfer device being selected from at least one of a drum device, a roll-to-roll device, a plate device or a belt device, each of the first strip regions comprising a stack of thin film electrochemical devices, each of the thin film electrochemical devices comprising at least an anode material, a cathode material, and an electrolyte material, the plurality of first strip regions being configured in a first direction along a length of the surface region of the substrate and being normal to a second direction, the second direction being normal to the first direction; forming a first gap region associated with each of the plurality of strip regions using a removal process, each of the plurality of first strip regions having a first thickness above the surface region, the removal process being selected from one of a shadow masking removal or ablation process or a laser ablation process to cause formation of a plurality of strips configured with the plurality of first gap regions, each of which is separating a pair of strips; forming a fill material overlying the plurality of first strips and plurality of first gap regions to substantially fill each of the first gap regions and substantially enclose each of the plurality of first strips and forming a planarized first upper surface region overlying the plurality of strips; successively repeating the process of forming the plurality of strip regions, the plurality of gap regions, and forming the fill material overlying the planarized first upper surface region n times, where n is an integer greater than two (2) to form multiple plurality of strips configured as a vertical stack structure enclosed in the fill material overlying the substrate member, removing the substrate member including the vertical stack structure including the multiple plurality of strips from the transfer device, while maintaining the substrate member having the multiple plurality of strips intact and enclosed in fill material; selectively separating one or more of the plurality of strips to form an encapsulated portion of one of the multiple strips enclosed in fill material; exposing a first conductor from a first side of the encapsulating portion of one of the multiple strips and exposing a second conductor from a second side of the encapsulating portion of one of the multiple strips; forming a first electrode member electrically and mechanically coupled to the first conductor and forming a second electrode member electrically and mechanically coupled to the second conductor; and providing a discrete battery device. 2. the method of claim 1 , wherein the forming of the first electrode member and the second electrode member are provided by at least one of vacuum deposition, plating, thermal spraying, dipping, coating, air or airless spraying or brushing. 3. the method of claim 1 , wherein the fill material for the first planarized upper surface region comprises an acrylated monomer or mixture of a plurality of monomers and curing initiators with a viscosity measured in cps at 20 degrees celsius between about 0.6 and 600. 4. the method of claim 1 , wherein exposing comprises an etching process, the etching process being at least one of a liquid etchant to selectively etch an anode current collector or a cathode collector or a plasma or plasma with ion assist including at least one background gas, the background gas being at least one of argon, oxygen, nitrogen, helium, cf 6 , cf 4 , ch 4 , sf 6 , h, and/or combinations thereof. 5. the method of claim 1 , wherein the plurality of strip regions is characterized by greater than 1000 strips in parallel arrangement. 6. the method of claim 1 , wherein the fill material is characterized as an electrical insulator deposited by at least one of pvd, cvd, pecvd, flash evaporation, thermal evaporation, electron beam evaporation, rf or dc or pulsed dc or mid frequency magnetron sputtering, or high power pulsed magnetron sputtering hppms. 7. the method of claim 1 , wherein the first electrode member and the second electrode member are made using a conductive material from as least one of chromium, nickel, monel, titanium, silver, gold, aluminum, copper, zinc, tantalum, tin, iridium, palladium, tantalum, or their alloys, and nitrides, the conductive material being provided using at least one of electroplating, electroless plating, pvd, cvd, plasma assisted cvd, sputtering, bias sputtering, ion assisted deposition, arc deposition, flame and plasma spraying, dipping, painting, ink jet printing, roll coating, or combinations thereof. 8. the method of claim 1 , wherein the first electrode member and the second electrode member are characterized by an adhesion factor to the first conductor and the second conductor, the adhesion factor being greater than 0.05 pounds per square inch. 9. the method of claim 1 , wherein each of the first conductor and the second conductor has greater thickness region within a vicinity of a termination with the first electrode member or the second electrode member. 10. the method of claim 1 , wherein one or more of the plurality of strips are configured with one or more different widths and/or lengths to form one or more different discrete battery devices. 11. the method of claim 1 , further comprising providing at least one function enhancement region configured between any pair of strips or between any one of the strips and the surface region or overlying an upper strip region or covering a entire three-dimensional shape of the one or more strips, the function enhancement region being provided to increase resistance to environmental degradation; to decrease lithium diffusion; to increase resistance to scratching; to increase resistance to solvents; to enhance printing ink adhesion; to provide color; to provide gloss; to provide reduced odor transmission; to provide thermal protection; to enhance thermal transfer; to help constrain expansion; to provide a gettering function to moisture; to provide a gettering function to oxygen; to provide a gettering function to nitrogen; to enhance tolerance to thermal shock; to enhance resistance to or transmission of emi interference; to minimize stress; to provide temporary adhesion for improvement of secondary manufacturing steps; to increase the frictional coefficient of the outer layer to increase ease of handling in assembly, packaging and use; to provide a removable protective layer to temporarily increase protection during storage, handling or work-in-progress; to provide temporary electrical insulation of the battery device terminals; or to provide adhesion of one stack of battery devices to another stack of battery devices or to a package in a separate down stream process. 12. the method of claim 11 , where the function enhancement region composed of at least one of polychlorotrifluoroethene (pctfe), polyvinylidenechloride (pvdc), epoxy compound, silicone compound, acrylate compound, urethane compound, buna, cellulose compound, block co-polymers, polyethylene terephthalate (pet), polyethylene naphthalate (pen), polyethylene (pe), high-density polyethylene (hdpe), ultra-high-molecular-weight polyethylene (umwpe), enamel compound, siox, al 2 o 3 , sioxnx, tinx, tanx, taox, glyptol, mica, mylar, natural rubber compound, or neoprene compound. 13. the method of claim 1 , wherein the selectively separating comprises using at least one of a diamond saw, diamond wire saw, carbide saw, tool steel saw, water jet, laser, ultrasonics, knife blades, scoring, breaking, punching, shearing, heat, cryogenics, etching and their combinations. 14. the method of claim 1 , further comprising attaching an active or passive electrical device to the discrete battery device, the electrical device being at least one of a pin or socket, electrical energy transmission device, parallel or serial data transmission device, led, fluorescent lamp, incandescent lamp, electroluminescence lamp, digital display, analogue display, sound producing device, vibration producing device, digital memory device, solar cell, heat producing device, thermistor or thermocouple, pressure sensing device, humidity sensing device, magnetism sensing device, acceleration sensing device, gravity sensing device, ph sensing device, blood sugar sensing device, odor sensing device, optical sensing device, x-ray sensing device, gamma ray sensing device, electric charge sensing device, mems based device, monolithic silicon analogue or digital device, energy management device, diode, transistor, resistor, capacitor, inductor, antenna, or rfid device. 15. the method of claim 1 , further comprising using a computed and engineered set of spatial dimensions for each anode material, cathode material, electrolyte material, first conductor, second conductor, and first electrode measured out of plane for a margin or measured in plane between a pair of dissimilar conductors and a termination, or to optimize or improve energy density for a termination region. 16. the method of claim 15 , wherein the margin is between about 5 and 100 microns and the set of spatial dimensions ranging from about 0.01 and 25 micron. 17. the method of claim 15 , further comprising an energy capacity of between 150 mah and 50 ah or the energy density is greater than 600 wh/l for the discrete battery device.
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cross-references to related applications the present invention is related to and incorporates by reference, for all purposes, the following u.s. pat. no. 7,945,344 and u.s. patent publication nos. 2009-0325063; 2012-0058380; 2012-0055633; and 2012-0058280; and u.s. patent application ser. no. 13/407,609, all assigned to sakti3, inc. background of the invention this present invention relates to manufacture of electrochemical cells. more particularly, the present invention provides a process and method for manufacturing a solid-state thin film battery device. merely by way of example, the invention has been described with the use of lithium based cells, but it is recognized that other materials such as zinc, silver, copper, cobalt, iron, manganese, magnesium and nickel could be designed in the same or like fashion. additionally, such batteries can be used for a variety of applications such as portable electronics (cell phones, personal digital assistants, music players, video cameras, and the like), power tools, power supplies for military use (communications, lighting, imaging and the like), power supplies for aerospace applications (power for satellites), and power supplies for vehicle applications (hybrid electric vehicles, plug-in hybrid electric vehicles, and fully electric vehicles). the design of such batteries is also applicable to cases in which the battery is not the only power supply in the system, and additional power is provided by a fuel cell, other battery, ic engine or other combustion device, capacitor, solar cell, etc. summary of the invention according to the present invention, a method related to the manufacture of electrochemical cells is provided. more particularly, the present invention provides a method of manufacturing a solid-state thin film battery device. merely by way of example, the invention has been provided with use of lithium-based cells, but it would be recognized that other materials described above, could be designed in the same or like fashion. additionally, such batteries can be used for a variety of applications such as portable electronics (cell phones, personal digital assistants, music players, video cameras, and the like), power tools, power supplies for military use (communications, lighting, imaging and the like), power supplies for aerospace applications (power for satellites), and power supplies for vehicle applications (hybrid electric vehicles, plug-in hybrid electric vehicles, and fully electric vehicles). the design of such batteries is also applicable to cases in which the battery is not the only power supply in the system, and additional power is provided by a fuel cell, other battery, ic engine or other combustion device, capacitor, solar cell, etc. in a specific embodiment, the present invention provides a procedure for the formation of one or more elements of an electrochemical cell using a complete process. benefits are achieved over conventional techniques. depending upon the specific embodiment, one or more of these benefits may be achieved. in a preferred embodiment, the present invention provides a process for complete deposition of all electrochemical cell materials, including anode, cathode, electrolyte, barriers, stress modifying layers, and embedded current collectors, including combinations thereof. in particular, it is the ability afforded by this invention to manufacture electrochemical cells without handling individual layers which gives the added benefit of embedded current collectors, allows the formation of a robust product while minimizing parasitic losses of non-energy producing layers and increasing yield due to handling and particulate issues. specific benefits seen over the conventional art include: a) the ability to utilize extremely thin layers without subjecting them to stresses and high aspect ratio surface features, such as rollers, in a roll-to-roll continuous process.b) the ability to manufacture large numbers of stacked battery cells in strip form, allowing for battery capacity to be later determined by the length of the battery cut from the strip.c) the ability to deposit a smoothing and/or insulating layer between stacked cells of a material, which exhibits a very high etching contrast ratio. this allows the embedded current collectors to be exposed and electrically terminated without physical contact, thus significantly reducing damage and increasing yield.d) the ability to terminate current collectors both very close together (<0.5 microns) to very far apart (>5 mm) in a single operation.e) the ability to utilize the termination itself for adhesion to the battery, and not add any stress to the current collectors, thus improving performance and yield.f) the ability to optimize the volume and mass of the terminations and gain the maximum energy density per battery. this is particularly true in batteries that are small as would be used in electronic communications and handheld devices.g) the ability to optimize the margin, as defined as the distance between anode and cathode layers and current collectors in plane, by a post deposition process and not burden the manufacturing process with extreme tolerance positioning of layers. this is especially true for batteries with a high number of layers and relatively thick total height.h) the ability to make extremely low impedance connection to very thin current collectors due to the vacuum deposited nature of the termination process and the ability to connect to the entire length of the current collector.i) the ability to tailor the materials of the termination to have components that provide adhesion, low electrical impedance, robustness, solderability, weldability, and the like.j) the ability to utilize an insitu ablation process, such as laser, brush, ion beam, wheel, roller, scraper, and the like in place of a shadow mask to delineate conductors and or other layers of the electrochemical device. it is further understood that the method itself may be a combination of methods and may affect the electrochemical properties of the thin film, and may be the cause of significant improvements in ionic conductivity, electrical resistivity, contact resistance, and the like, all of which are incorporated herein. depending upon the specific embodiment, one or more of these benefits may be achieved. of course, there can be other variations, modifications, and alternatives. the present invention achieves these benefits and others in the context of unique and non-intuitive process technology. however, a further understanding of the nature and advantages of the present invention may be realized by reference to the latter portions of the specification and attached drawings. brief description of the drawings the following diagrams are merely examples, which should not unduly limit the scope of the claims herein. one of ordinary skill in the art would recognize many other variations, modifications, and alternatives. it is also understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this process and scope of the appended claims. fig. 1 is a cross-section of an electrochemical cell; fig. 2 is a drawing showing removal a portion of the deposited material at the edge of the layer; fig. 3 is a schematic showing a cross-section of an electrochemical cell in which portions of the layers have been removed to facilitate termination; fig. 4 is a cross-section of an electrochemical cell depicting the cutting of an electrochemical cell into smaller strips; fig. 5 is a cross-section of an electrochemical cell with a smoothing layer deposited over the edge; fig. 6 is a drawing of a strap of embedded electrochemical cells; fig. 7 is a scanning electron microscope image of the cross-section of a multilayer cell; and fig. 8 is an apparatus for manufacturing the embedded solid-state battery device. fig. 9 is a simplified flow diagram illustrating a method according to an embodiment of the present invention. detailed description of the invention lithium ion batteries must occupy substantial three-dimensional volumes to be useful. by way of example, those used in the apple iphone 4® and the gm volt® achieve this usefulness by being deposited on a web or flexible substrate and stacked or wound with separator webs and current collector webs to form a size and electrical performance suitable for use. the wound or stacked devices are then terminated by a number of means, all of which use an excess of space and weight to compensate for small area electrical connections due to manufacturing problems associated with termination along the entire length of the current collectors. as for solid-state technology, those in the field have attempted to build multi-layer, or stacked solid-state batteries, deposited one upon the other, but have been limited to only a single layer of cells due to manufacturing problems. these manufacturing problems include the difficulties of building multiple stacks one upon the other without transmitting defects and systematically increasing the roughness of layers or stress in the layers. another inherent problem is the termination of a large number of opposite polarity, extremely thin current collectors in a minimum space with minimum weight and with the robustness required for commercial applications. the thin film batteries thus far produced are severely limited in energy and usefulness, and are not readily scalable. those skilled in the art have been unable to manufacture thin film solid-state batteries useful in replacing conventional technology, particularly those batteries for extended use in consumer electronics or in automobiles. one of the advantages of thin film solid-state batteries is their ability to be manufactured in precision sufficient to allow large numbers of parallel cells to form higher energy density devices without the detrimental effects often seen in conventional technology. these detrimental effects include: breakdown of the liquid dielectric, growth of films at the anode and cathode interface to the dielectric, dendrite growth of the anode materials, spot heating at particles and shorting. as noted above, the physics of the conventional state of inorganic materials useful in solid-state batteries overcomes almost all of these detrimental effects except for the very thin layers required to operate at charge and discharge rates that are useful. this, in turn, leads to vast numbers of these very thin cells being connected in parallel. furthermore, the subsequent manufacturing requirements of terminating this high number of current collectors, whose thicknesses can be in the range of 100 to about 5000 angstroms, onto terminals that can carry 10's of amps are extremely difficult. these very thin layers play an important role in the superior energy density of solid-state batteries, as the volume and mass they contribute is very minor; however, this same benefit represents a major manufacturing problem due to their delicate nature. added to these issues is the need for extreme robustness both physically and electrically, and the not insubstantial requirement to minimize the mass and size of the terminations. the conventional state of the art utilizes shaped current collectors ending in tabs, which contact only a portion of the width of the current collector. this can have serious deleterious effects on the interface impedance between the current collector and the termination. in fact, a substantial number of battery pack failures have been traced to poor terminations. another manufacturing problem with solid-state batteries is the glass or ceramic nature of the cathode and electrolyte. these films are thin and brittle having little strength, especially in tension. submicron sized defects, especially in the electrolyte layer, can cause performance degradation or complete failure. consequently, handling of these layers of thin films presents great challenges in product quality. further, in order to realize the true high energy density potential of solid-state batteries, little volume and mass can be given over to the type of bulky terminations and packaging used in present commercial batteries. what works for conventional wet technology does not make economic sense for solid-state. therefore, when designing a product and process for the manufacture of solid-state batteries, one must include all aspects of what is inside of the package, how the cell itself is shaped and how it is terminated. this is especially true of multilayer stacks of thin films with multiple different materials and high numbers of layers. this invention relates to a non-intuitive process of manufacturing robust multilayer electrochemical cells. referring to u.s. pat. no. 7,945,344 and u.s. patent publication nos. 2009-0325063; 2012-0058380; 2012-0055633; and 2012-0058280; and u.s. patent application ser. no. 13/407,609, all assigned to sakti3, inc., and incorporated by reference herein, we teach that the optimum design for energy density includes electrochemical cells with multiple repeating layers, thin current collectors, strategically placed smoothing layers and monolithic embedded terminations. according to the present invention, methods related to the manufacture of electrochemical cells are provided. one element of the invention relates to the ability to planarize the cross-section of the battery itself, compensating for the difference in step height caused by margins (as defined above and created by masking or by removal). a further element of the invention pertains to the ability to protect both layers and terminations from physical damage during the manufacturing process; this is the direct and inherent benefit of encapsulating all layers into a monolithic design. a further element of the invention pertains to the ability to utilize multiple deposition sources for the simultaneous deposition or manufacturing of layers, thus significantly decreasing the manufacturing time, output per capital dollar invested, and cycle time per batch. yet a further element of the invention results in the ability to manufacture stacked solid-state batteries, in numbers greater than 1000, without touching the layers. a further element of the invention, made possible by the above feature, is the ability to optimize energy density by controlling the parasitic volume and mass associated with margins, terminations, and substrates. a unique element of the invention is the non-intuitive ability to manufacture a complete multi-layer solid-state battery in a single operation and vacuum step, thus significantly reducing the manufacturing cost and increasing the product quality and yield. yet another novel element of the invention is the ability to deposit multiple strips of batteries of different widths and lengths thus creating finished batteries suitable for multiple customers and purposes in a single machine cycle. further, it is a unique ability to easily change process adjustment or subcomponents and optimize manufacturing parameters for individual product needs. examples enabled by the invention include, but are not limited to, varying the amounts of cathode to anode material throughout the thickness of a combination or multi-deposited depleted cathode layers, graded index or modulus films for the control and tailoring of stress or temperature and the control of their gradients. as further described and illustrated in fig. 1 , the elemental steps provided by this invention are as follows. referring to fig. 1 , describing a preferred embodiment of the invention particularly unique and useful for the manufacture of electrochemical cells. fig. 1 is a cross-section of an electrochemical cell depicting several key components of this invention. item 23 refers to the cathode current collector layer, item 25 refers to the cathode layer, item 27 refers to the electrolyte layer, and item 21 refers to the anode layer. variations of this arrangement may include an anode current collector layer disposed directly on top of the anode layer shown, coating an anode or a cathode on both sides of their respective current collectors, with or without an intermediate layer. items 21 and 23 , again depicting the anode and cathode current collectors respectively, are shown to protrude from the stack of layers in general. notice item 31 , which is symmetrical on both sides of the electrochemical stack. this item is the termination which connects in parallel all protruding anode and all protruding cathode current collector layers into a low impedance construct allowing direct connection to the electrochemical cell by spring loaded contact, soldering, welding, conductive materials, and the like. paying particular attention to item 29 we illustrate the smoothing and insulating layer described in detail above. it is noted that the etching contrast of this material against the anode and cathode current collector is very high in the presence of plasma-assisted or chemical etching. in another preferred embodiment, as depicted in fig. 2 , item 29 in fig. 1 above would not be necessary if the alternating margins of the anode and cathode layers are produced by removal. as shown in fig. 2 , item 86 depicts the belt or drum of the deposition tool described herein. on that belt or drum are coated multiple layers of electrochemical materials forming the product. here it can be seen that items 81 and 83 refer to the belt or drum or underlying layers where a portion of a layer 87 and 89 respectively are removed, as by laser ablation or other methods described above. this embodiment has several advantages over shadow masking and filling as described in fig. 1 . among these advantages are: ability to produce a sharp and precise edge not effected by the mean free path of the deposition material, ability to dynamically align the removed material via an optical feed-back mechanism, such as a camera, the ability to manufacture these margins in exceedingly thin sections, between 1 and 100 microns, thus allowing for the optimization of energy density not attainable by other manufacturing means. as illustrated in fig. 3 , the use of removal or ablation techniques, such as a laser, allows for the margin to be created and to preserve a solid layer edge to present to the termination operation but still separate the terminations of anode and cathode on, for example, each side of the cell. in fig. 3 above terminations made over the full surface of the cell edge depicted by item 91 results in contact to the anode and/or its associated current collector, and terminations made over the full surface of the cell edge depicted by item 93 results in contact to the cathode and/or its associated current collector. as shown in fig. 4 , it is possible to retain all of the beneficial features of this invention with this embodiment including cutting individual strips from the main strap, terminating them, and then cutting each strip into individual battery products. referring now to fig. 5 , we depict the strap of electrochemical cells as a cross-section in the cross machine direction. here we illustrate a similar layer structure to figs. 1 and 2 where item 51 is a cathode current collector, item 53 is a cathode layer, item 55 is an electrolyte layer, item 57 is an anode layer and item 61 represents the leveling-smoothing layer of high etch ratio. it will be noticed that four strips of electrochemical cells are depicted, however, it is the intention of this invention to include multiples of strips, both equal in width and different in width as explained in detail above. the arrows are shown at the place were separation of the strips is performed. after separation, the individual electrochemical strips would resemble fig. 2 , and after plasma or chemical etching and termination, fig. 1 ; hence, these figures depict the complete process of producing the strap of electrochemical devices composed of strips to be separated, and etched and terminated. it is also contemplated by this invention that the bottom and top of the strap may be preferentially coated or covered by a barrier layer; thus affording a high degree of integrity to the then separated electrochemical cell. it is further contemplated by this invention that the number of alternate layers may be in other arrangements, including cathode current collector, cathode. electrolyte, anode, cathode, cathode current collector as a repeating mer. it is further contemplated by this invention that the number of alternate parallel electrochemical cells may be as few as one and as numerous as several thousand. referring now to fig. 5 , depicting an electrochemical cell made according to one embodiment of this invention. as described above for fig. 1 , the cell includes anode layers 21 , cathode current collector layers 23 , cathode layers 25 , and electrolyte layers 27 . in this depiction, the leveling-smoothing layers items 41 are shown prior to plasma etching. in this depiction it is shown how the thin layers needing to be electrically connected in parallel are supported by complete embedding within the structure. turning now to fig. 6 , item 65 illustrates the strap of embedded electrochemical cells removed from the substrate transport device, i.e. drum, strap or sheet. item 67 indicates the rows of stacked cells in the machine direction. item 69 indicates the locations where the strap is to be separated into sub-strips according to the present invention. by way of illustration only, three sub-strips are depicted, but it is envisioned by this invention that many sub-strips may be manufactured in a strap, and that different width sub-strips may be simultaneously manufactured. this, combined with the inherent ability to separate the sub-strips into different lengths, provides the ability to manufacture many size and shapes of electrochemical devices in one step. by way of example of one embodiment of the invention, fig. 7 shows a scanning electron microscope image of the cross-section of multilayer cells separated by polymer interlayers, deposited according to one method of the current invention. the layers as indicated in fig. 7 are composed of: 1. item 99 cell 1 current collector; 2. item 101 cell 1 cathode; 3. item 103 cell 1 electrolyte; 4. item 105 cell 1 anode; 5. item 107 polymer interlayer; 6. item 109 cell 2 current collector; 7. item 111 cell 2 cathode; 8. item 113 cell 2 electrolyte; 9. item 115 cell 2 anode; and 10. item 117 polymer interlayer. as depicted in fig. 8 , the apparatus for manufacturing the present invention is illuminated. although it has been described in u.s. pat. no. 7,945,344 and u.s. patent publication nos. 2009-0325063; 2012-0058380; 2012-0055633; and 2012-0058280; and u.s. patent application ser. no. 13/407,609, all assigned to sakti3, inc., which are incorporated by reference herein, we present this information to help illustrate the fullness of the invention. turning to item 71 , we see a vacuum chamber enclosing all of the processing equipment. for illustration purposes only, a rectangular chamber is shown, but also suitable and contemplated by this invention are round, square, and other shapes, and multiple discrete chambers separated by load locks. contained within this processing chamber are several pvd deposition sources (item 75 ). again, these deposition sources have been described in full in u.s. pat. no. 7,945,344 and u.s. patent publication nos. 2009-0325063; 2012-0058380; 2012-0055633; and 2012-0058280; and u.s. patent application ser. no. 13/407,609, all assigned to sakti3, inc., which are incorporated by herein and are used for illustrative purposes as other deposition devices and arrangements are contemplated by this invention. item 73 illustrates a revolving belt upon which the present invention is manufactured. again, by way of illustration, a roll-to-roll arrangement, a rotating drum, or a linear movement of plates of substrates may be substituted. the belt is shown in a horizontal configuration, but again by way of illustration the drum or sheet or plate may be horizontal or vertical or any angle that is required to optimize the manufacturing of the present invention. finally, item 77 depicts the evaporation and energy curing of the substantially acrylated organic monomer integral to this invention. here we see this item mounted to the left side of the belt substrate transport device, but in full contemplation of this invention other locations may be more advantageous. it can be seen how the application of the evaporated organic monomer is directed and condensed on the substrate transport. control of the substrate temperature is a key process parameter of this invention with temperatures between about 3 degrees c. and 17 degrees c. most useful. high performance di- and tri-acrylate monomers or a mixture of the same are atomized in an ultrasonic nozzle and evaporated and condensed on the substrate. by way of example, the monomer or mixture of monomers may include tripropylene glycol diacrylate, trimethylolpropane triacrylate, dodecanediol dimethacrylate. the mixture may also include initiators for curing of the condensed material. curing can be achieved by a number of means including but not limited to electron beam, ion beam, uv, xenon lamp, or thermal treatment. so finally, it can be fully understood and envisioned that this invention is unique and non-intuitive for the manufacturing of thin film solid-state battery cells and devices. by rotating the belt, in this instance, various layers may be simultaneously deposited through a number of masks to deposit delineated strips of electrochemical thin film layers. upon condensation and cross linking of the organic monomer, these strips of layers are planarized and embedded into a solid matrix of organic and inorganic materials of certain thicknesses and in certain positions. the process may simply be continued, or repeated, until the necessary number of device cells or layers is deposited. as detailed above, later process steps outside or inside of the same process chamber, or chambers is used to separate, preferentially etch, or remove a portion of the embedded organic polymer exposing the integrated anode and cathode current collectors, allowing for a pvd termination layer or layers to be applied. additional steps outside the chamber may include additional processes using the same or similar essentially acrylate polymer for further enclosing or stacking the stacks of layered cells. this process may require different monomer mixtures or curing processes due to the change in environment. thus completing the battery device and making it ready for testing, packaging and sale. conventional practice does not address these needs or unique solutions in multilayer solid-state batteries. therefore presented below is an encapsulated solid-state battery and method of manufacture. 1. deposit with a single, continuous vacuum process, a strap or substrate containing all layers necessary for a useful and valuable solid-state battery suitable for replacement of existing battery technology. this deposition may contain any combination of masking or removal to achieve delineation of individual layers.2. remove the strap from the vacuum coater.3. cut the strap into strips.4. terminate the strips by any number of means including: etching back of insulating materials, plating, shooping, vacuum depositing, metal spraying, dipping, roller coating, and the like with a conductive material.5. cut the strips into individual batteries.6. add electrically conductive leads.7. if required, stack and combine the cells in a series or parallel to obtain the required voltage or current capability and then package the battery by any number of means including: sealing into a pouch, metal package, plastic package or other pre-formed enclosure, dipping, spraying, or otherwise coating in a suitable liquid compound, then curing or hardening the compound.8. using as a finished battery product. a method for manufacturing a battery device is outlined as follows, referring also to method 900 of fig. 9 . 1. (step 902 ) start; 2. (step 904 ) form using at least a process chamber, a plurality of first strip regions overlying a surface region of a substrate member coupled to a transfer device, the transfer device being selected from at least one of a drum device, a roll-to-roll device, a plate device or a belt device, each of the first strip regions comprising a stack of thin film electrochemical devices, each of the thin film electrochemical devices comprising at least an anode material, a cathode material, and an electrolyte material, the plurality of first strip regions being configured in a first direction along a length of the surface region of the substrate and being normal to a second direction, the second direction being normal to the first direction; 3. (step 906 ) form a first gap region associated with each of the plurality of strip regions using a removal process, each of the plurality of first strip regions having a first thickness above the surface region, the removal process being selected from one of a shadow masking removal or ablation process or a laser ablation process to cause formation of a plurality of strips configured with the plurality of first gap regions, each of which is separating a pair of strips; 4. (step 908 ) form a fill material overlying the plurality of first strips and plurality of first gap regions to substantially fill each of the first gap regions and substantially enclose each of the plurality of first strips and forming a planarized first upper surface region overlying the plurality of strips; 5. (step 910 ) successively repeat the process of forming the plurality of strip regions, the plurality of gap regions, and forming the fill material overlying the planarized first upper surface region n times, where n is an integer greater than two (2) to form multiple plurality of strips configured as a vertical stack structure enclosed in the fill material overlying the substrate member; 6. (step 912 ) remove the substrate member including the vertical stack structure including the multiple plurality of strips from the transfer device, while maintaining the substrate member having the multiple plurality of strips intact and enclosed in fill material; 7. (step 914 ) selectively separate one or more of the plurality of strips to form an encapsulated portion of one of the multiple strips enclosed in fill material; 8. (step 916 ) expose a first conductor from a first side of the encapsulating portion of one of the multiple strips and exposing a second conductor from a second side of the encapsulating portion of one of the multiple strips; 9. (step 918 ) form a first electrode member electrically and mechanically coupled to the first conductor and forming a second electrode member electrically and mechanically coupled to the second conductor; and 10. (step 920 ) provide a discrete battery device. as shown, the present method includes one or more of the above sequence of processes. variations to the processes also exist. for example, the forming of the first electrode member and the second electrode member are provided by at least one of vacuum deposition, plating, thermal spraying, dipping, coating, air or airless spraying or brushing. the fill material for the first planarized upper surface region comprises an acrylated monomer or mixture of a plurality of monomers and curing initiators with a viscosity measured in cps at 20 degrees celsius between about 0.6 and 600. the fill material is characterized as an electrical insulator deposited by at least one of pvd, cvd, pecvd, flash evaporation, thermal evaporation, electron beam evaporation, rf or dc or pulsed dc or mid frequency magnetron sputtering, or high power pulsed magnetron sputtering hppms. the exposing comprises an etching process, the etching process being at least one of a liquid etchant to selectively etch an anode current collector or a cathode collector or a plasma or plasma with ion assist including at least one background gas, the background gas being at least one of argon, oxygen, nitrogen, helium, cf 6 , cf 4 , ch 4 , sf 6 , h, and/or combinations thereof. in an example, the separating process uses at least one of a diamond saw, diamond wire saw, carbide saw, tool steel saw, water jet, laser, ultrasonics, knife blades, scoring, breaking, punching, shearing, heat, cryogenics, etching and their combinations. in an example, any of the above steps, and others described herein, further include attaching an active or passive electrical device to the discrete battery device, the electrical device being at least one of a pin or socket, electrical energy transmission device, parallel or serial data transmission device, led, fluorescent lamp, incandescent lamp, electroluminescence lamp, digital display, analogue display, sound producing device, vibration producing device, digital memory device, solar cell, heat producing device, thermistor or thermocouple, pressure sensing device, humidity sensing device, magnetism sensing device, acceleration sensing device, gravity sensing device, ph sensing device, blood sugar sensing device, odor sensing device, optical sensing device, x-ray sensing device, gamma ray sensing device, electric charge sensing device, mems based device, monolithic silicon analogue or digital device, energy management device, diode, transistor, resistor, capacitor, inductor, antenna, or rfid device. in an example, the first electrode member and the second electrode member are made using a conductive material from as least one of chromium, nickel, monel, titanium, silver, gold, aluminum, copper, zinc, tantalum, tin, iridium, palladium, tantalum, or their alloys, and nitrides. the conductive material is provided using at least one of electroplating, electroless plating, pvd, cvd, plasma assisted cvd, sputtering, bias sputtering, ion assisted deposition, arc deposition, flame and plasma spraying, dipping, painting, ink jet printing, roll coating, or combinations thereof. the first electrode member and the second electrode member are characterized by an adhesion factor to the first conductor and the second conductor, the adhesion factor being greater than 0.05 pounds per square inch. each of the first conductor and the second conductor has greater thickness region within a vicinity of a termination with the first electrode member or the second electrode member. in an example, one or more of the plurality of strips are configured with one or more different widths and/or lengths to form one or more different discrete battery devices. the plurality of strip regions is characterized by greater than 1000 strips in parallel arrangement. additionally, the method can also provide at least one function enhancement region configured between any pair of strips or between any one of the strips and the surface region or overlying an upper strip region or covering a entire three-dimensional shape of the one or more strips. as an example, the function enhancement region being provided: to increase resistance to environmental degradation; to decrease lithium diffusion; to increase resistance to scratching; to increase resistance to solvents; to enhance printing ink adhesion; to provide color; to provide gloss; to provide reduced odor transmission; to provide thermal protection: to enhance thermal transfer; to help constrain expansion; to provide a gettering function to moisture; to provide a gettering function to oxygen; to provide a gettering function to nitrogen; to enhance tolerance to thermal shock; to enhance resistance to or transmission of emi interference; to minimize stress; to provide temporary adhesion for improvement of secondary manufacturing steps; to increase the frictional coefficient of the outer layer to increase ease of handling in assembly, packaging and use; to provide a removable protective layer to temporarily increase protection during storage, handling or wip; to provide temporary electrical insulation of the battery device terminals; or to provide adhesion of one stack of battery devices to another stack of battery devices or to a package in a separate down stream process, and any combinations of the above. in an example, the function enhancement region composed of at least one of pctfe, pvdc, epoxy compound, silicone compound, acrylate compound, urethane compound, buna, cellulose compound, block co-polymers, pet, pen, pe, hdpe, umwpe, enamel compound, siox, al2o3, sioxnx, tinx, tanx, taox, glyptol, mica, mylar, natural rubber compound, or neoprene compound, or combinations thereof, and the like. in various embodiments, the method can include a method for the manufacture of a solid-state electrochemical device using at least a high speed evaporation process. the method can include using a computed and engineered set of spatial dimensions for each layer thickness measured out of plane, for margins, measured in plane between dissimilar conductors and a termination, and for the termination layers where each dimension is optimized for energy density of the electrochemical cell. the margin can be between about 5 and 100 microns, where the layer thicknesses are between about 0.01 and 25 microns. the energy capacity can be between 150 mah and 50 ah or the energy density is greater than 600 wh/l. the engineered set of spatial dimensions may be described in one or more of the following, including u.s. pat. no. 7,945,344 and u.s. patent publication nos. 2009-0325063; 2012-0058380; 2012-0055633; and 2012-0058280; and u.s. patent application ser. no. 13/407,609, each of which is incorporated by reference, and all assigned to sakti3, inc. in various embodiments, the method can include forming multiple thin layers of solid-state materials comprising an electrochemical cell resilient in bending and substantially environmentally protected from an ambient factory environment. the forming of the multiple thin layers of solid state materials can be further processed in the factory environment free from an exterior packaging designed to maintain the multiple thin layers of solid state materials free from contaminants. the multiple thin film layers of solid state materials can be shaped to conform to fit within an individual packaging to increase an energy density for an end use product or a completed electrochemical cell or alternatively forming the multiple thin layers of solid state materials directly onto a package of a consumer device or industrial device, the consumer device or the industrial device being one of a cell phone, computer tablet, laptop pc, or automobile. the completed electrochemical cell has a moisture ingress rate of less than 3×10 −4 gm/m 2 /day. while the above is a full description of the specific embodiments, various modifications, alternative constructions and equivalents may be used. therefore, the above description and illustrations should not be taken as limiting the scope of the present invention which is defined by the appended claims.
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093-294-713-408-859
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US
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[
"WO",
"US"
] |
B02C18/18,B02C18/00,B02C18/22,B02C18/16
| 2005-01-18T00:00:00 |
2005
|
[
"B02"
] |
self-healing cutting apparatus and other self-healing machinery
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self healing of a mechanical part in a mechanical system is provided, such as self healing part in a cutting apparatus. differential hardness of respective parts in contact with each other is used. undesirable damage from a foreign object in a mechanical system is managed by directing damage away from a part ( 118) that is not wanted to be damaged and towards a part ( 120) that may receive damage and be replaced. true zero clearance cutting on a commercial scale is provided via a cutting area including a sacrifice material that is relatively softer than the cutter.
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claims having thus described my invention, what i claim as new and desire to secure by letters patent is as follows: 1. a self-healing mechanical system, comprising: a first part which is solid; a second part which is sacrificial, wherein the sacrificial part is relatively softer than the first part and also relatively softer than a foreign object which undesirably may enter the mechanical system; wherein damage by the foreign object in the system is limited to damage to a damageable surface of the second part. 2. the self-healing mechanical system of claim 1, wherein the sacrificial part mechanically self-heals. 3. the self-healing mechanical system of claim 1, wherein the damageable surface of the sacrificial part faces the first part and occupies a position pi . 4. the self-healing mechanical system of claim 1 , the sacrificial part being movable, and after the damageable surface has been transformed by damage into a damaged surface, a new damageable surface integral with the sacrificial part is moved into the position pi formerly occupied by the damageable surface before being damaged. 5. the self-healing system of claim 1, wherein when the foreign object enters and travels through the mechanical system, the sacrificial part is damaged on the damageable surface, and the first part is not damaged or only minimally damaged. 6. the self-healing system of claim 5, there being a distance "d" between a surface of the first part and the damageable surface of the sacrificial part that is called "dl" in normal operation and when the sacrificial part is damaged, the distance "d" is increased to a larger distance "d2" at points where the sacrificial part has been damaged. 7. the self-healing system of claim 6, including restoring the distance "d2" to about the original distance "dl". 8. the self-healing system of claim 7, wherein the restoration of the distance "d2" back to about the original distance "dl" is by automatic movement of the sacrificial part. 9. the self-healing system of claim 7, wherein the restoration of the distance "d2" to about the original distance "dl" is by movement or reposition of the sacrificial part. 10. the self-healing mechanical system of claim 1, wherein at least one of the first part and the sacrificial part is a moving part. 11. the self-healing mechanical system of claim 1 , wherein in standard operation the first part and the sacrificial part contact each other in a zero-clearance design. 12. the self-healing mechanical system of claim 1 , wherein in standard operation a certain non-zero distance is maintained between the first part and the sacrificial part by design. 13. the self-healing mechanical system of claim 1, wherein the sacrificial part self-heals mechanically. 14. the self-healing mechanical system of claim 1 , wherein the first part is a cutter. 15. the self-healing mechanical system of claim 1 , not including ice. 16. the self-healing mechanical system of claim 1, wherein the sacrificial part is circular or cylindrical shaped. 17. the self-healing mechanical system of claim 1 , wherein the sacrificial part is a blade shape automatically advanced towards the first part.
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self-healing cutting apparatus and other self-healing machinery field of the invention the present invention generally relates to machinery, more particularly, to cutting systems and, more particularly, to cutting systems capable of reducing material to either a shredded form or an unrecoverable fiber or powder form. also, the present invention generally relates to cutting very thin materials, including very thin materials alone (such as paper, etc.) and very thin materials present with other components (such as a credit card, data card, compact disk, floppy disk, cassette tape, etc.); thick materials also may be cut. non- homogeneous input loads may be cut. background there are many types of cutting systems used to destroy documents and other sensitive materials. these cutting systems may include, for example, shredders, pulverizers, grinders and other cutting systems. however, none of the currently known and used systems are capable of completely destroying a document or other sensitive material into an information-unrecoverable form using a simple "one-step" cutting approach. existing document-destruction machines are intricate, complex, and delicate. this poses a problem in high security applications, such as highly sensitive or classified government documents that need to be easily and efficiently destroyed for various security or business reasons. also, many of the known cutting systems are prone to wear, failure and other problems which require constant maintenance and/or refurbishment. the maintenance and/or refurbishment of these complex systems, of course, requires considerable "down-time" which, in turn, also adds to the overall,costs of the system. an additional shortcoming of many of these systems is their single use nature, i.e., only capable of shredding, for instance, paper. by way of example, u.s. patent no. 5,340,034 to jang shows a paper grinder. in this system, a paper document is capable of being ground to a powder form; however, this system uses both a complex arrangement consisting of a corrugation system and an impacting or pulverizing system. in this system, if one of the components fails, for example, the corrugation system, then the document cannot be pulverized. this may result in a significant security risk. it is further noted that this system includes a complex array of rollers and cutters in order to perform the dual purpose of corrugation and pulverizing. this may lead to additional (i) component failure, (ii) maintenance and (iii) downtime, thereby increasing the cost of the entire system. also, in the pulverizing step, it is necessary to repeatedly pulverize the material over an extended time period in order to achieve the powder form, thus resulting in a disadvantage of the system. it is lastly noted that this system appears to be capable of performing its functions only on paper products, but not other materials which may also need to be destroyed. this is a limiting feature of the jang apparatus. in another example, u.s. patent no. 6,079,645 to henreckson shows a desktop shredder. in this shredder, a shredding knife simply shreds paper; however, this system does not and, in fact, appears to be incapable of completely shredding paper into an information- unrecoverable product. instead, the paper is merely cut into strips. also, this same system seems applicable only to paper products, thus limiting its applicability to other products (such as polyester ("mylar") tape) which require shredding or destruction. see, also u.s. patent no. 5,975,445 to ko. similarly, u.s. patent no. 5,320,287 to li also shows a paper shredder which is provided for the limited use on paper, and which also is incapable of providing an information-unrecoverable product. in fact, li only discloses that the paper may be shredded into smaller pieces than "strip" shredders. of course other materials may also be destroyed for high security purposes. these materials may be, for example, mylar or other thin films that carry printed, punched, magnetically recorded, optically recorded, or otherwise recorded information. such materials may also need to be destroyed in a high security fashion. conventionally, this could heretofore only be performed by high-security document "disintegrators", which are heavy (several hundred pounds), expensive, power-hungry, and very noisy. conventional shredding machines, including "disintegrators", tend to jam with such materials (like mylar), which tend to stretch and spindle, rather than be cut properly by the shredding or "disintegrating" apparatus. as indicated at http://www.sdiasac.com/ndsdest.doc, the u.s. national security agency (nsa) has evaluated certain conventional equipment as meeting, or not meeting, the requirements for routine destruction of classified and sensitive material, including high tensile strength paper tape, paper mylar-paper tape and plastic key tape as mentioned above. existing "high-security disintegrators" have the further disadvantage of limited effectiveness, in that the current department of defense standard for such machines specifies a 3/32" output screen. this means that a particle as large as 3/32" on a side may pass through the disintegrator and still meet the destruction standard. in many cases, a particle of this size may carry a considerable amount of recoverable optical or digital information. such films or film-containing papers could, of course, be destroyed by incineration, but this method is undesirable for reasons of health (toxic fumes from burning), convenience, and secrecy. acceptable standards for high-security destruction of paper and other products are being redefined to demand destruction into smaller-size particles. an unmet need remains for machines, devices, methods and systems by which to completely destroy to-be-destroyed materials, while providing ease, reliability and simplicity. scissoring is a cutting mechanism that has been conventionally applied to paper destruction, albeit with limitations. the limitations of conventional scissoring may be appreciated by considering a simple pair of hand-held scissors. spring loading pushes one blade against the other blade. the blades are not completely straight, but are intentionally curved with a slight bow, sometimes with one blade bowed more than the other blade. as the scissors close, the structure is forcibly uncurved, which is how zero-clearance is conventionally achieved by spring loading in scissoring technology. initially, when the scissors are new, at contact there are two sharp edges, which is what is wanted for cutting action. however, eventually the sharp edges get worn off, blunted, and ground away. eventually at the traveling point of contact, blunting and voids in the edges occur, and clearance rather than zero-clearance occurs. certain conventional rotary shears have been attempted, to provide conventional shredders. a disk of tooled steel is notched. when that notched disk wipes past another part, cutting happens. however, if there is any clearance, a to-be-cut material does not get cut, but rather, goes between the cutting edges. such an apparatus gets dull because the action of parts rubbing against each other wears away the material of each. when the parts are dull, the assembly must be taken apart and the head replaced. zero-tolerance between parts can be kept by using spring-loading but such an arrangement is not actually cutting but rather is bludgeoning and takes more power than cutting. to get a cross-cut operation, complex helical shapes are needed, and certain shapes have been used conventionally. helically-fluted is the best of such conventional technology. non-helically fluted shapes do not provide the cross-cut, but only the strip-cut. strip-cutting cannot reduce the output to a size as small as desired, because the there is a limit to how thin the cutters can be made, which in turn limits how thin the resulting strips can be. cross- cutting is needed to get smaller output. a multiple-head (three-head) conventional cross-cutting destruction device is in use for high-security paper shredding. however, that device has these limitations (among others): 1) multiple heads are needed to sequentially re-shred the material. this requires a costly and complex machine. 2) even with multiple heads, the shredding cutter elements must be tightly spaced and thin, to get small-sized output. the cutting elements must therefore be somewhat delicate, which leads to shorter overall cutter life, greatly reduced reliability, and greatly increased susceptibility to damage from the introduction of staples, paper clips, etc. into the shredding process along with the paper. this is a problem for all high-security shredders, and the finer the output, the greater the problem. 3) even with multiple heads, there is a possibility of oversized particles getting past all of the heads. the conventional thinking has been that, as a practical matter, the output can be gotten only so small, from a length x width perspective, because of design and manufacturing limitations. namely, the conventional three-head device used two fluted rotating, meshing cylindrical parts with scissoring action, with a precision fit established between scissoring parts. strips with length and width dimensions are the output of the operation of the two fluted rotating, meshing cylindrical parts. the strip is then permitted to drop down, into a second set of the same arrangement of two fluted rotating, meshing cylindrical parts with scissoring action. such conventional scissoring action, multi-head machines suffer from inherent limitations both through machining tolerances and through the impossibility, at a certain point even if a smaller parts can be made, of providing support for the reduced-size parts, and providing force to shred the paper without bending or breaking the delicate shredder parts. adding to the concerns and problems discussed above for paper and paper-like products, there is further considered the problems, perhaps even more technically complex, of destroying information stored on or in other media besides paper. for example, there is a need to be able to completely, reliably and easily destroy other kinds of information-bearing media, such as photographs, photo negatives, compact disks, credit cards, data cards, so- called "smart" cards (containing electronic data storage circuits as well as magnetic and optical data), plastic film, cassette tapes, magnetic tape, etc. summary of the invention the present invention is directed to overcoming one or more of the problems as set forth above. the present inventor has found that zero-clearance cutting is provided in an arrangement in which a material-to-be-cut is disposed between a relatively hard cutter material and a relatively soft sacrifice material. the present invention exploits use of a relatively soft sacrifice material in conjunction with a cutter or cutting system. in another preferred embodiment, the invention provides a method of reducing a to- be-destroyed material to very small particles, comprising: subjecting the to-be-destroyed material to zero-clearance cutting including a sacrifice system. in another preferred embodiment, the invention provides zero-clearance cutting, by a cutting area including at least one cutting edge and at least one sacrifice material. advantageously, the zero-clearance cutting may (but is not required to) be on a commercial- scale, i.e., may include cutting repetitions on the order of thousands, tens of thousands, hundreds of thousands, even millions, without dulling of the cutting edge. a particularly preferred example of a commercial-scale zero-clearance cutting system comprises: a cutting area including at least one cutting edge (wherein the at least one cutting edge is suitable for cutting a material-to-be-cut) and at least one sacrifice material (wherein the at least one sacrifice material is relatively softer than the at least one cutting edge), with the at least one cutting edge and the at least one sacrifice material arranged to receive therebetween a material-to-be-cut. any one or more of the following may be adjusted: a material of a cutting edge, a size of a cutting edge or edges, a pattern of a plurality of cutting edges, a manner of movement of the cutting edge or edges, a shape of the sacrificial material, a disposition and/or movement of the sacrificial material, and/or a feed of the material-to-be-cut. by such adjustments, to-be-destroyed materials may be cut into smaller pieces in many different piece patterns, with a most preferred example being cutting to-be-destroyed materials (such as paper, key-tape, photographs, credit cards, data cards, atm cards, smart cards, data chips, data-chip containing materials, compact disks, floppy disks, cassette tapes, verichips, flash drives, biometric chips, etc.) into small pieces passing security standards and from which data cannot be recovered. zero-clearance cutting according to the invention is particularly useful and advantageous where some relatively thin layer to be destroyed, whether the relatively thin layer is alone or in conjunction with another layer (such as a thick layer, e.g., a laminate). in a particularly preferred embodiment, the invention generally provides rotating cutter systems in which the cutter includes many small cutting edges that respectively take tiny "nibbles" out of the to-be-destroyed planar material, with the axis about which the cutter rotates being parallel to the to-be-destroyed material. the cutter preferably rotates about a fixed axis of rotation, which axis preferably is itself generally non-moving. the cutter is generally configured so that a to-be-destroyed material, once first-cut by the rotating cutter, may be further cut and multiply re-cut by the raised cutting edges of the rotating cutter (preferred examples of which cutter are a cutter with raised cutting edge patterning in a crosscut pattern or other strategic pattern). the initial cutting interaction generally occurs with the to-be-destroyed material tightly sheared between the rotating cutter edges and at least one solid sacrificial plate or blade or rod that is of a relatively-softer material than the cutter. the to-be-destroyed material is controllably fed into this tight shearing sandwich of sacrifice material/to-be-destroyed-material/rotating cutter. the invention also provides cutting action comprising rotary scissoring, where one "blade" of the scissors rotates, and the other "blade" is a stationary sacrifice material. a to- be-destroyed material is fed (preferably controllably fed) between the respective rotating blade and sacrifice blade, preferably with continued rotary scissoring until the to-be- destroyed material has been destroyed (such as wherein the to-be-destroyed material has been converted into a security-level fine material). another embodiment provided by the present invention is that of a rotary scissors device comprising a first scissors blade and a second scissors blade, wherein the first scissors blade rotates and the second scissors blade is stationary, the stationary blade comprising a stationary sacrifice material that is relatively softer than the rotating blade. such a rotary scissors device preferably includes a feeder receiving a to-be-destroyed material and providing the to-be-destroyed material between the respective rotating blade and sacrifice blade. preferably such a feed is controllably metered. preferably such a feeder accommodates paper. preferably the rotary scissors device in continued operation provides zero-clearance yet does not suffer significant blade blunting or dulling that affects cutting due to the zero-clearance. in a most preferred embodiment, the inventive rotary scissors device's output is a security-level fine material. where the invention provides rotary scissoring or a rotary scissors device, preferably the rotating blade preferably is serrated. the two respective scissors blades are in zero- clearance or essentially-zero-clearance shearing contact with each other. in yet another embodiment, the invention provides a method of destroying a to-be- destroyed planar material, comprising: passing the to-be-destroyed planar material through a rotating cutter system, wherein the cutter includes a plurality of cutting edges that respectively take tiny nibbles out of the to-be-destroyed planar material, with the axis about which the cutter rotates being parallel to the to-be-destroyed planar material. in such a method, preferably the cutter rotates about a fixed axis of rotation; and/or the cutter rotation axis is itself generally non-moving. in most preferred embodiments, preferably the method includes initial cutting of the to-be-destroyed material by at least one cutting edge of the rotating cutter, followed by further cutting by at least one other cutting edge of the rotating cutter; and/or comprises multiple further cutting; and/or the cutting edges of the rotating cutter are arranged in a strategic pattern. the present invention in another embodiment provides a cutting system comprising shearing a to-be-destroyed planar material between (1) cutter edges provided on a rotating cutter and (2) at least one solid sacrificial material that is of a relatively-softer material than the cutter edges. such a cutting system preferably includes a tight shearing sandwich of sacrifice material/to-be-destroyed-material/rotating cutter (and, in a further preferred embodiment, the to-be-destroyed-material is controllably fed into the tight shearing sandwich). the tight shearing sandwich is zero-clearance or essentially zero-clearance. preferably, the cutter is cowled (most preferably, further including a secondary cowling such as, e.g., most preferably, a first secondary shredder at one end of the cutter and a second secondary shredder at the other end of the cutter). preferably, the cutting system includes auger action for transporting initially-cut to-be-destroyed material. in one aspect of the present invention, a cutting mechanism for disintegrating a material is provided. the cutting mechanism includes a mechanism for feeding the material at a predetermined, positively-controlled rate and at least one cutter (such as a rotary cutter) positioned downstream from the feeding mechanism. in the particularly preferred example of a rotary cutter, the edge of at least one sacrificial plate, preferably of softer material than the cutter, just barely contacts a portion of the rotary cutter during a phase of rotation of the rotary cutter. the contacting zone is a zero clearance portion between a portion of the rotary cutter and the sacrificial plate. the material is metered to the zero clearance zone by the metering mechanism for disintegrating the material into a fiber or powder form. a "sacrificial plate" and "sacrificial blade" are mentioned as shapes of sacrificial material according to the invention. other shapes for sacrificial material in the invention may be used, such as, e.g., a round bar. in another aspect of the present invention, the cutting mechanism includes a guiding mechanism and a metering mechanism downstream of, and in line with the guiding mechanism. a cutting mechanism having a zero clearance zone is also provided. the cutting mechanism includes a cutting blade array disposed concentrically about a shaft and at least one sacrificial plate or round bar having an arc zone conforming to a shape of the cutting blade. the zero clearance zone is disposed between at least a cutting portion of the cutting blade and the sacrificial plate or round bar. in still further embodiments, a cutting mechanism includes a positively controlled feeding mechanism and a cutting mechanism having a zero clearance portion formed therebetween. the cutting mechanism includes a cutting blade disposed concentrically about a shaft and at least one rotatable sacrificial rod having an initial cutout portion. the zero clearance portion is disposed between at least a cutting portion of the cutting blade and the rotatable sacrificial rod. in further embodiments, a method of destroying polyester material, paper or other material is provided. in these methods, for example, the polyester material is fed at a predetermined positively controlled rate towards a zero clearance portion formed between a cutter and at least one sacrificial blade or round bar. the polyester material is grabbed by a tooth of the cutter and pulled into the zero clearance portion with the tooth of the cutter. the polyester material is then sheared and/or crushed between the cutter and the sacrificial blade or round bar at the zero clearance portion.. this same method can be used for material or other product, and the feeding rate may vary. one preferred embodiment of the invention provides a zero clearance cutting apparatus, comprising: at least one cutter; and positively-controlled material feed mechanism for controlling a feeding rate of material to be destroyed; and at least one sacrificial blade or round bar abutting a portion of the at least one cutter during a rotation of the at least one cutter, the sacrificial blade or round bar being relatively softer than the cutter. another preferred embodiment of the invention provides a cutting mechanism for cutting a material, comprising: a metering mechanism for feeding in the material at a predetermined, positively controlled rate; a rotary cutter positioned downstream from the metering mechanism; and at least one sacrificial blade or round bar which contacts a portion of the rotary cutter during a phase of rotation of the rotary cutter, the contacting portion being a zero clearance portion between a portion of the rotary cutter and the sacrificial blade or round bar, wherein the material is metered to the zero clearance portion by the metering mechanism for disintegrating the material into a fiber or powder form. the invention in a further preferred embodiment provides a cutting mechanism, comprising: a guiding mechanism; a metering mechanism downstream and in line with the guiding mechanism; and a cutting mechanism having a zero clearance portion, the cutting mechanism including: a cutting blade disposed concentrically about a shaft; and at least one sacrificial plate or round bar having an arc portion conforming to a shape of the cutting blade, the zero clearance portion being disposed between at least a cutting portion of the cutting blade and the sacrificial plate or round bar. another preferred embodiment of the invention provides a cutting mechanism, comprising: a positively controlled feeding mechanism; and a cutting mechanism having a zero clearance portion, the cutting mechanism including: a cutting blade disposed concentrically about a shaft; and at least one rotatable sacrificial rod having an initial cutout portion, the zero clearance portion being disposed between at least a cutting portion of the cutting blade and the rotatable sacrificial rod. additionally, the invention in a preferred embodiment provides a positively controlled feeding mechanism, comprising: a first side plate having a vertical slot and an opening; a second opposing side plate having a vertical slot and an opening; a driven capstan mechanism positioned between the first side plate and the second opposing side plate; and a roller mechanism having a roller shaft, the roller shaft being captured within the vertical slot of the first side plate and the vertical slot of the second opposing side plate, the roller shaft further being positionable relative to the opening of the first side plate and the opening of the second side plate for removal thereof. in another preferred embodiment, the invention provides a method of destroying polyester material, comprising the steps of: feeding the polyester material at a predetermined positively controlled rate towards a zero clearance portion formed between a cutter and at least one sacrificial blade or round bar; grabbing the polyester material with a tooth of the cutter; pulling the polyester material into the zero clearance portion with the tooth of the cutter; and disposing the polyester material between the cutter and the sacrificial blade or round bar at the zero clearance portion. an additional preferred embodiment of the invention provides a method of destroying paper, comprising the steps of: feeding the paper at a predetermined positively controlled rate towards a zero clearance portion formed between a cutter and at least one sacrificial blade or round bar; grabbing the paper with a tooth of the cutter; pulling the paper into the zero clearance portion with the tooth of the cutter; and disposing the paper between the cutter and the sacrificial blade or round bar at the zero clearance portion. the invention also provides, in a preferred embodiment, a method of destroying a material, comprising the steps of: feeding the material at a predetermined positively controlled rate towards a zero clearance portion formed between a cutter and at least one sacrificial blade or round bar; grabbing the material with a tooth of the cutter; pulling the material into the zero clearance portion with the tooth of the cutter; and disposing the material between the cutter and the sacrificial blade or round bar at the zero clearance portion. additionally, in another preferred embodiment, the invention provides a method of protecting a cutter longevity and/or achieving zero-clearance cutting, comprising: sacrificing at least one solid blade bed or round bar against a cutter, wherein the blade bed is (a) relatively softer than the cutter and (b) relatively harder than an object or a material being destroyed by the cutter. in the inventive apparatuses, mechanisms, methods, systems and products, the following are mentioned as preferred perfecting details and not as limitations on practicing the invention. with regard to the at least one cutter, a rotary cutter is mentioned as an example that may be used. the cutter may destroy a to-be-destroyed object by such preferable destruction as cutting, grinding, slicing, crushing, chopping and/or shredding. the positively-controlled material feed mechanism may control particle size of the material being destroyed by controlling both (a) the feed rate of the material entering between the at least one sacrificial blade or round bar and the at least one cutter and (b) the rotational speed of the at least one cutter. the output may be one of an information-unrecoverable product or a shredded product, and a disintegrated product. the sacrificial blade may be one of a plate and a rotatable rod. the rotary cutter may be made from a first material and the sacrificial blade or round bar may be made from a second material which is softer than the first material (such as the first material being one of steel and carbide and the second material being aluminum). the sacrificial blade or round bar may include an edge (such as an arc shaped edge) which conforms to a shape of the path of the rotary cutter at the contacting portion. a mechanism may be included for incrementally moving the sacrificial blade or round bar into contact with the rotary cutter as the sacrificial blade or round bar wears down. the incrementally moving mechanism may be a rotating jackscrew mechanism coupled to the sacrificial blade or round bar. the jackscrew may include an outward extending plate or screw-tapped-plate which is adapted to lift the sacrificial blade or round bar into contact with the rotary cutter. there may be included a motor for driving the rotary cutter, the metering mechanism and the rotation of the jackscrew; and/or a gear reduction system between the motor and the jackscrew. the metering mechanism may include a pressure roller and a friction feed capstan. also, with regard to the two rollers, one or both may be driven. when a rotary cutter is used, the arrangement may be that at least one tooth of the rotary cutter grabs the material prior to the material being metered into the zero clearance portion. it may be provided for the combination of the rotary cutter and the sacrificial blade or round bar to cut the material into the fiber or powder form. there may be included a mechanism adapted to ensure the at least one sacrificial plate or round bar is in contact with the cutting blade during a rotation of the cutting blade. there may be included a pressure plate contacting the sacrificial plate or round bar, the pressure plate adapted to at least maintain a position of the sacrificial plate or round bar with respect to the cutting blade and substantially eliminating vibrations caused during a cutting procedure. there may be included a mechanism coupled to the pressure plate for providing pressure to the pressure plate. the pressure plate may be of such material density and size as to provide inertial damping of vibrations, in addition to simple spring-driven pressure. in the disposing step, to-be-destroyed material may be shred into an information- unrecoverable form. the feeding may be incremental. an example of a feeding rate is 13 feet per minute in a practical embodiment. in feeding the solid blade bed or round bar being sacrificed, examples of feeding may be feeding continuously or intermittently to the cutter (such as sacrificing by continuous feeding of the solid blade bed at a rate proportional to a rate of cutting and/or feeding the to- be-destroyed material or object; sacrificing by feed of the solid blade bed being sacrificed at a rate that is intermittent, adjustable, or in fixed increments, etc.). in another preferred embodiment, the invention provides a residue exit method for a destruction machine, comprising a step, after at least one destruction step has been performed or attempted, of: splitting direction of exiting residue into at least a first screenless exit path and a second screenless exit path and compelling residue to move via the screenless exit paths. a further preferred inventive embodiment provides a machine for destroying a material, comprising: a destruction zone wherein material having passed through and/or by the zone is residue; and at least two screenless exit paths, with the residue mechanically compelled to exit via the screenless exit paths. a preferred example of such an inventive machine is a machine comprising: a rotating primary cutter, at least two secondary shredders disposed on the same axis about which the primary cutter rotates, wherein the secondary shredders (which may be, but need not be, identical as a group) differ from the primary cutter. in another preferred embodiment, the invention provides a method of destroying material, comprising the steps of: disposing the material in a destruction zone (such as, e.g., a destruction zone including a rotary cutter and two secondary shredders, with the cutter and the secondary shredders rotating about a fixed axis of rotation); followed by compelling material that has escaped being reduced to powder size to travel via one of at least two screenless exit paths, during which secondary cutting is performed on the bigger-than-powder size material. in such inventive residue exit methods, destruction methods, and machines, some perfecting details, which are preferred but not required, are as follows. a secondary destruction step may be performed on residue moving along a screenless exit path towards a screenless exit. residue moving along a screenless exit path may be forced to travel a non- straight path gauntlet (such as, e.g., a chopping gauntlet). there may be included a rotating secondary shredder system useable with a rotating primary cutter, comprising at least two secondary shredders, wherein the secondary shredders (which may be, but need not be, identical as a group) and the primary cutter are non-identical. the at least two secondary shredders preferably are exactly two rotating secondary shredders. when a primary cutter and two secondary shredders are used, preferably the primary cutter may be between the two respective secondary shredders on each end of a common axis. when using rotating secondary shredders and a rotating primary cutter, including a single shaft common to the rotating secondary shredders and the rotating primary cutter is preferred. it is preferred to include for each secondary shredder at least one residue vacuum port. when a first secondary shredder and a second secondary shredder are used, preferably each of the secondary shredders respectively acts on residue. when at least one secondary shredder comprising a rotating element is used, preferably there is included an optional step of detecting conditions conducive to clogging one or more stator holes in a stator enclosing the rotating element of the secondary shredder, such as a detecting step comprising one or a combination of, e.g., temperature sensing (such as, e.g., setting a temperature sensor to detect a temperature range relevant to each material being processed into residue), optical sensing, differential air pressure sensing, air flow sensing, mass flow sensing, etc. when such a detecting step is performed, preferably there also is included, upon sensing conditions (such as, e.g., temperature conditions, etc.) conducive to clogging, an optional step of stopping or slowing material infeed for a time permitting conditions (such as, e.g., temperature) to return to safe limits. in a preferred example, while material infeed is stopped or slowed, air flow is continued through the stator holes. non-limiting examples of a material that may be cut into high-security fine pieces by such inventive residue exit methods, destruction methods and inventive destruction machines are, e.g., one or more (including a mixture) of paper; polyester material; a compact disk; a magnetic tape; a laminated data-bearing card; a credit card; a bank card; a dvd; a smart card; a photograph; a verichip, a flash drive, a biometric chip, etc. by the inventive methods, machines and systems, such material (and other materials) may be converted into a security- level fine material. a load fed into the inventive machines optionally, and preferably, may be a non-homogeneous load, and preferably a non-homogeneous load fed may be fed into an inventive machine or be processed by an inventive method and destroyed into only high- security fine pieces. in another preferred embodiment, the invention provides a self-healing mechanical system, comprising: a first part which is solid; a second part which is sacrificial, wherein the sacrificial part is relatively softer than the first part and also relatively softer than a foreign object which undesirably may enter the mechanical system; wherein damage by the foreign object in the system is limited to damage to a damageable surface of the second part; such as, e.g., a self-healing mechanical system wherein the sacrificial part mechanically self-heals; a self-healing system wherein when the foreign object enters and travels through the mechanical system, the sacrificial part is damaged on the damageable surface, and the first part is not damaged or only minimally damaged; a self-healing mechanical system wherein at least one of the first part and the sacrificial part is a moving part; a self-healing mechanical system wherein in standard operation the first part and the sacrificial part contact each other in a zero-clearance design; a self-healing mechanical system wherein in standard operation a certain non-zero distance is maintained between the first part and the sacrificial part by design; a self-healing mechanical system wherein the sacrificial part self-heals mechanically; a self-healing mechanical system wherein the first part is a cutter; a self-healing mechanical system not including ice; a self-healing mechanical system wherein the sacrificial part is circular or cylindrical shaped; a self-healing mechanical system wherein the sacrificial part is a blade shape automatically advanced towards the first part; etc. brief description of the drawings the foregoing and other objects, aspects and advantages will be better understood from the following detailed description of a preferred embodiment of the invention with reference to the drawings, in which: figure 1 shows a cross sectional view of a cutting system of the present invention, wherein a sacrificial blade is featured; figure 2 shows an embodiment of a rotary cutter according to the present invention; figure 3 shows another embodiment of a cutting system of the present invention, wherein a round bar of sacrificial material is featured; figures 4a-4d show a pressure system and quick change mechanism of the pressure roller of figures 1 and 3; figures 5a-5d show a to-be-destroyed material in various positions within a cutting system of figure 1, with a sacrifice blade being used in conjunction with a rotary cutter, with the view enlarged to show the interaction between the material to be destroyed m, the rotary cutter, and the sacrifice blade. figures 6a-6d show a to-be-destroyed material in various positions within a cutting system of figure 3, with a round sacrificial material being used in conjunction with a rotary cutter, with the view enlarged to show the interaction between the material to be destroyed m, the rotary cutter, and the sacrifice material. figures 7-8 show exemplary reciprocal cutter systems according to the invention, with figure 7 showing an exemplary inventive embodiment in which a sacrificial blade is diagonally-fed towards a shearing blade and figure 8 showing an exemplary inventive embodiment in which a to-be-cut material is diagonally-fed and a round sacrifice material is used with a shearing blade. figure 9 shows an exemplary inventive embodiment in which more than one sacrifice material is used. figures 10a- 1oc show conceptual diagrams according to the present invention, in which a to-be-cut material m is cut. figure 11 shows, close-up, an embodiment of a cutting mechanism that is especially preferred for destroying standard 8 vi inch wide paper, with the close-up view particularly showing that the leading edges of the serrations are laterally offset slightly. figures 12a-12d are views of an exemplary paper destruction device according to the invention. figure 12a is a side view (with stator 600 (see figure 12b) removed) of an exemplary paper destruction device. figure 12b shows the removed stator corresponding to figure 12a. figure 12c is a paper-feed view. figure 12d is a top view, showing an exemplary arrangement in a paper-destruction system, of an inventive primary cutter and secondary shredder. figure 13 is a flow-chart according to an inventive embodiment in which size of cut pieces is taken into account. figure 14a is a block diagram of an inventive residue exit method when destroying a material. figure 14b is a perspective view of an inventive rotating cutting system including two secondary shredders (i.e., a double secondary shredder system). figure 15 is a cross-sectional view of an exemplary self-healing mechanical cutting system. figure 15a is an enlarged depiction of the region around o (to which the downward arrow points) in figure 15. figures 15a-15h are side cross-sectional views of a foreign object traveling through an exemplary self-healing mechanical cutting system. figure 16 is a cross-sectional geometric representation of a section of a mechanical system including an inventive self-healing region. detailed description of preferred embodiments of the invention in an important aspect, the invention provides zero-clearance cutting, by a cutting area including at least one cutting edge and at least one sacrifice material. it will be appreciated that at least one cutting edge is selected with regard to the material or materials desired to be cut, i.e., the cutting edge should be suitable for cutting the material or materials desired to be cut. the sacrifice material is selected with regard to the material of the cutting edge, namely, the sacrifice material must be relatively softer than the at least one cutting edge. a suitable sacrifice material should be firm enough to provide support so that a to-be-destroyed material is properly sheared and/or cut, and yet preferably should be no harder than necessary. excessive hardness of a sacrifice material is avoided so as not to wear the cutting edge that contacts the sacrifice material more than necessary. generally, a pair of a cutter material and a respective sacrifice material is selected based on the characteristics of the to-be-destroyed material. preferably, the sacrifice material is selected so that the wear component due to the sacrifice material is trivial compared to the wear component due to the to-be-destroyed material. paper is a common material sought to be destroyed. paper can be generally very abrasive, and tends to wear out a cutting blade applied to paper. typically, a hardened steel (coated or uncoated) cutter is used for cutting paper. preferred examples of a sacrifice material to use with a typical machined, hardened steel (coated or uncoated) cutter include, for example, common aluminum (with most preferred examples being alloys 6063, 3003, 5052, etc.), etc. when a harder cutter material is used (such as, e.g., diamond or carbide), the desirable sacrificial material is still, of course, relatively softer than the cutter, but the sacrifice material will be particularly selected based both on the cutter material and on the thing being cut. by so pairing a relatively-softer sacrifice material with a hard cutting edge, repetitions of zero-clearance cutting advantageously may be achieved on a commercial scale, i.e., may include cutting repetitions on the order of thousands, tens of thousands, hundreds of thousands, even millions, without significant dulling of the cutting edge due to the sacrifice material. of course, optionally, non-commercial or fewer-repetition zero-clearance cutting operations also may be provided by the invention. reference is made to figures 10a- 1oc, which are a conceptual depiction, in which the arrows for c h and s s conceptually mean the general use of a relatively hard cutting system and a relatively soft sacrifice material. referring to figure 1oa, it will be appreciated that at an initial time before a to-be-destroyed material m enters a cutting system used with a sacrificial material, there exists a gap between into which the to-be-destroyed material m can be inserted. as the material m travels through the gap between the cutting system c h and the sacrificial material s s the cutting system c h and/or the sacrificial material s s are operated so that the gap is only open for a relatively short time and that only a small part m' of material m passes before zero-clearance is forcibly established. zero-clearance having been forcibly established so that original material m is separated into still-advancing piece m' and piece m" which has passed through the cutting area, piece m" then travels separately from piece m'. the process of figures loa-loc is repeated for m'. it will be appreciated that c h and s s are conceptual and do not necessarily represent a single cutter or cutting edge or a single sacrificial material. for example, advancing material m may encounter a first cutting edge, then, reduced to m', may encounter a second cutting edge, etc. it further will be appreciated that m" in figure 1oc may be subjected to further processing (such as further cutting). a particularly preferred example of a commercial-scale zero-clearance cutting system comprises: a cutting area including at least one cutting edge and at least one sacrifice material, with the at least one cutting edge and the at least one sacrifice material arranged to receive therebetween a material-to-be-cut. in mechanically arranging any cutting edges and sacrifice material used, there is taken into account the to-be-cut material, including the width, length, thickness, and overall composition of the to-be-cut material. the cutting edge(s) and sacrifice material are arranged so that the to-be-cut material is disposed in an opening between a cutting edge and the sacrifice material, and that cutting may occur with the cutting edge extending entirely through the to-be-cut material to directly contact the sacrifice material, resulting in a piece of the to-be-cut material separating from the to-be-cut material. any one or more of the following may be adjusted: a material of a cutting edge, a size of a cutting edge or edges, a pattern of a plurality of cutting edges, a manner of movement of the cutting edge or edges, a shape of the sacrificial material, a disposition and/or movement of the sacrificial material, and/or a feed of the material-to-be-cut. by such adjustments, to-be-destroyed materials may be cut into smaller pieces in many different piece patterns, with a most preferred example being cutting to-be-destroyed materials (such as paper, key-tape, photographs, credit cards, data cards, compact disks, floppy disks, cassette tapes, etc.) into small pieces passing security standards and from which data cannot be recovered. the zero-clearance cutting of the invention may be used in different ways, with a preferred example of use of zero-clearance cutting being cutting to achieve an output no bigger than a certain predetermined target size (such as an output meeting industry security standards, an output from which no data is recoverable, an output that is satisfyingly small from a naked eye visual perspective, etc.). a general embodiment of such a use of zero- clearance cutting to achieve an output no bigger than a predetermined target size may be appreciated with regard to figure 13, showing a zero-clearance cutting system with size- sensitivity as to the cut pieces. a to-be-destroyed material m is disposed (900) in a cutting area including a sacrifice material, whereby piece(s) are created (901). if the size of a piece is less than a predetermined size, the piece is permitted (903) to exit the cutting system. such exit of appropriately-small size pieces can be mechanically provided by providing suitable cowling around the cutting area and adjusting size of any egress hole(s) for the sufficiently- small size pieces. it will be appreciated that where the particles are so small as to be dust-like (as may be achieved in a particularly preferred embodiment of the invention), preferably a vacuum system is used to collect and remove the small particles. still referring to figure 13, if the size of a piece is greater than a predetermined size, the piece is subjected (902) to further size-reduction, and more piece(s) are created (901). it will be appreciated that the further size-reduction may be cutting including a sacrifice material (in the same or different cutting area including a sacrifice material), or may be cutting not involving a sacrifice material, or may be non-cutting size-reduction. in a preferred example, there is used a rotary cutter patterned with strategically arranged cutting edges, and a to-be-cut material is first disposed in a cutting area including a sacrifice material working with a first cutting edge, and then a resulting piece or pieces are next disposed in a cutting area including the sacrifice material working with a second cutting edge. in another preferred example, zero-clearance cutting using a sacrificial material is used as an initial cutting system, and too-large particles are then further subjected to a no-sacrificial material secondary shredder system (such as, e.g., most preferably, a double secondary shredder system (such as, e.g., the double secondary shredder system as in example 7 below and fig. 14b)). a particularly preferred use of the present invention is to cut a starting material into high-security fine pieces. examples of a starting material with which the present invention is useable and which may be made into high-security fine pieces include: paper (such as a single sheet of paper, a stack of paper, etc.), a compact disk, key tape, magnetic tape (such as magnetic tape pulled from a cassette or cartridge, magnetic tape still within a cassette, etc.), a laminated data-bearing card, a credit card, a bank card, stored computer-readable data (such as in a diskette, hard disk, floppy disk, etc.). the invention in one embodiment provides cutting action comprising rotary scissoring, where one "blade" of the scissors rotates, and the other "blade" is a stationary sacrifice material (most preferably a sacrifice material that is relatively softer than the rotating blade that it contacts). the stationary sacrifice material may be formed in the shape of any shape (such as a bar, etc.) that does not interfere with the cutting action of the sacrifice blade with the rotating blade when a to-be-destroyed material is fed between the respective rotating blade and sacrifice blade. while in this embodiment of the invention, the general arrangement of blades has some characteristics of a reel-type lawn mower, a reel-type lawn mower design would not be suitable for precision cutting at security-level standards, for at least several reasons, including the impossibility of getting the same-hardness, non-serrated blades sufficiently close together for reliably cutting a material-to-be-destroyed. the present invention exploits the advantages of rotary scissoring and rotary cutting, and solves the problems (such as rapid dulling of blades) associated with bringing two same-hardness blades in contact with each other. the present inventor has recognized that the contacting blades need not be of the same hardness, and preferably are not of the same hardness, and further has recognized advantages of using different hardness blades in cutting (preferably in rotary cutting), e.g., the ability to provide zero-clearance cutting action or essentially-zero-clearance cutting action. an embodiment of the present invention is directed to a cutting apparatus used to shred or cut paper, tape or other materials or products into a shredded, cut or information- unrecoverable, disintegrated form such as a fine fiber or powder form. in a preferred embodiment, the fine fiber or powder form makes data or image recovery impossible and is thus very advantageous for security and other confidentiality reasons. the present invention is capable of providing such shredded or fine fiber or powder form through a single cutting process which thus minimizes component parts and maintenance issues while increasing efficiency and productivity. in order to provide the advantages of the present invention, the cutting apparatus incorporates a zero clearance cutting surface between a cutting mechanism and at least one sacrificial blade or plate or bar. the material or product is supplied to the zero clearance portion of the apparatus of the present invention at a predetermined feed or metering rate via a manual feeding or, alternatively, a feeding or metering mechanism such as, for example, motor and gear-driven rollers and the like. this invention in a particularly preferred embodiment makes use of distinct and deliberately determined feeds, one for the material being cut, and the other for the gradual advancement of the sacrificial material into the cutting zone. either may be automated or manually controlled. the style of the cutter (e.g., the pattern, the teeth) is directed by the application. for example, a helically-fluted cutter with "chip-breaker" serrations on the flutes can be implemented to: (1) create small chips of residue, and (2) capture and direct the flow of the residue for secondary processing, when used in conjunction with a suitable cowling to keep the residue particles captivated by the flutes. preferred examples of a cutter pattern are a rotary cross-cut or a herringbone file type of pattern. in another embodiment, the cutter can be like a helically-fluted milling cutter, preferably with "chip-breaker" serrations, off-set from each other, flute-to-flute, to produce tiny chips. for a tape-destruction machine, an exemplary cutter is one according to figures 1, 2, 3, 5a-6d, with a preferred tape-destruction cutter having 24 helical teeth, interrupted by reverse-helix pattern grooves, with each helical tooth spiraling across the entire cutter length, interrupted by the reverse-helix groove pattern (with the reverse-helix groove pattern being ground on later in the manufacturing process in a preferred method of making such a cutter). for an 8 1 a inch wide paper-destruction machine, a preferred cutter is one with flute-grooves (especially suited to carry the chips to a secondary shredder section). the invention particularly exploits the relative hardness relationship between a cutter (such as, e.g., rotary cutter 118 in figure 1) and a relatively less-hard sacrificial material (in a shape such as, e.g., sacrificial plate 120 or sacrificial rod 220). by way of example, the cutter may comprise tool steel, carbide or other high strength, relatively hard material. on the other hand, the sacrificial material may be aluminum or other relatively-soft material. for any given cutter, the sacrifice material composition may appropriately be varied or selected, and may be used in various shapes and compositions, and disposed in various movements and patterns relative to a cutting edge with which the sacrifice material is desired to contact. the cutting systems of the present invention may be used to destroy various materials, including paper, key-tape, paper-like material, etc., of various dimensions (such as various widths, such as key-tape-width, 8 1 a inch width, etc.); compact disks; photographs; floppy disks; film; credit cards, smart cards, magnetic tape; verichips; flash drives, biometric chips, etc. referring now to figure 1, an overview of an exemplary cutting system of the present invention is shown. (figure 1 is the most preferred system for destroying tape; another embodiment is set forth below with reference to other figures, as the most preferred system for destroying standard 8 1 a inch wide paper.) the cutting system in figure 1 is generally depicted as reference numeral 100 and includes a housing or frame 102. a material guide 104 is mounted to the frame 102 via any conventional mechanism. the material guide 104 includes a pivotally attached upper mechanism 106a and a lower stationary guide plate 106b. in this arrangement, to-be-destroyed material such as, for example, tape (e.g., mylar or other polyester film, etc.), paper or other product is guided to a cutting mechanism (described below) for disintegrating the to-be-destroyed material. the materials being fed may have information written thereon or punched thereinto or may simply be other types of product such as produce or the like. the arrangement of figure 1 can be used to destroy, otherwise difficult to destroy products, such as the mylar tape and other products. a motor 108, of any conventional type, is mounted on the frame 102. in a specific embodiment, the motor is a 300 watt motor which uses 100-130 vac or dc; however, any motor may be used including a motor capable of using an optional back-up battery system. still referring to figure 1, a feeding mechanism 110 is provided downstream and, in embodiments, in-line with the material guide 104. the feeding mechanism 110 includes a rubber pressure roller 112 and a friction feed capstan 114. the friction feed capstan 114 is preferably driven by the motor 108 which may provide, in embodiments, a predetermined, controlled feed rate of the product at approximately 13 ft/min (4 meters/min) or other rate. it should be readily recognized by those of ordinary skill in the art that the friction feed capstan 114 may provide a different metering rate by adjusting the revolutions per minute (rpm) of the firiction feed capstan 114, itself. for example, the friction feed capstan 114 may be adjusted to 120 rpm, or a lower or higher rpm depending on the particularly desired feed rate. the feeding mechanism may also provide a very firm retardation (hold back) of the product being fed into the cutting mechanism. by increasing the feed rate (assuming a constant cutter rotational speed), a perforation (rather than a cutting) may be performed on the product. in embodiments, a user may also manually feed the product to the cutting mechanism. the cutting mechanism, generally depicted as reference 116, includes a rotary cutter 118 and sacrificial material in the form of a sacrificial plate 120. in the embodiments of the present invention there is a zero clearance 119 zone between at least a portion of the rotary cutter 118 and the sacrificial plate 120; that is, a cutting surface of the rotary cutter 118 contacts the sacrificial plate 120 during the cutting process. the sacrificial plate 120 includes an edge 120a which substantially conforms to the arc shape of the rotary cutter 118. due to the arrangement between the sacrificial plate 120 and the rotary cutter 118, any product supplied to the rotary cutter 118 will be either shredded or disintegrated to an information- unrecoverable fine fiber or powder form by passing through the zero clearance 119 zone depending on the particular cutter type used with the present invention. there is a preferential geometric relation between the cutter, sacrifice contact zone, and point of material entry. specifically, 1. assume that the material approaches the cutting zone from the left of the cutter's center of rotation. 2. drawing a line downwards vertically originating from the center of cutter rotation, and then another line downwards (same origin) at an angle of approximately 45 degrees, biased towards the left of the origin, the point where this line intersects the periphery of the cutter is the preferential material entry point, and also the point of contact with the sacrifice material. this is the location identified as reference numeral 119 in figures 1, 3, 5a-5d, 6a- 6d. 3. this approximate position 119 is preferential because material entering at this point will tend to be captured by the advancing cutter points or blades, but not tend to be dragged through the cutter/sacrifice interface any more than necessary. it should be understood that if the material were to be fed above this point 119, there is less and less capturing tendency as the point of entry is raised. if the feed point is raised above the center of the cutter, the cutter will tend to push the material away, rather than draw it in. also, if the point of entry is lowered, there is greater and greater tendency of the cutter to capture and drag the material through the cutter/sacrifice interface, which places unnecessary stress on the feeding mechanism, whose purpose is to force the material feed at a predetermined rate (not more, and not less). in an extreme case, the cutter mechanism could drag the material through with such force as to stretch or break the material, rather than "nibble away" at it. it is the controlled, "nibbling away" of the material by the cutter which allows the machine to produce the superior shredding action intended. this being the case, positive control of material in-feed is essential, and achieved partly by an advantageous, appropriate geometry. it is preferred that the rotary cutter 118 be made from a material which is harder than the sacrificial plate 120. by way of example, the rotary cutter 118 may comprise tool steel, carbide or other high strength, relatively hard material. on the other hand, the sacrificial plate 120 may be made from aluminum or other softer material. in embodiments, the sacrificial plate 120 is made from material which allows approx. 30,000 feet of product to be fed through the rotary cutter 118 prior to a one-inch-length of sacrificial plate 120 completely being consumed. similarly, the rotary cutter 118 is made from material that allows 40,000 feet of paper product to be fed through the rotary cutter 118 prior to the rotary cutter 118 wearing down due to usage. polyester and other materials may cause much faster cutter wear. of course, the sacrificial plate 120 and the rotary cutter 118 may wear down or become duller at other rates depending on the particular materials used to make the sacrificial plate 120 and the rotary cutter 118 and the product being fed and the feed rate therethrough; however, it is preferred that the sacrificial plate 120 be designed to wear down much more slowly than the rotary cutter 118. it should further be recognized by those of ordinary skill in the art that the rotary cutter 118 is driven by the motor 108, and may be driven at a different rate than the feeding mechanism 110. by adjusting the feeding rates of the rotary cutter and the feeding mechanism 110, different types of cuts or shredding patterns may be accomplished. also, the rotary cutter 118 may be any type of rotary cutter such as, for example, a helical cutter, a milling cutter with helical pitches or flutes, razor blade cutting edges, a perforator, or the like. the rotary cutter 118 may additionally have various diameters such as 1 a inch diameter and should, preferably, be concentrically mounted to a shaft 118a. the motor 108 may additionally drive a jackscrew 122 or other lifting mechanism that is designed to incrementally move the sacrificial plate 120 into contact with the rotary cutter 118. this ensures that contact remains between the rotary cutter 118 and the sacrificial plate 120, even as the sacrificial plate 120 wears down due to usage. the jackscrew 122, in embodiments, includes an outward extending non-rotating jacknut plate 213 which contacts a portion of the sacrificial plate 120. the jacknut plate 213 lifts the sacrificial plate 120 as the jackscrew 122 rotates, via the motor 108 (through a suitable gear train). to incrementally move the sacrificial plate 120, via the jackscrew 122, a gear reduction system 124 is provided between the motor 108 and the jackscrew 122. by way of example, a gear reduction system may revolve the jackscrew one-half revolution/hour at a cutter speed of 15,000 rpm. figure 1 further shows a pressure plate 126 and a spring plunger 128. the pressure plate 126 is provided for two purposes: (i) ensuring that the sacrificial plate 120 is maintained in a proper position with relation to the rotary cutter 118 and (ii) minimizing or dampening the vibration created by interaction of the rotary cutter 118 and the sacrificial plate 120 during the cutting process. the latter feature is provided by the pressure provided by the spring plunger 128 and the simple inertia of the pressure plate 126 itself. the pressure plate 126 should preferably allow sliding movement of the sacrificial plate 120 towards the rotary cutter 118 during the operations thereof. it is noted that the pressure plate 126 should, however, not be in contact with the rotary cutter 118, although it is deliberately positioned so as to provide pressure and vibration dampening to the sacrifice plate in as close a proximity as practicable to the cutting zone 119. a vacuum source and collection bag (not shown) may also be used with the present invention. the vacuum source and collection bag will ensure that no fiber or fine powder contaminates the mechanisms and surrounding area. the vacuum source and collection bag also allow for easy clean up and the like. the rotary cutter 118 may include many different types of cutting patterns, with the type of cut or shredding of the product depending on the type of cutting blade. for example, a helical cutting blade will not cut an entire strip of the product, but will instead cut chunks or nibbles from the product. on the other hand, a straight cutting blade or array of razor blades, for example, may cut the product into strips. this provides additional flexibility to the system of the present invention. a plain rotary file is not considered a preferred design, because the output might be slivers rather than chips, and the slivers theoretically could be as long as the tape is wide (1") which is undesirable. figure 2 shows an embodiment of one rotary cutter 118 used with the present invention and especially suited to tape destruction. in figure 2, the rotary cutter 118 is shown to include a concentrically mounted shaft 118a and a rotary file style cutter with a helical pattern 118b. a cross-cut rotary file-type cutter pattern provides tiny chips laterally (across the tape width). (a) a cut zone follows a line drawn touching the cutter exterior surface and parallel to the cutter shaft; moving across the tape in the line of the cut zone, the individual teeth of the cutter are in varying phases of engagement along the line of the cut zone, which results in short widths of each chunk. (b) the length of the resulting chip (along the tape length) is determined by the relationship between the rotary speed of the cutter and the speed of the tape feed into the cutter. individual teeth engage the tape in the cutting zone in very rapid succession as the cutter rotates. because only a very small length of tape is fed into the zone for each passage of a tooth, the resulting chips are very short. the net result is that the chips are both short and narrow. by arranging combinations of rotary speed and rate of feed of to-be-destroyed material, the destruction device can be configured to produce dust-like particles. one successful embodiment of the cutter uses a cross-cut herring-bone pattern for the cutter surface (as shown) which could be made from a cutter such as manhattan supply co. part #60469665, a commercially available cross-cut rotary file. the cutter may also be made by using a common 1/2" diameter, 2-flute or 4-flute milling cutter, with its two ends ground down to a diameter suitable for the bearings selected. an ordinary tool-steel twist drill could have its flutes reground and be similarly modified for use as a cutter. in further embodiments, the cutter may also be made from an elongated spur gear of hardened material, with the external cylindrical-shaped surface ground so that the tooth ends are sharp, with its two ends ground down to a diameter suitable for the bearings selected. the sharpened teeth would then nibble off the to-be-shredded material trapped between the teeth and the sacrificial bed material. as to size, the cutter diameter may be about 1/2" but is not required to be a particular diameter, except that if the cutter is very long (e.g., 9 or more inches for full-size paper shredding), it must be of sufficient diameter to be stiff enough not to bend or whip around at its middle section during high speed rotation. it should also be rigid enough so that its cutting surfaces stay engaged to the sacrifice material throughout rotation. figure 3 shows another embodiment of the present invention. in this embodiment, the sacrificial material is in the form of a rotary-mounted sacrificial blade 220. that is, the sacrificial blade 220 is a rotating sacrifice rod which is gear driven at preferably 0.01 revolutions/hour. the rod is preferably 3/8" in diameter. of course, other revolution rates and diameters are also contemplated for use with the present invention. the cutting action and associated behaviors will be the same as that of the embodiment shown in figure 1. as seen in figure 3, a notch 220b is provided at the cutting surface for initial installation of the sacrifice blade 220. figures 4a-4d show a pressure system and quick change mechanism adapted for use with the feeding mechanism 110 and more particularly the rubber pressure roller 112 of the present invention. beginning with figure 4a, side plates 130 are positioned on opposing sides of the pressure roller 112. a roller shaft 112a, positioned concentrically within the pressure roller 112, extends between the two side plates 130 and more particularly is captured by vertical slots 132 which are machined in the side plates 130. the slots 132 include through-holes 132a. the roller portion of the pressure roller 112 will freely rotate on the roller shaft 112a via bearings or bushings affixed concentrically inside of roller 112. pressure screws 134 protrude down into the slots 132 which, in conjunction with spacers 136, establish a maximum distance that roller shaft 112a can be pushed downwards by the pressure screws 134 towards the capstan 114. in this manner, the rubber material of the pressure roller 112 provides a pinching of the material to be shredded against the capstan 114. that is, the force of the screw ends are able to travel a certain distance (established by screw length and spacer thickness) which then, in turn, forces a predetermined deflection of the rubber-like material of the roller 112. this provides positive control of material feed, as established by the capstan 114 rotation, and this also eliminates the need for a separate spring. the deflection determination is fixed by design (thickness of the spacers), but relieves the operator from making any routine pressure adjustment. this provides a significant operational advantage of simplicity. this mechanism also eliminates the need for a separate swing-arm and associated pivots or bearings and other hardware to mount and control and provide pressure to the roller. as further discussed with reference to figures 4b-4d, the present configuration of the side plates 130 further allows for a quick changing scheme of the roller 112. specifically, in figure 4b, it is shown that the pressure screws 134 are loosened and backed out part- way. the entire roller 112, together with the roller shaft 112a is then raised (figure 4c) to the height of the opening 132a. then, as seen in figure 4d, the roller shaft 112a can easily be removed through (e.g., slipped through) either one of the openings 132a of the side plates 132. the roller 112 is now free to be pulled out and replaced. reassembly takes place by reversing the disassembly order of figures 4b-4d. this mechanism provides for very fast and easy disassembly for jam clearance, inspection, roller shaft 112a, or roller 112 replacement. it provides an irreducibly minimal parts count, with no need for adjustment. the roller is simply replaced when it is worn out. figures 5a-5d show the various operational positions of the to-be-destroyed material being metered through the cutting system of the embodiment of figure 1. a machine according to figures 1 and 5a-5d has been particularly useful in the example where the to- be-destroyed material is paper/polyester tape, or polyester tape. however, other material such as paper or the like may equally be used with the present invention. figure 5a shows the to-be-destroyed material m prior to engagement between the rotary cutter 118 and the sacrificial plate 120. figure 5b shows the material m being engaged by a tooth 118c of the rotary cutter 118. in this manner, the material m begins to be pulled into the zero clearance zone 119 between the rotary cutter 118 and the sacrificial plate 120. in figure 5c, the material m is positioned within the zero clearance zone 119 between the tooth 118c of the rotary cutter 118 and the edge 120a of the sacrificial plate 120. in figure 5d, an extremely small portion x of the material m is sliced off between the rotary cutter 118 and the sacrificial plate 120. the steps of figures 5a through 5d are repeated until no further material m is available for metering to the cutting mechanism. the material may be destroyed at various rates such as, for example, four seconds for a segment of approximately 10 inches; however, other destruction rates may also be provided depending on the specific rotation of the cutting mechanism and the metering mechanism. akin to figures 5a-5d in which a sacrificial plate 120 is shown, figures 6a-6d show a product in various positions within the cutting system when the sacrifice material is a sacrifice rod 220. figure 6 a shows the material m prior to engagement between the rotary cutter 118 and the sacrifice rod 220. figure 6b shows the material m being engaged by a tooth 118c of the rotary cutter 118. in this manner, the material m begins to be pulled into the zero clearance zone 119 between the rotary cutter 118 and the sacrificial rod 220. in figure 6c, the material m is positioned within the zero clearance zone 119 between the tooth 118c of the rotary cutter 118 and the sacrificial rod 220. in figure 6d, an extremely small portion of the material m is sliced off between the rotary cutter 118 and the sacrificial rod 220. the steps of figures 6a-6d are repeated until no further material m is available for metering to the cutting mechanism. using the apparatus of figures 1 or figure 3 on to be destroyed paper, polyester or other types of products advantageously provides an output of high security material, most preferably a powder of finely grained material of a granular size. in this manner, the data previously recorded in or on the disintegrated product will be information-unrecoverable. as should also be understood by those of ordinary skill in the art, the present invention may also increase the number and variety of the materials which may now be written on, printed on, punched into or the like by allowing the total destruction of such materials, which was not otherwise practical. plastic recording tapes containing video, audio, and digital information have heretofore been very difficult to destroy, even with existing large, heavy, expensive, and noisy high-security disintegrators. it should now also be understood that the sacrificial plate or rod takes the place of, and performs the function of, a "blade bed" in a conventional cutting arrangement, such as might be found in a reel-type lawn mower, and many types of cutting machines. in the familiar example of the mower, the blade bed is usually of a hard material, and is manually adjusted so as to allow the closest practicable approach of the reel blades, without actually coming into contact with the reel blades. if the blade bed were to actually contact the reel blades, either the reel blade or the blade bed edge would be quickly worn away. if there is any eccentricity in the path of even one reel blade, wear on one part or the other would immediately result in some clearance between the reel blades and blade bed. now, if we imagine that the "grass" is thin polyester film, or some other very tough, thin material, one can readily see that the desired cutting would not take place, because the material might well be thinner than the blade-to-bed clearance. the material would simply "slip" between blade and bed. constant re-adjustment of the bed blade clearance would be required, and this would result in intolerable wear to blades and bed. by providing a suitable sacrificial blade bed with an automatic feed (at minimal rates) of the "sacrificial" bed material, the present invention overcomes this difficult problem. very thin, tough materials can now be cut or shredded easily with this arrangement. it will be appreciated that the invention thus provides cutting machines, products and methods in which true zero clearance cutting clearance is effectively achieved. cutting machines heretofore had some clearance between blades or between blades and beds. for example, scissors use spring tension to cause a wiping action between blades, but because scissors blades are both hard materials, a mechanical, automated scissors would dull or wear rather quickly. the present invention solves that problem with mechanical, automated scissors. in operation of a cutting system according to the invention, a particularly preferred rate for feeding sacrifice material is approximately 30 millionths of an inch of sacrifice material per foot length of destroyed material (in the case of a sacrificial blade material) and a feeding rate of approximately 30 micro-inches of sacrifice material per foot length of destroyed material, or about 400,000 inches of destroyed material per inch of sacrifice material (in the case of round sacrifice bar, see also example 2 below). additionally, the invention may be applied regarding a non-rotary cutter. a scheme according to the invention may be adapted for use with a scissors-like, reciprocating, or guillotine-like cutter. an ordinary office-type hand-operated paper cutter may be modified so that instead of the usual hardened-steel stationary bed blade, the bed blade is of a sacrifice material, with a mechanism to advance the sacrifice material in minute increments. above, a round bar has been mentioned, and a round bar is thought the easiest implementation. instead of a round bar, a flexible material incrementally fed from a roll may be used. it will be appreciated that the invention may be used for destruction of to-be- destroyed materials of various dimensions. when the to-be-destroyed material is key tape, or of key tape width, a preferred example of a destruction machine is that of example 1 below. when the to-be-destroyed material is paper of standard 8 vz inch width, a preferred example of a destruction machine is that of example 3 below, in which a 9 inch wide sacrificial plate is used. the sacrificial plate or blade size may be adjusted to the width of the to-be-destroyed product. for a relatively wide to-be-destroyed product, appropriate engineering considerations may be made to account for the relative width, such as jacking up the sacrifice plate at two points. a particularly preferred embodiment of the present invention is a destruction machine for to-be-destroyed 8 vz inch-wide paper. a particularly preferred embodiment of such a destruction machine for 8 vz inch wide paper may be appreciated with reference to figure 12a. for a destruction machine particularly suited for 8 vz inch wide paper, the cutter used should be relatively harder than the sacrifice material. particularly preferred is a cutter made from cobalt steel, coated with titanium nitrate (to enhance its hardness). the cutter for use in destroying 8 vz inch wide paper should be strategically patterned with raised cutting edges (with serrated cutting edges being preferred, and strategic patterning as in figures 11, 12c and 12d being most preferred). a basic principle according to the invention, namely, the use of a plurality of small edges that take tiny nibbles of the to-be- destroyed material, is used. preferably, a cutter with vertical serrations is used. most preferably, a small lateral or axial offset distance (such as 7/1000 inch (0.007 inch)) is provided for the vertical serrations, as shown as offset 800 on figure 11 . the preferred pattern resembles what in the machining trade is called "chip breakers." the preferred small- offset design is particularly helpful in cutting the last strip of paper or to-be-destroyed material, which, when the length-wise material reaches the end of its travel into the machine, has nothing controlling its travel path. also, preferably the entire cutter assembly is cowled (enclosed in a close-fitting cylindrical construction). referring to figure 11, a close-up view of a rotary cutter 318 with cutting edges 318a suitable for use in destroying 8 vz inch wide paper, the strategic patterning of a rotary cutter may be further appreciated. a tiny horizontal offset 800 between leading edges of serration teeth, the offset occurring between successive flutes, is shown. the tiny serration teeth successively bite off minute chunks width- wise due to the offset 800, as the cutter 318 rotates. the serration teeth and flutes successively bite off minute chunks length- wise due to the relationship between the rate of material feed and cutter 318 (fig. 12a) rotation speed (number of flutes passing per unit length of fed material). the sacrifice plate for use in destroying 8 vi inch wide paper is wider than 8 vz inches, preferably 9 inches or more wide to facilitate document loading. more generally, referring to all embodiments of the invention, it will be appreciated that the width of the sacrifice plate is adjusted to the width of the to-be-destroyed item. in the case of the 8 vz inch wide paper, requiring a sacrifice plate at least slightly wider than 8 vz inches, and that width being relatively wide for engineering considerations, the sacrifice plate preferably is supported at more than one point, such as at two points for the device of fig. 12a. by synchronously driving the jackscrews 322 in fig. 12a, the jacknuts 399 can advantageously advance the sacrifice plate 320 upwards in an even and level fashion, thus promoting uniform contact between the upward edge of the sacrifice plate 320 and the cutting edges. with reference to figures 11 and 12a, cutting of the to-be-destroyed paper occurs between the cutter edges 318a and the sacrifice plate 320. preferably, augering (screw conveyer) techniques are used and applied (and preferably used and applied repeatedly) to particles of cut to-be-destroyed material (such as cut paper). augering is a well-known material conveying technique and is particularly useful in this high-security destruction application. for example, most preferably, a 45 degree helical design is considered optimal for moving the cut particles laterally. referring to the cutter of figure 11 and the destruction machine of figures 12a-12d, a cut particle is urged in a lateral direction by the helical design. lateral movement of the particles and the promotion of re-cutting and multiple re- cutting are applied to accomplish ultimate cutting into fine, powdery particles. thus, destruction of the end strip of paper fed into the destruction machine is addressed by the cowling feature and by a secondary shredder 370 (see figures 12c-12d). by action of the rotating cutter, all of the cut particles get flung outward at the same rate. a relatively big particle flung outwards will get re-chopped at the sacrifice plate 320 (which presents a sharp edge). all particles are captured by the cowling, and no particle can exit radially. the only way for a particle of to-be-destroyed material to leave is axially, by way of a plurality of holes in the stator walls of the secondary shredder (also called a comminuter) 370. the secondary shredder's rotating cutter segment 370 uses the same general fluted and serrated design as in the primary cutter 380, with grooves (preferably such as 2/10 inch (0.2 inch) grooves). the groove size is selected for proper clearance between the drilled stator walls and the sides of the cutting flutes. upon entering a side hole, an entering particle is sheared between the stator wall and the side of a cutter flute as it tries to go through the side hole. multiple chopping of a particles that enter the side hole is provided, with 10 being a suitable number of chopping times, but the number of chopping times not being required to be 10. each hole in the stator wall provides two shearing edges, one on each side of the wall. since the cutter has multiple flutes, each hole, in combination with the multiplicity of flutes, can do a great deal of rapid shearing. further, since each stator wall has a multiplicity of holes, and is engaged successively by a multiplicity of rotating flute side-edges, the secondary shredder assembly has a large capacity to do the shearing job in a very small physical space. clearances preferably are not greater than 0.002 inch between the rotor (blade) and the stator walls, due to practical machining tolerances. the secondary shredder 370 shown in figures 12c-12d has no sacrifice plate, therefore it does not provide the zero-clearance feature. rather, clearances as close to zero as practicable are utilized, and both stator and cutter are of similar hardness. for designing the holes and the cutting edges that will be applied to a particle that travels through the holes, a preferred arrangement is as follows. the holes go straight through. the strategic pattern of the cutting edges and flutes on the secondary shredder 370 is such that, from the perspective of a particle, one cannot see straight through, without seeing one or more blades blocking the path through. preferably, vacuum technology is applied so that a particle that has traveled through the secondary shredder 370 is sucked out by vacuum suction. centrifugal force drives particles outward, and augering (screw conveyer action) drives particles sideways; vacuum application furthers those objectives. because dust is being made, a vacuum should be used anyway to collect and dispose of the dust. by the configuration according to figures 12c- 12d, positive air pressure is generated by the cutter geometry and rotation because, as with a screw compressor, the particles and air are accelerated sideways as well as radially. it will be appreciated that, although figure 12a implies a standard desktop device with paper fed parallel to a desk surface, a destruction device also may be configured so that paper is fed vertically (i.e., perpendicular to a desk surface), or in some other feed configuration. vertical feeding may be preferable because any particles that bounce out as a result of the violence of the shredding action will fall and be sucked back in. thus, a rotary cutter with cutting edges in a strategic pattern, a relatively-softer sacrifice material in zero-clearance disposition to the cutting edges, cowling technology and augering technology may be combined to achieve destruction of information-bearing paper (such as standard 8 vi inch wide paper) and paper-like materials into fine, powdery particles of high-security size (i.e., smaller than u.s. national security agency (nsa)'s newly promulgated in 2002 smaller-size destruction requirements). it is believed that, before the present invention, a commercially practical technique was not known for reliably converting paper and paper-like materials into such fine, powdery particles, and only into such fine particles, leaving no undestroyed material. the nearest approximation would have been a "disintegrator", which operates very differently, is much, much larger, and can only guarantee fine-particle output if fitted with a very fine screen. such a fine screen greatly reduce the rate of material processing, so much as to make the machine impractical. the cutter and relatively-softer sacrifice material, and strategic augering and cowling and secondary shredder having been thus mentioned above, the following further engineering details are mentioned for advantageously achieving high security destruction of 8 1 a inch wide paper, but are not necessarily required exactly as shown in the accompanying figures in a destruction machine. referring to figure 12a, material guide 304 guides the to-be-destroyed material m (such as paper). pressure rollers 312 are disposed below and above the to-be-destroyed material m, applying spring pressure to squeeze the to-be-destroyed material m to provide exact metering (exact metering being important). the 9-inch wide sacrifice plate 320 (made of a material relatively softer than the cutter) is supported by a bolster block 305. the sacrifice plate 320 can be incrementally moved into contact with the cutter (i.e., with the cutting edges of the cutter) by a jacknut 399, which moves the sacrifice plate at a slow rate, for gradually using up the sacrifice plate. the jacknut 399 pushes the sacrifice plate 320 upwards. a fixed clamp bar 397 pushes against the bolster block 305, with the pushing being accomplished by spring plungers 396 mounted within clamp bar 397. the sacrifice plate 320 is eventually resisted by the static block 398. the static block 398 provides the location and support for the sacrifice bar 320. the static block 398, bolster block 305, springs, spring plunger, and the fixed clamp bar 397 operate together to constrain the sacrifice bar to only move vertically. a tight sliding fit is provided for the sacrifice bar. the sacrifice bar 320 is slidably supported by the static block 398. as seen on figure 12a, starting with the cutting zone on the rotary cutter 318 and proceeding 360 degrees counterclockwise, the cowling around the cutter may be appreciated as follows. for about the region from 0 to 45 degrees, the cowling is provided by the sacrifice bar 320 and the first half of the bolster block 305. for about the next 90 degrees, still moving counterclockwise, the cowling is provided by the second half of the clamp bar 397, together with all of the fixed clamp bar 397. the final 180 degrees, moving counterclockwise along the rotary cutter 318, is provided by the cowling 395. the amount left on the cutter 318, namely, about 45 degrees, is the opening, where to-be-destroyed material m enters. this zone is largely blocked by the feed rollers 312, so that any particles flung out by the cutter 318 will tend to rebound back in to the cutter and cowled space. note also that there must be an opening for air to enter, in order for the vacuum to entrain cut particles and carry then through the cutter system for collection. the air-space gap between the interior surface of the cowling and the exterior surface of the cutter 318 is relatively small, with the cowling being quite tightly fitting around the cutter 318, while of course not touching the cutter 318 in operation. the tight cowling fit is desired to keep to-be-destroyed material in the cutting system and to keep the to-be-destroyed material and pieces thereof moving. referring to figure 12a, the static block 398 supports the sacrifice plate 320. the cowl reaches all the way across axially and covers 180 degrees. the cowl is a half-moon shape, for the full 9 inch length. attachment is by bolting to a plate (not seen in the figure), with bolting only on the top of one side. this allows for rapid and easy removal of the cowling for inspection, cleaning, and maintenance. an approximately 45 degree open gap is provided, from about the 90 degree point, down to the paper, so that the paper can enter. an almost complete enclosure "tube" is thus provided as considerable blocking is provided by the rollers immediately adjacent. importantly, a significant advantage of the inventive system is mechanical simplicity. the secondary shredder cutter array is merely an additional section grooved into one end of the cutter 380. a suitable stator assembly 600 (made in two halves) is simply bolted around one end of the rotating cutter, with apertures suitable for exhaust of the particles by a simple vacuum. this is very different from conventional shredders using multiple heads. referring to figure 12 a, vacuum air entry is shown by small arrows between the pressure roller 312 and rotary cutter 318. the vacuum aspects, and other aspects, of an exemplary system according to the invention may be further appreciated with respect to the paper-feed view of figure 12c, from which we can see particle motion froni combined action of: augering by cutter flutes, centrifugal force, and vacuum air flow. rotation is depicted on the figure, with the top of the cutter rotating towards the viewer. a vacuum plenum 390 is shown, and a vacuum residue collection system 389. the part of the rotary cutter 318 that is the primary rotary cutter is shown as primary cutter 380 on figures 12c-12d; the part of the rotary cutter 318 that is the secondary shredder is shown as secondary shredder 370 on figures 12c-12d. referring figure 12 a, and an example in which the to-be-destroyed material is paper, the destruction operation will be further appreciated as follows. as the paper advances into the device, the paper undergoes a cut and drag process. if the rotary cutter 318 is fast enough, the motion of the paper is trivial. depending on the cutter motion and speed, and on the paper feed, a certain bite pattern on the paper results. a non-serrated cutter would give a slice. a serrated cutter is needed to get the tiny nibbles rather than the less-desirable larger slice. (a serrated cutter also is called a "chip-breaker" cutter, also called a "roughing end mill", generally use for initial, rough-cutting work on metals.) destruction devices according to figures 12a-12d advantageously take into account possible clogging, by providing for unclogging by simple cowling removal, whereupon blowing and vacuuming can be performed. a wire keeper (not shown on figure 12a) optionally may be disposed to prevent to- be-destroyed paper (such as flimsy older facsimile paper or very thin film) from undesirable curling down and around roller 312, between the top of guide 304 and the top of the static block 398 across the rollers. a deliberate gap is shown on figure 12a (between the bottom of guide 304 and the machine base), so that if paper does curl, it has a way out. the wire keeper also can be used on a machine according to figure 1, and provides especial advantages there because there is no exit gap on the design of figure 1 for curling paper. it will be appreciated that advantageous features mentioned above with regard to figures 12a-12d, while particularly favorable for use in destroying paper (especially letter- width paper) also may be applied to destruction of other to-be-destroyed materials. thus, the present invention provides for high-security destruction of various to-be- destroyed materials that are planar and relatively thin, with preferred examples being ordinary paper; key tape (e.g., paper alone; mylar alone; paper/mylar bonded together; paper/mylar/paper bonded together); photographs; film; transparencies; compact disks; credit cards, smart cards, cardboard; magnetic tape; diskettes, thin plywood; a whole cassette (with or without the screws removed); verichips; flash drives, biometric chips, etc. while particular mention has been made of destruction of thin materials, and objects contacting thin materials, the invention also may be applied to destroy thicker materials. when feeding a thicker material, the horsepower of the cutter, the speed of the cutter, and/or the feeder speed is adjusted compared to a thin material. a single machine may be provided that is adjustable for a range of various thicknesses and compositions of materials to be destroyed. further favorable details for devices according to the invention are as follows, understanding that the invention is not limited thereto. the following perfecting details may be appreciated with reference to an inventive embodiment such as the example shown in figure 1. namely, there may be included side plates on opposing sides of the pressure roller and the friction feed capstan, the side plates retaining the pressure roller and the friction feed capstan in a predetermined position. when such an arrangement is used, optionally each of the side plates may comprise a slot and opening; and the pressure roller may further include a roller shaft with the roller freely rotating thereabout, the roller shaft being captured by the each slot of the side plates. there may further be included pressure screws insertable within each slot for adjusting a downward pressure on the pressure roller against the friction feed capstan. there may further be included spacers which, in combination with the pressure screws, provide an adjustable deflection of rubber-like material of the pressure roller against the friction feed capstan. the deflection determination is fixed by design (thickness of the spacers), but relieves the operator from making any routine pressure adjustment. this provides a significant operational advantage of simplicity. when side plates are used, the opening of each of the side plates may allow the roller shaft to be removed from between the side plates in order to quickly and easily remove the pressure roller. also, when side plates are used, there may be included a first screw positionable within the vertical slot of the first side plate and contacting a first end of the roller shaft in a first position; and a second screw positionable within the vertical slot of the second side plate and being able to contact a second end of the roller shaft in the first position. there may be included first and second spacers positionable with respect to the first and second opposing side plates, respectively. it may be configured wherein the first and second spacers in combination with the first and second screws provide an adjustment deflection of rubber-like material of the roller mechanism against the driven capstan. the deflection determination is fixed by design (thickness of the spacers), but relieves the operator from making any routine pressure adjustment. this provides a significant operational advantage of simplicity. the metering mechanism may provide positive control of feed of the to-be-destroyed material as established by the capstan rotation. in additional embodiments, a positively controlled feeding mechanism may be provided, such as one in which the feeding mechanism includes a first and a second side plate, both having a vertical slot and an opening. additionally, a driven capstan mechanism may be positioned between the first side plate and the second side plate. a roller mechanism having a roller shaft also may be provided. the roller shaft may be captured within the vertical slot of the first side plate and the vertical slot of the second opposing side plate. the roller shaft further may be positionable relative to the opening of the first side plate and the opening of the second side plate for removal therefrom. in embodiments, a first and a second screw are positionable within the respective vertical slots of the first and second side plates. spacers may also be provided. the spacers, in combination with the screws, provide an adjustable deflection of rubber-like material of the roller mechanism against the driven capstan. the deflection determination is fixed by design (thickness of the spacers), but relieves the operator from making any routine pressure adjustment. this provides a significant operational advantage of simplicity. there may be included a pressure plate in contact with the sacrificial blade or round bar, the pressure plate substantially preventing vibrations caused by interactions of the rotary cutter and the sacrificial blade or round bar. there may be included a spring plunger contacting the pressure plate, the spring plunger forcing the pressure plate against the sacrificial plate or round bar. there may be included a guide mechanism upstream from the metering mechanism, the guide mechanism being in line with the metering mechanism and providing a guide for the to-be-destroyed material to be fed into the metering mechanism. while figures 1 and 3 for simplicity and as a preferred embodiment show destruction devices each using a single sacrificial material, it will be appreciated that the invention also includes using sacrificial material in two or more locations. figure 9 is only one example of using sacrifice material at more than one location. in figure 9, a to-be-destroyed material m is being fed towards a rotating cutter 118 provided within a relatively-tightly cowled housing. as in figure 1, a sacrifice blade 120 is disposed for contact with the rotating cutter. additionally, a second sacrifice blade 120' is disposed at another location for similar contact with the rotating cutter, for providing a second zero-clearance cutting zone. each of sacrifice blades 120 and 120' could be replaced by a round bar material appropriately arranged. in the invention, the shape of a to-be-destroyed material may be generally regular (such as generally planar (such as a sheet of paper, photograph, etc.), etc.), or may be irregular (such as cut, torn, wrinkled, bunched, etc.), so long as the to-be-destroyed material is suitably disposed in a cutting system including at least one sacrificial material. the invention not only provides zero-clearance cutting systems and methods, but, such zero-clearance cutting systems and methods are maintainable. for example, maintainable zero-clearance cutting of the present invention provides on the order of millions of cuts with the same configuration of sacrifice blade and cutting edge without changing the sacrifice blade or cutter. above, a secondary shredder has been mentioned. further perfecting details regarding a secondary shredder are as follows. the secondary shredder may include a single shaft common to the rotating secondary shredder and the rotating primary cutter. such a use of a common shaft provides advantages of simplicity, low cost, ease of manufacturing, and reduced number of parts. the secondary shredder may be an extension of the primary cutter, with no change in basic cutter geometry from the primary cutter. the cutter may be grooved to accommodate a stator. on the secondary shredder may be created a very large number of individual cutting stations (such as 600 to 800 cutting stations in a cylindrical envelope of 1.3 " diameter x 1.3" long). converting a radial cutting action into an axial cutting action may be provided. the helix of the basic cutter may be exploited to block straight-through passage of a particle through the secondary shredder, thus guaranteeing multiple cuts. a very large number of cutters may be provided in a very small space. the geometry of the stator walls may be kept extremely simple (such as straight-through common-axis holes through all of the stator walls). the stator may itself be simple and easy to attach (such as a split housing which simply clamps over the cutter). there may be provided a very simple means to clean, inspect, and maintain the secondary shredder, by removing a few screws. there may be exploited the helical geometry (such as the helical flutes) of the cutter and the secondary shredder section (or other suitable geometry) to "pump" air laterally towards the secondary shredder and the residue vacuum port and/or to "pump" already-cut particles laterally towards the secondary shredder and the residue vacuum port. a vacuum may be used to enhance transport of already-cut particles laterally towards the secondary shredder section. a vacuum may be used to enhance transport of the particles out of the machine for collection. without the invention being in any way limited thereto, some examples of using the invention, in various embodiments, are mentioned as follows. example 1 a prototype machine (and, subsequently, a production machine) was built, model kd- 100 (key tape disintegrator), one instance of the more general class of machines which the present inventor calls "micro-disintegrators". this class of machines is so named for two principle reasons: 1) because the machines are physically small, considering their function, 2) the output (or "residue", as it is designated in the art) produced by such machines is composed of extremely small dust-like particles, similar to those from a disintegrator, but finer. the actual kd-100 resembles that depicted in figure 1. it utilizes only a single motor which performs all four of these functions: a) drives the cutter; b) drives the vacuum dust collection system; c) drives the positively-controlled material capstan feed (through gear trains); d) drives the extremely slow and gradual upwards motion of the sacrifice plate (through an additional gear train). the actual machine is in full compliance with department of defense (dod) requirements lists, meeting or exceeding all "must-have" requirements and meeting or exceeding all "desirable" requirements, specifically for the destruction of key tape. in this (kd- 100) machine, the cutter is made from high-speed steel, and (optionally) a solid-carbide cutter is available, with a life of 2-to- 10 times that of high-speed steel. the kd- 100 uses ordinary 1/16" or 3/32" thick soft aluminum for its sacrifice blade. the model kd-100 machine destroys materials made of paper; made of a blend of plastics (such as polyester) and paper; and made from polyester (or other thin plastics) alone, more completely than by shredding alone, leaving no useable or recoverable information, reducing such materials to dust-like particles. the model kd-100 machine provides extremely high security, because it reduces the information to an absolutely information-unrecoverable form, i.e., dust. the model kd-100 machine is fast— it declassifies a 10" strip of key tape to dust in about 4 seconds (very desirable in the event that an emergency requires rapid data destruction). the model kd-100 machine is easy and safe to use, requiring no special operator skill, even under conditions of high operator stress. there are no doors or drawers to open; no buttons to push; no latches, catches, levers or hasps to operate. there are no exposed moving parts. the model kd-100 machine is simply switched on, and the key tape is inserted. the feed system automatically captures the tape, and feeds it to the cutting system. switch off when done. the model kd-100 machine is low in cost, because it is physically small, light in weight, mechanically simple, and uses a minimum of moving parts to perform its function. the model kd- 100 machine consumes very little energy to perform its function (typically under 300 watts) and is thus practical to use with a small and low-cost back-up battery system. the model kd- 100 machine is rugged due to its simplicity of design and the robust character of its components and attachments. for example, it uses a heavy-duty nema 4x fiberglass sculpted, gasketed enclosure. the model kd- 100 machine is relatively quiet (75 dba, measured at the operator's ear), for an unobtrusive operation in an office environment. the model kd- 100 machine is friendly to the environment, because it merely cuts material, producing no high temperatures, airborne dust, smoke, toxic fumes, or residue. it simply makes a cool, harmless powder. the model kd- 100 machine is easy to maintain because of its basic simplicity, small number of moving parts, and quick-release mechanisms. examples: cutter replacement, along with cutter bearings (done in one operation) takes under 10 minutes. in an additional 2 minutes, the sacrifice blade can be replaced. motor replacement can be performed in about 5 minutes. rubber roller replacement can be performed in under 1 minute. these are the only parts that one might normally need to replace to due normal wear and tear. no lubrication required. requires no special tools to fix or adjust it. the model kd- 100 machine provides the possibility of almost-silent covert operation (by reducing speed). the model kd- 100 machine allows for emergency high- volume operation as follows: a) snap open the lid; b) remove the bag; c) insert an exhaust tube; d) operate. the model kd- 100 machine contemplates and allows for the possibility of power loss: the tape can just be pulled out. the model kd- 100 machine is compact, having a size of 8 x 10 x 6-1/2" (h) (i.e., 205 x 255 x 65 mm). the model kd-100 machine is light, weighing 9.1 lbs. (4.1 kg). the model kd-100 machine is a desk-top design, by virtue of this small, light-weight size. the model kd-100 suits a right-handed or left-handed operator simply by rotating the entire machine 90 degrees to suit. the model kd-100 machine provides superior residue processing and disposal using a low-cost disposable filter bag, which is quickly and easily changed. the kd-100 machine destroys materials made of paper; made of a blend of plastics (such as polyester) and paper; and made from polyester (or other thin plastics) alone, more completely than by shredding alone, leaving no useable or recoverable information, reducing such materials to dust-like particles. example 2 (round-bar sacrifice material) in this example there is assumed a round sacrifice bar 3/8" diameter, or 1.17" circumference. a full revolution of the bar would present 1.178 million micro-inches to the cutter. at about __4l~ 13 ft/minute, the sacrifice feed would be 30x13 (or 390) micro-inches circumferentially per minute, which works out to 390/ 1,178,000 (or .000331) sacrifice bar revolutions per minute, or .0198 (or 1/50.34) sacrifice bar revolutions per hour. the bar will last about 50 hours, or 46,800 feet. in this case, a feed rate of approximately 30 micro-inches of sacrifice material per foot length of destroyed material, or about 400,000 inches of destroyed material per inch of sacrifice material is provided, for this round-bar sacrifice material example. this may be compared to about .500 sacrifice jackscrew revolutions per hour in a sacrifice plate embodiment. correspondingly, more worm-gear drive ratio reductions are needed to operate with the round bar. example 3 (docustroyer/cryptostroyer paper-destruction machine) a destruction machine for to-be-destroyed 8 vi inch- wide paper was constructed according to figures 12a-12d. a cutter was made from cobalt steel, coated with titanium nitrate (to enhance its hardness). a cutter as in figure 11 was used. the cutter had raised cutting edges with vertical serrations, with a 0.007 inch offset pattern to the serrations. a 9- inch wide sacrifice material of 3/16 inch thick soft aluminum was used. a destruction machine for 8 v% inch wide paper was constructed as described above with regard to figures 11-12d. the inventive docustroyer/cryptostroyer machine was tested on 10 paper pages in rapid sequence, fed one at a time (generating 10 end-strips). the end-of-page strip processed through the secondary shredder. all that remained of the 10 paper pages was powdery dust. in addition to the excellent destruction capability provided by the docustroyer/ cryptostroyer device of this example, the inventive machine has mechanical advantages over conventional paper-destruction machines. number of rotating cutter parts inventive example 3 1 conventional commercial 3 -head paper destruction machines 6 examples 1-3 reflect cutting systems have been accomplished which are capable of cutting a material such as, for example, tape or paper, into a fiber or powder. in these examples using a rotary cutter and a relatively-softer sacrifice material, the contacting portion was observed to have zero clearance during the cutting operation. zero clearance during the cutting operation enhanced the ability to destroy the material. also, destruction of material was further enhanced by advantageous strategic patterning of cutting edges on a rotary cutter (such as applying an offset to the cutting edge pattern), and further by secondary shredding features (such as the secondary shredder of example 3 and figures 12c- 12d). the invention was observed in the testing of examples 1-3 above to provide systems for reducing to-be- destroyed paper and other relatively-thin planar materials to a dust or powder-size. example 4 (maintainability of zero-clearance cutting " ) for a paper destruction machine according to example 3, in which a sacrifice blade is used with the cutter of example 3, maintainability is calculated as follows, where operation of the cutter is at 15,000 rpm, with 24 cuts per cutter revolution. 2500 feet of paper are processed at 4 seconds/foot, which is 10,000 seconds which is 166 minutes of operation. 166 minutes of operation multiplied by 15,000 rpm is 2.49 million revolutions. 2.49 million cutter revolutions multiplied by 24 zero-clearance cuts per revolution is 59.76 million zero- clearance cuts. after 59.76 million zero-clearance cuts of paper (which is very abrasive), the cutting blade is expected to then be dulled by the paper (rather than dulled by interaction with an object other than that being cut). the sacrifice material is relatively unspent, and may still have miles to go (enough material remaining for another 30,000 feet of key tape). from these calculations, the advantage is seen of how very many precision zero-clearance cuts may be provided without the cutter being dulled. for conventional zero-clearance cutting, it would not be possible to provide millions or tens of millions of cuts without blade dulling. example 5 (reciprocal cutter systems) another example of usage of a sacrifice material is with a reciprocal cutter system, such as a reciprocal cutter system in which a sacrificial blade is used with a shearing blade (such as, for example, in figure 7) or a round sacrifice material is used with a shearing blade (such as, for example, in figure 8). in the reciprocal cutter system of figures 7 and 8, a tight fitting guide 701 is shown. a blade (such as a steel blade) goes up and down. in figure 7, a sacrificial blade or bar or plate 720 (constrained by its own tight-fitting guide) is very slowly advanced towards a shearing blade 702 (such as a steel reciprocating shearing blade). the sacrifice material slowly advances to the point of cutting. the arrangement of figure 7 is particularly suited for thin materials. in figure 8, a round sacrifice material 820 is used with a shearing blade 702. to-be- cut material m is fed on a tangent to the rotating sacrifice material 820. the rotation of the sacrifice material 820 is extremely slow. (the diagonal feeding of to-be-cut material m shown in figures 7 and 8 also may be used in other embodiments of the invention and is not restricted to embodiments in which a reciprocal cutter is used.) example 6 referring to the inventive example depicted in figs. 11-12, if there are 10 holes in each wall, and 6 cutter flutes, and 10 wall edges, then a single revolution of the cutter results in 600 shearing operations. if an 8-flute cutter is used, then a single revolution of the cutter results in 800 shearing operations. the inventive example depicted (figs. 11-12) is so configured, and has been built and tested successfully with both 6-flute and 8-flute cutters. even at a relatively slow cutter speed of 1,500 rpm, there would be 0.9 to 1.2 million shearing operations/ minute (or 15,000 to 20,000 shearing operations/per second). the inventive example depicted (figs. 11-12) has been successfully tested at 4 times this speed. those conversant in the art can easily see that no particle could pass through the secondary shredder's blizzard of cuts without being reduced almost to dust. in fact, a large percentage of this machine's output actually is dust. example 7 (double secondary shredder) in an inventive machine including one secondary shredder where the secondary shredder is smaller than the primary cutter, the secondary shredder usually is the throughput rate limiting feature. a way to improve throughput rate was desired, and providing two secondary shredders disposed at separate locations from each other was found to be a solution to throughput rate improvement. an example of a double secondary shredder is shown in fig. 14b. disposition of the double secondary-shredder assembly 1402 of fig. 14b in a machine is not particularly limited, with horizontally or vertically being preferred arrangements. the double secondary- shredder assembly 1402 of fig. 14b, by putting a secondary shredder 1401 at each end along the same axis about which a rotating primary cutter 1400 rotates, achieves significantly higher destruction capacity compared to a comparable assembly without the second secondary shredder. for example, permitting two secondary shredders to process a quantity that otherwise would be processed by one secondary shredder, provides a large gain in machine performance for a small increase in complexity and parts count. with added horsepower, but the same machine package (such as a typical approximate machine size of 20 inches wide by 12 inches deep by 13 inches tall, with the "head" size being smaller, such as about 16 inches by 10 inches by 12 inches), capacity can be approximately doubled. compared to the machines having a single-secondary shredder in the above examples, horsepower could be doubled by simply coupling the motor shafts, end-to-end. even further advantages can be achieved by an inventive double secondary-shredder system, compared to the already-advantageous inventive machines using one secondary shredder: double secondary-shredder comparable single secondary destruction machine shredder machine machine package (x, y, z) (x, y, z) capacity ~ 2n n example 7a (splitting residue exit) while fig. 14b shows a preferred example of a double secondary shredder system, the invention is not limited thereto. as shown with reference to the flowchart of fig. 14 a, the general basic principle is, after a destruction step 140 has been performed (which may result in residue some of which is larger than powder-size), to split 141 the residue exit into at least two exit paths, preferably into two opposite residue exit paths. as residue exits via the two respective exit paths, secondary cutting 142 is performed to reduce the residue to powder- size. exiting residue exits via one or the other exit paths, with the two exit paths being positioned to be mutually exclusive. advantageously, screens (as required in conventional disintegrators) are not needed for the exit paths in this inventive example. gravity need not be considered in establishing residue exit paths, as forces of gravity are trivial compared to forces of air flow established by application of vacuum and forces generated by propeller action of the cutting elements, i.e., residue exit paths need not be in the direction of gravity. example 8 (destroying nog-homogeneous loads) conventional paper shredders respond poorly to being fed torn paper, stapled paper and the like, and generally can become jammed or inoperable when fed a non-homogeneous or imperfect load. moreover, conventionally a paper shredder machine cannot also accommodate non-paper loads, i.e., feeding a non-paper item such as a cd or dvd into a conventional paper shredder would only jam or break the conventional machine and in no event would the cd or dvd be successfully destroyed. however, the present invention advantageously provides, in a particularly preferred embodiment, for construction of a single machine which can receive and successfully destroy, with minimal operator intervention, different materials (such as paper, polyester material, plastic cards, smart cards, cds, dvds, film, wood, photographs, verichips, flash drives, biometric chips, etc.). namely, a zero-clearance cutting zone in which a relatively- softer sacrifice material is used with a relatively-harder material can be configured to accommodate a non-homogeneous load. the inventive zero-clearance machines are self- healing, while conventional machines lacking the sacrifice material are not self-healing. so that a non-homogeneous load may be accommodated by the zero-clearance cutting zone automatically, minimizing user intervention (such as disassembling or re-setting the machine), a load self-evaluative system may be included. for example, a load self-evaluation system may include automatically measuring cutter-motor current, and feeding back this information to control (even reverse) the feed system. also, actual thickness of the fed-in load can be automatically measured, with the measurement being used, as needed, to pre- slow the feed in anticipation of a thicker load. for example, thickness measurement can be using a spring-loaded, swinging vane that is pushed by the load thickness, with the vane actuating a switch, connected to the feed speed-control circuit. additionally, temperature- sensing can be used to anticipate a possible jam or overload. example 9 a destruction machine (example 9) was constructed including a pair of secondary shredders sharing a common axis with a rotating primary cutter. weight (approximate) example 9 -80 lbs sem model 200 disintegrator -375 lbs. the inventive example 9 machine is substantially lighter, and also smaller-dimensioned, than the sem model 200 disintegrator. example 10 conventional paper shredder. conventionally, the respective surfaces between which to-be-cut paper is passed are both (or all) of steel or some such relatively-hard material. when such relatively-hard surfaces encounter paper, which is relatively much weaker than the steel cutting surfaces, the paper is cut. however, when such steel surfaces encounter something (like a paper clip or a staple) that is too hard or too strong to be cut by the steel surfaces, that paper clip or staple or the like will instead jam the system and/or cause damaging wear. thus, it has been wanted for paper shredders not to suffer from such jamming and damage, however, a workable solution had not been conventionally presented. inventive self-healing the present invention uses self-healing of a mechanical part to solve the problem of jamming and damage in a paper shredder due to hard foreign objects, and additionally may be extended for other useful applications. examples of a foreign object may vary according to the particular mechanical system and are not particularly limited. examples of a foreign object in a paper shredder include, e.g., staples, paper clips, binder clips, other steel articles, etc. examples of a foreign object in a cassette destruction apparatus include, e.g., screws, which conventionally were required to be unscrewed and removed before feeding the cassette for destruction. in a harvesting machine, examples of a foreign object may include, e.g., stones, etc. according to the invention, differential hardness may be manipulated in mechanical systems (such as cutting mechanical systems or non-cutting mechanical systems) for imparting self-healing to the system. for example, an inventive cutting embodiment is as follows. in a system in which a material-to-be-cut (such as paper, etc.) passes between two surfaces, in the invention, the relative hardness of one of the two surfaces is manipulated. it will be appreciated that of the two surfaces, at least the first surface must be hard enough to cut the material-to-be-cut. in the invention, the second surface is relatively softer than the first surface. the self-healing invention can be applied for cutting (such as shredding, etc.) materials that are cut by steel, materials that are cut by a steel alloy, materials that are cut by diamond, etc. in the invention, the material-to-be-cut may possess a foreign object (such as to-be- cut paper including a staple, paper including a paper clip, etc.), with the foreign object being something which is not itself needed or desired to be cut. in the invention, the foreign object damages the relatively softer second surface and imparts little or no damage to the relatively harder first surface. the cutting machinery can thus be made self-healing by managing damage caused by a foreign object to the system. mechanical self-healing according to the present invention may be used in zero- clearance mechanical systems (such as, e.g., zero-clearance cutting systems, etc.) and in nonzero-clearance mechanical systems. mechanical self-healing of a sacrificial part refers to re-positioning or change in position of a sacrificial part to restore its original intended function. for example, movement into place of a renewing edge of the sacrificial part preferably occurs by automatic mechanical advancement of the sacrificial part. optionally, such motion of the renewing edge can be accelerated by action of a manual or automatic control system, should the operator become aware of (or if the machine senses and responds to) the damage, or likelihood of damage to the sacrificial part. referring to figure 16, the mechanical self-healing invention may be further appreciated. in figure 16, geometric space is represented with lines drawn for simplicity of representation; actual parts in use in an actual mechanical system may assume different shapes than those represented. figure 16 is from a perspective that a sacrificial material in normal operation is designed to advance in a direction from x n towards xo, with (xo, y 0 ) being a point which is the closest the sacrifice material is designed to be to a relatively-harder component (such as a cutter or other part) which is positioned to occupy some space that, x- wise, is to the left of (xo, yo). in the case of zero-clearance operation, the relatively-harder component may pass through (xo, yo). in near-zero-clearance operations, the relatively-harder component passes through a point which is near (xo, yo). in other embodiments (including cutting and non-cutting embodiments), the relatively-harder component passes through a point which x-wise is more to the left of (xo, yo). advance of sacrificial material in a left-wise direction from x n towards xo is mentioned for simplicity and discussed with regard to figure 16. other advance of sacrificial material may be based on other linear configurations or on non-linear configurations, such as advance of sacrificial material according to a rotational pattern. advance of sacrificial material other than as shown in figure 16 is permitted in other embodiments. returning to the geometric representation which is figure 16, in an inventive self- healing mechanical system, the sacrificial material in normal operation is designed to occupy a cross-sectional area a including ash which is a part that is near to the relatively-harder component (such as a cutter) disposed to the left of a. the sacrificial material in normal operation is advanced (automatically and/or manually) to the left through area a. some examples of suitable materials have been mentioned hereinabove for a sacrificial material, but the sacrificial material is not limited to the mentioned examples and may be any material suitable for use in a mechanical system, with the particular sacrificial material being selected with reference to the particular material used for the relatively-harder component with which it is used. in normal operation area a s h is occupied by sacrificial material as is the rest of area a. however, a hard foreign object (such as a screw, paper clip, stone, etc.) which could be harmful to the mechanical system may force itself into the cross-sectional area a sh - it will be appreciated that the foreign object can more easily force itself into the area a s h which is composed of sacrificial material than into a nearby area which is occupied by the relatively- harder component (such as a cutter, etc.). that is, area a s h in operation of accommodating a hard foreign object may be occupied by that foreign object, with the sacrificial material that previously occupied that area a sh having been pushed, compressed, nicked, separated or otherwise moved out of the area a s h- it is particularly preferred that the sacrificial material be prevented from retracting (due to the pressure caused by ingestion of a foreign object) by a very rigid and unyielding mechanical system, such as by way of a lead-screw, which inherently resists "back-driving", especially if the pitch of the lead-screw is not too coarse. for example, an ordinary 20 thread-per-inch-pitch lead screw has been extensively tested, and found to be quite satisfactory. other methods could be used, such as, e.g., a ratcheting mechanism, etc. in figure 16, area as h is shown as a region bounded by (xo,yo), (xsh,yo) and (x la ysh)- the shape of area a s h will depend on the shape of the foreign object and is not limited to the shape shown in figure 16 for representational purpose. area as h may be a regular or irregular shape. at a subsequent time, the foreign object exits area a s h, such as by the foreign object being manually removed by an operator, by being gradually cut-up, by being dislodged by a mechanical intervention, etc. when the foreign object has exited area a s h, area ash is then unoccupied (i.e., is a vacant space) or may be occupied, in whole or part, by material intended for use in the mechanical system (such as, e.g., paper intended to be cut). subsequently, self-healing area a s h is re-occupied by sacrificial material that has moved from area a into self-healing area a s h- thus, according to the invention, a mechanical system encounters a hard foreign object and self-heals, with minimal damage to the relatively-hard component. thus, the invention manipulates and directs damage by a foreign object away from one component towards a sacrificial component that is intended to receive damage. example iqa with reference to figures 15a-h, an exemplary inventive self-healing mechanical system is shown. the vertical arrow shows the path of to-be-destroyed material (such as, e.g., paper, etc.) that is being intentionally fed for destruction. the point o (figures 15, 15a- c, 15f) below the arrow corresponds to the point (x 0 ,yo) in figure 16. the point o represents a certain volume in the mechanical system which at certain times may be occupied by air and at other times may be occupied by one or more solids. in figure 15 a, a rotating cutter 1501 is solid and relatively hard (and rotating relatively fast, such as, e.g., about 1500 rpm). the rotating cutter 1501 preferably is of very hard material with sharp edges. a sacrificial part 1502 is relatively softer (such as, e.g., aluminum) than the material of the rotating cutter 1501. the sacrificial part 1502 has a damageable section 1503. the sacrificial part 1502 is moved extremely slowly (such as at about 1 inch in 50-100 hours) in a left- ward direction as shown by the left-pointing arrow. the shape of the sacrificial part 1502 is by way of illustration and the invention is not limited thereto; for example, the sacrificial material may be shaped as a round bar (such as a round bar turning with extreme slowness to restore the zero-clearance edge of the round bar, etc.). a foreign object (fo) which is not the intended to-be-destroyed-material may get fed. the foreign object (fo) which is shown as a screw in figure 15b is for illustration and the invention is not limited to foreign objects that are screws or screw-like. the foreign object (fo) may be known to be part of the input load, such as a screw in a cassette tape where the tape itself is the material that is wanted to be destroyed or staples in paper that is wanted to be destroyed. or, the foreign object may be inadvertently present. in figure 15c, the foreign object (fo) is drawn in the destruction area o. in figure 15d, the foreign object (fo) is caught in the destruction area o. the damageable surface 1503 is transformed by the foreign object (fo) into a damaged surface 1503'. it will be appreciated that the foreign object (fo) applies relatively more damage to the damageable surface 1503 than to the relatively-harder cutter 1501. especially in a case where the cutter 1501 is moving relatively rapidly compared to the sacrificial part 1502 being stationary or only moving relatively very slowly, the applied forces will result in a foreign object (fo) which is of the order of relative hardness of the cutter 1501 and therefore relatively harder than the sacrificial part 1502 doing relatively little or minimal damage to the cutter 1501, because damageable surface 1503 will deform, compress, split, or otherwise yield to the foreign object (fo) with the foreign object (fo) moving into the position that the damageable surface area 1503 had been occupying. referring to figure 15e, the foreign object (fo) is being chopped, and the sacrifice part 1502 is damaged at the damageable surface area 1503'. referring to figure 15f, the foreign object (fo) has been chopped into pieces, fo 0 and foi. the sacrificial part 1502 has been damaged and damageable surface area 1503 is gone, with damaged surface area 1503 ' remaining and now being the region of sacrificial part 1502 that is closest to the cutter 1501. referring to figure 15g, the foreign object is gone and mechanical self-healing is beginning where damaged surface 1503' is being advanced towards the first part 1501 but is not quite fully restored to the original position that had been occupied by damageable surface 1503. referring to figure 15h, self-healing is completed. damaged surface 1503' has now moved left- ward into position and is a new damageable surface 1503 ' . preferably, damageable surfaces (1503, 1503' etc.) are integral with the sacrificial part 1502 and can be moved leftward into position. that is, preferably sacrificial part 1502 is a unitary s ~ oljd. in a self-healing system such as that of figures 15a-15h, there is a closest distance "d" between the cutter 1501 and the sacrificial part 1501 in normal operation that is called "dl" in normal operation when the damageable surface area 1503 is in place. referring to figures 15a-15h, "dl" is zero or approximately zero, i.e., the cutter 1501 and the sacrificial part 1502 are designed to be in zero-clearance or near-zero-clearance contact with each other in normal operation. (however, it will be appreciated that in other embodiments of the invention, "dl" is not required to be close to zero and, depending on the particular mechanical system, may even be a relatively large value.) when the sacrificial part 1502 has been damaged, the distance "d" is increased to a larger distance "d2" at points 1503' where the sacrificial part 1502 has been damaged. for example, referring to figures 15c- 15f, it can be seen that the sacrificial part 1502 is now separated from the cutter 1501 by more space than before the damage. in this example 1oa referring to figures 15a-15h, the self-healing system includes restoring the distance "d2" to about the original distance "dl" (such as, for example, wherein the restoration of the distance "d2" back to about the original distance "dl" is by automatic movement of the sacrificial part or wherein the restoration of the distance "d2" to about the original distance "dl" is by movement or reposition of the sacrificial part 1502). that is, referring to figure 15h, there once again is the same amount of space between the cutter 1501 and the sacrificial part 1502 as before the foreign object (fo) entered and traveled through the system. referring to figures 15a-15h, an example has been shown in which the foreign object (fo) has been cut. however, in another case a foreign object may interact in a different way with a self-healing mechanical system, such as a foreign object could be so hard and rigid that it might pass through un-cut, by being dragged through the interface of the sacrificial material and the harder part (such as the cutter), taking a chunk out of the sacrifice interface. in such a case of a foreign object being dragged through the sacrifice interface uncut, healing would still occur, and the amount of sacrificial needing to be advanced so that healing occurs would depend on the amount taken out of the sacrificial interface. returning to a case where the foreign object is sheared, in a system such as that of figure 15 , the sacrificial material would be damaged and part of the cutter 1501 may (but is not required to and is preferred not to) receive damage. because a rotary cutter 1501 has relatively many cutter parts, such damage to one part may be tolerated relatively well and performance effects may be unnoticeable. example 11 (destruction of flash drives, biometric chips') a destruction machine was constructed including a pair of secondary shredders sharing a common axis with a rotating primary cutter. flash drives and biometric chips were fed into the destruction machine, and were destroyed into a powder. the flash drives and biometric chips were thus securely destroyed into information unrecoverable form. while the invention has been described in terms of preferred embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the appended claims.
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093-767-546-773-177
|
US
|
[
"EP",
"US"
] |
H04L29/06,H04L12/26,H04L9/00
| 2007-08-21T00:00:00 |
2007
|
[
"H04"
] |
method and apparatus for checking round trip based on challenge response as well as computer readable medium having recorded thereon program for the method
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an apparatus and method of checking adjacency between devices are provided. a challenge response based round trip time (rtt) checking method includes: generating a random number; encrypting the random number using a symmetrical key; transmitting a challenge request message including the encrypted random number to a device; receiving a challenge response message including the random number from the device which received the challenge request message and decrypted the encrypted random number using the symmetrical key, from the device; and determining an rtt based on a time when the challenge response message is received and a time when the challenge request message is transmitted.
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a method of checking a round trip time (rtt) based on a challenge response, the method comprising: generating a random number; encrypting the random number using a symmetrical key; transmitting a challenge request message including the encrypted random number to a device; receiving a challenge response message including the random number from the device which received the challenge request message and decrypted the encrypted random number using the symmetrical key; and determining an rtt based on a time when the challenge response message is received and a time when the challenge request message is transmitted. the method of claim 1, wherein the encrypting the random number using the symmetrical key comprises: generating a random number mask using the symmetrical key; and combining the random number and the random number mask according to an xor operation. the method of claim 1, further comprising authenticating the device by comparing the random number with the random number included in the challenge response message, if the rtt is less than a time limit. the method of claim 3, wherein if the rtt is equal to or greater than the time limit, the method is repeated up to a maximum number of repetitions. the method of claim 1, further comprising: transmitting a preparation request message to the device; and receiving a preparation response message from the device in response to the preparation request message. a method of checking a round trip time (rtt) based on a challenge response, the method comprising: receiving a challenge request message including an encrypted random number , from a device, wherein the encrypted random number is encrypted using a symmetrical key; decrypting the encrypted random number using the symmetrical key; and transmitting a challenge response message including the decrypted random number to the device. the method of claim 6, further comprising, before the receiving the challenge request message, generating a random number mask using the symmetrical key, wherein the decrypting the encrypted random number comprises combining the encrypted random number included in the challenge request message with the random number mask according to an xor operation. the method of claim 6, further comprising: receiving the preparation request message from the device; and transmitting the preparation response message from the device in response to the preparation request message. an apparatus for checking a round trip time (rtt) based on a challenge response, the apparatus comprising: a random number generation unit (615) which generates a random number; an encryption unit (620) which encrypts the random number using a symmetrical key; a communication unit (635) which transmits a challenge request message including the encrypted random number to a device, and receives a challenge response message including the random number from the device which received the challenge request message and decrypted the encrypted random number using the symmetrical key; and an rtt determination unit (640) which determines an rtt based on a time when the challenge response message is received and a time when the challenge request message is transmitted. the apparatus of claim 9, wherein the encryption unit (620) comprises: a random number mask generation unit (630) which generates a random number mask using the symmetrical key; and a combination unit (625) which combines the random number and the random number mask according to an xor operation. the apparatus of claim 9, further comprising: a comparison unit (650) which compares the rtt with a time limit; and an authentication unit (655) which authenticates the device by comparing the random number with the random number included in the challenge response message if the rtt is less than the time limit. am apparatus for checking a round trip time (rtt) based on a challenge response, the apparatus comprising: a communication unit (665) which receives a challenge request message including an encrypted random number which is encrypted using a symmetrical key, from a device; and a decryption unit (670) which decrypts the encrypted random number using the symmetrical key, wherein the communication unit transmits a challenge response message including the decrypted random number to the device. the apparatus of claim 12, wherein the decryption unit (670) comprises: a random number mask generation unit (675) which generates a random number mask using the symmetrical key before the communication unit (665) receives the challenge request message; and a combination unit (680) which combines the encrypted random number included in the challenge request message with the random number mask according to an xor operation. a computer recording medium having recorded thereon a program for a method for checking a round trip time (rtt) based on a challenge response, the method comprising: generating a random number; encrypting the random number using a symmetrical key; transmitting a challenge request message including the encrypted random number to a device; receiving a challenge response message including the random number from the device which received the challenge request message and decrypted the encrypted random number using the symmetrical key; and determining an rtt based on a time when the challenge response message is received and a time when the challenge request message is transmitted. a computer recording medium having recorded thereon a program for a method for checking a round trip time (rtt) based on a challenge response, the method comprising: receiving a challenge request message including an encrypted random number which is encrypted using a symmetrical key, from a device; decrypting the encrypted random number using the symmetrical key; and transmitting a challenge response message including the decrypted random number to the device.
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cross-reference to related patent application this application priority from u.s. provisional application no. 60/956,986, filed on august 21, 2007 in the u.s. patent and trademark office, and korean patent application no. 10-2007-0115504, filed on november 13, 2007 in the korean intellectual property office, the disclosures of which are incorporated herein in their entirety by reference. background of the invention 1. field of the invention methods and apparatuses consistent with the present invention relate to checking adjacency between devices, and more particularly, to a method for checking adjacency between devices by using an rtt measured value. 2. description of the related art with the recent development of an internet protocol (ip) network infrastructure, a home network technology of networking devices within a house is attracting much attention. one of the issues of the home network technology is localization, that is, how to determine whether devices in an ip network are physically located within a single house or within different houses. this issue is very important because the localization is a premise for a policy that allows only the devices included in a single house to freely share contents. fig. 1 illustrates a general network environment to which localization is applied. referring to fig. 1 , a contents provider 110 provides contents to a device a 122 located in a home network 120 of an authorized contents user. the authorized contents user should be able to use not only contents stored in the device a 122 but also contents stored in a device b 124, a device c 126, and a device d 128 that are included in the home network 120. however, the contents provided by the contents provider 110 may not be allowed to flow into a device e 132 located in an external network 130 other than the home network 120. accordingly, in order to control contents transmission from the device a 122 to other devices, adjacency between the device a 122 and each of the other devices needs to be checked first. the adjacency check may be performed according to a round trip time (rtt) checking method or a hop count restricting method. in the rtt checking method, a time required for a specific message to make a round trip between devices is measured, and a determination as to whether the measured time is less than or equal to a predetermined period of time is then made. in the hop count restricting method, the number of routers that a specific message can pass through until it reaches a destination device via an ip network is restricted. examples of the rtt checking method include an rtt checking protocol of digital transmission content protection over internet protocol (dtcp-ip). the dtcp-ip rtt checking protocol uses a method of exchanging authentication codes between two devices based on a sequence number. in other words, in the authentication code exchanging method, two devices generate message authentication codes (macs) by using a key value and a sequence number that sequentially increases by 1 from 0, and exchange the macs with each other. rtt checking is performed by measuring a period of time required to transmit the macs. summary of the invention preferred embodiments of the present invention aim to provide a method and apparatus for checking rtt based on a challenge response by using an encryption algorithm in order to efficiently check adjacency between devices, and a computer readable recording medium which records a program for the method. preferred embodiments of the present invention aim to provide a method and apparatus for checking an rtt based on a challenge response by using an encryption algorithm, wherein the method is different from an authentication code exchanging method based on a sequence number, and a computer readable recording medium which records a program for the challenge response rtt checking method. according to an aspect of the present invention, there is provided a challenge response based rtt checking method comprising: generating a random number; encrypting the random number by using a symmetrical key; transmitting a challenge request message including the encrypted random number to a predetermined device; receiving a challenge response message including the encrypted random number decrypted using the symmetrical key, from the predetermined device; and determining an rtt by using a point in time when the challenge response message is received and a point in time when the challenge request message is transmitted. the encrypting the random number using the symmetrical key may comprise the sub-operations of generating a random number mask by using the symmetrical key and combining the generated random number and the random number mask according to an xor operation. the challenge response based rtt checking method may further comprise authenticating the predetermined device by comparing the generated random number with the decrypted random number included in the challenge response message, if the rtt is less than a predetermined time limit. if the rtt is equal to or greater than the predetermined time limit, generating the random number through the determining of the rtt may be repeated within a predetermined maximum number of repetitions. the challenge response based rtt checking method may further comprise transmitting a preparation request message to the predetermined device and receiving a preparation response message from the predetermined device. according to another aspect of the present invention, there is provided a challenge response based rtt checking method comprising: receiving a challenge request message comprising a random number encrypted using a symmetrical key, from a predetermined device; decrypting the encrypted random number by using the symmetrical key; and transmitting a challenge response message comprising the decrypted random number to the predetermined device. the challenge response based rtt checking method may further comprise, before the receiving the challenge request message, generating a random number mask by using the symmetrical key, wherein the decrypting of the encrypted random number comprises combining the encrypted random number included in the challenge request message with the random number mask according to an xor operation. the challenge response based rtt checking method may further comprise receiving the preparation request message from the predetermined device and transmitting the preparation response message from the predetermined device. according to another aspect of the present invention, there is provided a challenge response based rtt checking apparatus comprising: a random number generation unit generating a random number; an encryption unit encrypting the random number by using a symmetrical key; a communication unit transmitting a challenge request message including the encrypted random number to a predetermined device and receiving a challenge response message including the encrypted random number decrypted using the symmetrical key, from the predetermined device; and an rtt determination unit determining an rtt by using a point in time when the challenge response message is received and a point in time when the challenge request message is transmitted. according to another aspect of the present invention, there is provided a challenge response based rtt checking apparatus comprising: a communication unit receiving a challenge request message comprising a random number encrypted using a symmetrical key, from a predetermined device; and a decryption unit decrypting the encrypted random number by using the symmetrical key, wherein the communication unit transmits a challenge response message comprising the decrypted random number to the predetermined device. according to another aspect of the present invention, there is provided a computer recording medium having recorded thereon a program for a challenge response based rtt checking method comprising the operations of: generating a random number; encrypting the random number by using a symmetrical key; transmitting a challenge request message including the encrypted random number to a predetermined device; receiving a challenge response message including the encrypted random number decrypted using the symmetrical key, from the predetermined device; and determining an rtt by using a point in time when the challenge response message is received and a point in time when the challenge request message is transmitted. according to another aspect of the present invention, there is provided a computer recording medium having recorded thereon a program for a challenge response based rtt checking method comprising the operations of: receiving a challenge request message comprising a random number encrypted using a symmetrical key, from a predetermined device; decrypting the encrypted random number by using the symmetrical key; and transmitting a challenge response message comprising the decrypted random number to the predetermined device. brief description of the drawings the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: fig. 1 illustrates a general network environment to which localization is applied; fig. 2 illustrates a challenge response based rtt checking system according to an exemplary embodiment of the present invention; fig. 3 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention; fig. 4 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention; fig. 5 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention; fig. 6 is a functional block diagram of a challenge response based rtt checking apparatus according to an exemplary embodiment of the present invention; fig. 7 is a flowchart illustrating a challenge response based rtt checking method according to an exemplary embodiment of the present invention; and fig. 8 is a flowchart illustrating a challenge response based rtt checking method according to another exemplary embodiment of the present invention. detailed description of exemplary embodiments of the invention the present invention will now be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. fig. 2 illustrates a challenge response based round trip time (rtt) checking system according to an exemplary embodiment of the present invention. referring to fig. 2 , a device a 205 and a device b 210 share symmetrical keys (sks) 220 and 225 through a process such as an authentication and key exchange (ake) operation 215 before rtt checking is executed. hereinafter, it is assumed that the device a 205 and the device b 210 share the sks 220 and 225 for use in performing rtt checking. a method of sharing sks is well known to one of ordinary skill in the art to which the present invention pertains, so a detailed description thereof will be omitted. challenge response based rtt checking according to the exemplary embodiment of fig. 2 is performed according to the following sequence. when rtt checking starts, although not shown, an rtt checking apparatus may set to 0 a counter n that is installed in the device a 205 in order to indicate the number of times of rtt checking between the device a 205 and the device b 210. the setting of the counter n is repeated a predetermined maximum number of times in consideration of the variability of a traffic of a transmission path such as a network, thereby measuring an rtt. according to the results of several times of measurements of an rtt, if only one of the measured rtts is within a predetermined critical time, the device a 205 and the device b 210 are considered adjacent to each other. thereafter, in operation 230, the device a 205 generates a random number r. every time the counter n increases, the random number r is changed. in operation 235, the device a 205 encrypts the random number r by using the sk 220. next, in operations 240 and 245, the device a 205 and the device b 210 transmit and receive a preparation request message rtt_ready.command and a preparation response message rtt_ready.response which are used for performing rtt checking. in a modified exemplary embodiment, the operations 240 and 245 may be omitted. this modified exemplary embodiment will be described later with reference to fig. 4 . in another modified exemplary embodiment, the operations 240 and 245 of the device a 205 and the device b 210 transmitting/receiving the preparation request message rtt_ready.command and the preparation response message rtt_ready.response may be performed before the operations 230 and 235 of generating the random number r and encrypting the random number r by using the sk 220. the device a 205 generates a challenge request message rtt_challenge(e sk (r)) including an encrypted random number e sk (r) that results from the operation 235. thereafter, in operation 250, the device a 205 starts measurement of the rtt by transmitting the challenge request message rtt_challenge(e sk (r)) to the device b 210 and simultaneously measuring a point in time when the challenge request message rtt_challenge(e sk (r)) is transmitted. the device b 210 parses the challenge request message rtt_challenge(e sk (r)) in order to obtain the encrypted random number e sk (r). then, in operation 255, the device b 210 decrypts the encrypted random number e sk (r) using the sk 225. in operation 260, the device b 225 generates a challenge response message rtt_response(r') including a decrypted random number r' that results from the operation 255, and transmits the challenge response message rtt_response(r') to the device a 205. the device a 205 receives the challenge response message rtt_response(r') including the decrypted random number r' from the device b 210. at the same time, the device a 205 measures a point in time when the challenge response message rtt_response(r') is received. the device a 205 calculates a period of time ranging from when the device a 205 sends the challenge request message rtt_challenge(e sk (r)) to the device b 210 and when the device a 205 receives the challenge response message rtt_response(r') from the device b 210, thereby determining the rtt. according to this rtt determination based on a challenge response method, when a device a transmits a challenge request message including a random number property to a device b, the device b derives a challenge response message by applying a predetermined arithmetic operation to the received challenge response message, and transmits the challenge response message to the device a. in other words, since the device b can generate the challenge response message only when receiving the challenge request message, it can be found out that the challenge response message is generated after generation of the challenge request message. in addition, since the rtt determination includes the arithmetic operation, which uses a secret value (that is, an sk) pre-shared by the devices a and b, in order to determine the challenge response message, authentication with respect to the device which sends the challenge response message is possible. next, in operation 265, the device a 205 determines whether the determined rtt is less than a predetermined time limit (tl). when the determined rtt is less than the predetermined tl, the device a 205 compares the random number r included in the challenge request message rtt_challenge(e sk (r)) with the decrypted random number r' received from the device b 210 in order to authenticate the device b 210. when the random number r is equal to the random number r', the device a 205 determines that the rtt check is successful. in other words, the device a 205 determines that the device b 210 is adjacent to the device a 205. on the other hand, when the determined rtt is equal to or greater than the tl, the device a 205 increases the counter n by 1. thereafter, in operation 275, the device a 205 determines whether the value of the counter n has reached a maximum number of repetitions n mr . the maximum number of repetitions is predefined in consideration of the variability of a traffic of a transmission path such as a network. when the value of the counter n is equal to or greater than the maximum number of repetitions n mr , the device a 205 determines that the device b 210 is not adjacent to the device a 205 itself. on the other hand, when the value of the counter n is less than the maximum number of repetitions n mr , the device a 205 repeats the operations 230 through 265. in other words, the device a 205 generates and encrypts a new random number and transmits the new random number to the device b 210, the device b 210 decrypts the received encrypted random number and transmits the decrypted random number to the device a 205, and the device a 205 determines the rtt by using a point in time when the encrypted random number is transmitted and a point in time when the decrypted random number is received. at this time, when the device b 210 receives a preparation request message rtt_ready.command from the device a 205 in operation 280, the operation 245 of the device b 210 transmitting the preparation response message rtt_ready.response is re-performed. fig. 3 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention. when the exemplary embodiment of fig. 2 is implemented in an actual system, if a processor does not have a good arithmetic operating performance, the device b 310 requires much time to calculate the challenge response message rtt_response(r'). consequently, the reliability of the rtt checking may degrade. accordingly, the exemplary embodiment of fig. 3 provides a method of minimizing the time required for the device b 310 to calculate the challenge response message rtt_response, in order to enable even systems having relatively low arithmetic operating performances to perform more accurate rtt checking. thus, the exemplary embodiment of fig. 3 provides a method that uses an encoding method which can perform pre-computation. referring to fig. 3 , first, an rtt checking apparatus may set to 0 a counter n that is installed in a device a 305 in order to indicate the number of times of rtt checking between the device a 305 and the device b 310, although not shown. next, the device a 305 generates a random number r and a random number mask r_mask for encrypting the random number r. examples of an encryption algorithm capable of pre-computation used in the exemplary embodiment of fig. 3 include a stream code (for example, rc4), a ctr mode (for example, aes-ctr), etc. in the present exemplary embodiment, each of the processes of generating a challenge request message and a challenge response message by pre-computation is divided into two operations. in a preliminary operation for encrypting the random number r, the device a 305 generates the random number r and the random number mask r_mask. the random number mask r_mask denotes a random number sequence generated by using the encryption algorithm and an sk that is secretly shared by the devices a and b 305 and 310. the random number r is randomly generated regardless of the sk, whereas the random number mask r_mask is generated using the sk. thereafter, the device a 305 generates a ciphertext by combining the random number mask r_mask with the random number r according to an xor operation. in general, it takes much time to generate the random number mask r_mask. however, according to the present invention, it only takes a very small amount of time to perform an xor operation. then, in operation 330, the rtt checking apparatus encrypts the random number r by combining the random number r with the random number mask r_mask according to an xor operation. next, in operation 335, the device a 305 transmits a preparation request message rtt_ready.command for performing an rtt check to the device b 310. in a modified exemplary embodiment, operations 335 and 345 of transmitting/receiving the preparation request message rtt_ready.command and a preparation response message rtt_ready.response between the device a 305 and the device b 310 may be omitted. in a preliminary operation of decrypting an encrypted random number e sk (r) resulting from the encryption of the random number r, the device b 310 generates a random number mask r_mask, in operation 340. an important feature of the present exemplary embodiment is that the device b 310 should generate the random number mask r_mask before receiving the challenge request message rtt_challenge(e sk (r)). for example, the device b 310 may receive the preparation request message rtt_ready.command from the device a 305 in operation 335 and then generate the random number mask r_mask by using the sk in operation 340. after the generation of the random number mask r_mask, the device b 310 transmits the preparation response message rtt_ready.response to the device a 305 in operation 345. in a modified exemplary embodiment, the device b 310 may transmit the preparation response message rtt_ready.response to the device a 305 before the generation of the random number mask r_mask and may generate the random number mask r_mask before the reception of the preparation request message rtt_ready.command. the device a 305 generates a challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r), transmits the same to the device b 310 in operation 350, and measures a point in time when the challenge request message rtt_challenge(e sk (r)) is transmitted. the device b 310 receives the challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r) and then combines the random number mask r_mask with the encrypted random number e sk (r) according to an xor operation in order to generate a decrypted random number r', in operation 355. thereafter, in operation 360, the device b 310 generates a challenge response message rtt_response(r') including the decrypted random number r' and transmits the challenge response message rtt_response(r') to the device a 305. the device a 305 receives the challenge response message rtt_response(r') including the decrypted random number r' from the device b 310 and measures a point in time when the challenge response message rtt_response(r') is received. the device a 305 can determine an rtt by calculating a period of time ranging from when the device a 305 sends the challenge request message rtt_challenge(e sk (r)) to the device b 310 to when the device a 305 receives the challenge response message rtt_response(r') from the device b 310. as described above, the device b 310 can minimize a period of time from when the device b 310 receives the challenge request message rtt_challenge(e sk (r)) and when the device b 310 sends the challenge response message rtt_response(r'). operations 365 through 380 are similar to the operations 265 through 280 of fig. 2 , so detailed descriptions thereof will be omitted. fig. 4 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention. the present exemplary embodiment is the same as the exemplary embodiment of fig. 3 except that transmission and reception of the preparation request message rtt_ready.command and the preparation response message rtt_ready.response between devices a and b is omitted. if an arithmetic operating performance of a device b 410 is equal to or greater than that of a device a 405, the device a 405 is able to generate a random number mask r_mask while generating a challenge request message rtt_challenge(e sk (r)). thus, transmission and reception of a preparation request message rtt_ready.command and a preparation response message rtt_ready.response between the device a 405 and the device b 410 may be omitted. accordingly, the device b 410 may generate a random number mask r_mask in operation 435 before receiving the challenge request message rtt_challenge(e sk (r)) from the device a 405 in operation 440, and may generate the challenge response message rtt_response(r') by combining the encrypted random number e sk (r) received from the device a 405 with the generated random number mask r_mask according to an xor operation in operation 445. the remaining operations operate in manners similar to those used in figs. 2 and 3 , so descriptions thereof will be omitted. fig. 5 illustrates a challenge response based rtt checking system according to another exemplary embodiment of the present invention. in figs. 2 through 4 , a device a encrypts the random number r and transmits the result of the encryption as the challenge request message rtt_challenge(e sk (r)), and a device b transmits, as the challenge response message rtt_response(r'), a decrypted random number r' resulting from the decryption of the encrypted random number e sk (r). however, in the exemplary embodiment illustrated in fig. 5 , a device a 505 transmits a challenge request message rtt_challenge(r) including a non-encrypted random number r to a device b 510 in operation 515, and a device b 510 encrypts the random number r included in the challenge request message rtt_challenge(r) and transmits a result of the encryption as a challenge response message rtt_response(e sk (r')) in operation 520. the device a 505 can determine an rtt by measuring a point in time when the challenge request message rtt_challenge(r) is transmitted and a point in time when the challenge response message rtt_response(e sk (r')) is received. measurements are performed within the maximum number of repetitions. in addition, the device a 505 decrypts the received encrypted random number e sk (r') included in the challenge response message rtt_response(e sk (r')) and compares a result of the decryption with the random number r transmitted to the device b 510, thereby determining whether the device a 505 and the device b 510 are adjacent to each other. fig. 6 is a functional block diagram of a challenge response based rtt checking apparatus according to an exemplary embodiment of the present invention. the challenge response based rtt checking apparatus according to the current exemplary embodiment may be included in either a device a 610 or a device b 660. the challenge response based rtt checking apparatus in the former case is referred to as a first rtt checking apparatus, and the challenge response based rtt checking apparatus in the latter case is referred to as a second rtt checking apparatus. the first rtt checking apparatus includes a random number generation unit 615, an encryption unit 620, a communication unit 635, an rtt determination unit 640, and an adjacency determination unit 645. when rtt checking starts, the random number generation unit 615 generates the random number r. the encryption unit 620 encrypts the random number r generated in the random number generation unit 615 by using an sk shared by the device a 610 and the device b 660. the encryption unit 620 may include a random number mask generation unit 630 for generating the random number mask r_mask by using the sk, and a combination unit 625 for combining the random number mask r_mask with the random number r according to an xor operation. generation of the random number mask r_mask has been described above, so a description thereof will be omitted. the communication unit 635 transmits the challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r) to the device b 660, and receives the challenge response message rtt_response(r') including the decrypted random number r' from the device b 660. alternatively, the communication unit 635 may transmit the preparation request message rtt_ready.command to the device b 660 and receive the preparation response message rtt_ready.response from the device b 660. the rtt determination unit 640 determines an rtt by measuring a point in time when the challenge request message rtt_challenge(e sk (r)) is transmitted and a point in time when the challenge response message rtt_response(r') is received. the adjacency determination unit 645 may include a comparator 650 for comparing the rtt with a predetermined time limit (tl), and an authenticator 655. the predetermined tl is used to determine whether the device a 610 and the device b 660 are adjacent to each other, and has a predetermined value. tl may have different values according to the circumstances of the user. when the rtt is less than the tl, the authenticator 655 compares the random number r with the random number r' included in the challenge response message rtt_response(r') so as to authenticate the device b 660. although not shown, when the rtt is equal to or greater than the tl, the comparator 650 may generate a feedback signal for repeating rtt checking within the predetermined maximum number of repetitions and provide the feedback signal to the random number generation unit 615, the random number mask generation unit 630, etc. the second rtt checking apparatus includes a communication unit 665 and a decryption unit 670. the communication unit 665 receives the challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r) from the device a 610. the communication unit 665 transmits the challenge response message rtt_response(r') including the decrypted random number r' to the device a 610. alternatively, the communication unit 665 may receive the preparation request message rtt_ready.command from the device a 610 and transmit the preparation response message rtt.ready.response to the device a 610. the decryption unit 670 decrypts the encrypted random number e sk (r) by using the sk so as to generate the random number r'. the decryption unit 670 may include a random number mask generation unit 675 and a combination unit 680. the random number mask generation unit 675 generates the random number mask r_mask using the sk before the challenge request message rtt_challenge(e sk (r)) is received by the communication unit 665. the combination unit 680 combines the encrypted random number e sk (r) included in the challenge request message rtt_challenge(e sk (r)) with the random number mask r_mask according to an xor operation and outputs a result of the combination to the communication unit 665. fig. 7 is a flowchart illustrating a challenge response based rtt checking method according to an exemplary embodiment of the present invention. referring to fig. 7 , in operation 705, a counter n is set to be 0. in operation 710, the random number r is generated. in operation 715, the random number r is encrypted using an sk. the operation 715 of encrypting the random number r may include the sub-operations of generating the random number mask r_mask by using the sk and combining the random number r with the random number mask r_mask according to an xor operation. in operation 720, the challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r) is transmitted to a predetermined device, and a point in time when the challenge request message rtt_challenge(e sk (r)) is transmitted is measured. in operation 725, the challenge response message rtt_response(r') including the decrypted random number r' is received from the predetermined device, and a point in time when the challenge response message rtt_response(r') is received is measured. in operation 730, an rtt is determined based on a difference between the point in time when the challenge response message rtt_response(r') is received and the point in time when the challenge request message rtt_challenge(e sk (r)) is transmitted. in operation 735, the rtt is compared with a predetermined tl. if it is determined in operation 735 that the rtt is less than the predetermined tl, the random number r is compared with the random number r' included in the challenge response message so as to authenticate the predetermined device, in operation 740. if the random number r is equal to the random number r' included in the challenge response message, the predetermined device is determined to be adjacent to another device with which rtt checking is performed, in operation 745. on the other hand, if the random number r is not equal to the random number r' included in the challenge response message, rtt checking is determined to be a failure, in operation 750. if it is determined in operation 735 that the rtt is equal to or greater than the predetermined tl, the counter n increases by 1, in operation 755. if it is determined in operation 760 that the counter n is less than a predetermined maximum number of repetitions, the method may be repeated by starting from operation 710. on the other hand, if it is determined in operation 760 that the counter n is equal to or greater than the predetermined maximum number of repetitions, the predetermined device is determined to be not adjacent to another device with which rtt checking is performed, in operation 765. the challenge response based rtt checking method according to the current exemplary embodiment may further include an operation (not shown) of transmitting the preparation request message rtt_ready.command to the predetermined device and receiving the preparation response message rtt_ready.response from the predetermined device. fig. 8 is a flowchart illustrating a challenge response based rtt checking method according to another exemplary embodiment of the present invention. referring to fig. 8 , in operation 810, before the challenge request message rtt_challenge(e sk (r)) is received, the random number mask r_mask is generated using an sk. in operation 820, the challenge request message rtt_challenge(e sk (r)) including the encrypted random number e sk (r) is received from a predetermined device. in operation 830, the encrypted random number e sk (r) is decrypted using the sk so as to generate the decrypted random number r'. the encrypted random number e sk (r) included in the challenge request message rtt_challenge(e sk (r)) may be combined with the random number mask r_mask according an xor operation. in operation 840, the challenge response message rtt_response(r') including the decrypted random number r' is transmitted to the predetermined device. the challenge response based rtt checking method according to the current exemplary embodiment may further include an operation (not shown) of receiving the preparation request message rtt_ready.command from the predetermined device and transmitting the preparation response message rtt_ready.response to the predetermined device. according to the exemplary embodiments of the present invention, adjacency between devices can be efficiently checked by applying a challenge response method using an encryption algorithm to rtt checking. in addition, due to the use of an encryption method capable of pre-computation during rtt checking, a time required to generate a challenge response message is minimized, and the reliability of rtt checking improves. the invention can also be embodied as computer readable codes on a computer readable recording medium. the computer readable recording medium is any data storage device that can store data which can be thereafter read by a computer system. examples of the computer readable recording medium include read-only memory (rom), random-access memory (ram), cd-roms, magnetic tapes, floppy disks, optical data storage devices, etc. the computer readable recording medium can also be distributed over network coupled computer systems so that the computer readable code is stored and executed in a distributed fashion. while the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. all of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. the invention is not restricted to the details of the foregoing embodiment(s). the invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
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093-848-922-154-172
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JP
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[
"US",
"JP"
] |
H01L21/336,H01L27/115,H01L21/8247,H01L29/788,H01L29/792
| 2005-12-28T00:00:00 |
2005
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[
"H01"
] |
semiconductor memory device and method of fabricating the same
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a semiconductor memory device includes: a semiconductor substrate, on which an impurity diffusion layer is formed in a cell array area; a gate wiring stack body formed on the cell array area, in which multiple gate wirings are stacked and separated from each other with insulating films; a gate insulating film formed on the side surface of the gate wiring stack body, in which an insulating charge storage layer is contained; pillar-shaped semiconductor layers arranged along the gate wiring stack body, one side surfaces of which are opposed to the gate wiring stack body via the gate insulating film, each pillar-shaped semiconductor layer having the same conductivity type as the impurity diffusion layer; and data lines formed to be in contact with the upper surfaces of the pillar-shaped semiconductor layers and intersect the gate wirings.
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1 . a method of fabricating a semiconductor memory device comprising: forming a plurality of polycrystalline silicon films, which are stacked and separated from each other with insulating films interposed therebetween, in a cell array formation area of a semiconductor substrate; etching the stack structure of the polycrystalline silicon films and the insulating films to form a gate wiring stack body with an elongate pattern, in which a plurality of gate wirings are stacked via the insulating films; forming a gate insulating film on a first side surface of the gate wiring stack body, in which an insulating charge storage layer is formed; forming a plurality of pillar-shaped semiconductor layers with the same conductivity type as the impurity diffusion layer and a lower impurity concentration than the impurity diffusion layer, which are arranged in the elongated direction of the gate wiring stack body and opposed to the first side surface of the gate wiring stack body via the gate insulating film; forming a metal film on the second side surface of the gate wiring stack body, and annealing it to make the gate wirings silicides; and forming data lines to be in contact with the upper surfaces of the pillar-shaped semiconductor layers and intersect the gate wirings. 2 . the method according to claim 1 , wherein the procedure of forming the gate insulating film comprises: sequentially depositing a first silicon oxide film, a silicon nitride film serving as the charge storage layer and a second silicon oxide film or another insulator film with a dielectric coefficient higher than the silicon oxide to form the gate insulating film; and removing the gate insulating film except that disposed on the first side surface of the gate wiring stack body. 3 . the method according to claim 1 , wherein the procedure of forming the pillar-shaped semiconductor layers comprises: forming a semiconductor layer on the semiconductor substrate, on which the gate wiring stack body is formed with the gate insulating film formed on the first side surface of the gate wiring stack body; annealing the semiconductor layer to crystallize it; and patterning the semiconductor layer to divide it into a plurality of the pillar-shaped semiconductor layers.
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cross-reference to related application this application is a continuation of u.s. ser. no. 11/616,522, filed dec. 27, 2006, which claims priority under 35 u.s.c. 119(a)-(d) to japanese patent application no. 2005-379017, filed on dec. 28, 2005, the entire contents of both of which are incorporated herein by reference. background of the invention 1. field of the invention this invention relates to an electrically rewritable and non-volatile semiconductor memory device (eeprom), more particularly relates to such a device that multiple memory cells are stacked on a semiconductor substrate to constitute a nand cell unit, and a method of fabricating the same. 2. description of the related art a nand-type flash memory is known as one of eeproms. in the nand-type flash memory, multiple memory cells are connected in series in such a manner that adjacent two cells share a source/drain diffusion layer, thereby constituting a nand cell unit. by use of this cell array arrangement, the unit cell area is smaller that that of a nor-type one, and it is easy to increase the capacitance. further, since the nand-type flash memory uses tunneling current for writing data, the consumption current is smaller than that of the nor-type one, which uses hot-carrier injection. therefore, it is possible to make a page capacitance defined as a simultaneously written cell range large, whereby it becomes possible to perform high-speed write/read. to make the storage density of a unit area higher with the conventional structure, in which memory cells are formed in a single layer, it is in need of progressing the miniaturization or using a multi-level storage scheme. however, there is a limit for miniaturization. the increase of memory density based on the multi-level storage scheme also has a limit defined by data reliability. by contrast, to make a nand-type flash memory highly integrated, there has already been provided such a scheme as to stack memory cells on the semiconductor substrate (for example, refer to patent document 1: unexamined japanese patent application publication no. 2005-85938). however, there are some problems in the disclosed method in this document as follows. first, the channel regions and source/drain regions of memory cells in the nand cell unit are formed to have different conductivity types from each other like that in the conventional, planar type nand cell unit. therefore, as the nand cell unit is more miniaturized, the short-channel effect will become larger. second, in case the number of stacked memory cells is increased, i.e., the height of the memory cell unit (unit length) is enlarged, the aspect ratio also is increased. it will not only injure the process reliability but also cause the memory cell's operation delay. third, to achieve such a structure that a floating gate and a control gate are stacked in perpendicular to the side wall of a semiconductor pillar, it is necessary to repeatedly bury a highly resistive dielectric film for every memory cell formation process. therefore, the number of processes is increased in proportion to the number of memory cells, and it leads to reliability reduction. another nand-type flash memory, which has a possibility of solving the above described problems, has already been provided prior to the above-described patent application (refer to patent document 2: unexamined japanese patent application publication no. 10-93083). in this document 2, there is disclosed a nand-type flash memory with vertical memory cells stacked, in which a gate wiring stack structure is previously formed, and semiconductor activation layers are formed opposite to the sidewalls of the gate wirings, respectively, with gate insulating films interposed therebetween. however, in the patent document 2, after having patterned the gate wiring stack body and prior to the silicon layer formation, the source diffusion layer of nand cell units (nand strings) is formed by a selective diffusion method. this is because of that in case of p-type of channel bodies, and n-channel type of nand cell units, it is in need of making the p-type silicon layer contacted with the p-type substrate. however, according to this method, the select gate transistor formed at the lowest portion of the silicon layer becomes to have an offset gate structure, in which the source diffusion layer is formed as separated from the gate edge. there is not provided a measure for avoiding such the problem. if as it is, it is impossible to achieve a desired operation of a nand-type flash memory further, in the patent document 2, a polycrystalline silicon film is used as word lines and select gate lines. therefore, there is a limit for making the resistance of the word lines and select gate lines low, and it is difficult to achieve a usual nand-type flash memory. summary of the invention according to an aspect of the present invention, there is provided a semiconductor device including: a semiconductor substrate; an impurity diffusion layer formed in a cell array area of the semiconductor substrate to serve as a common source line in the cell array; a gate wiring stack body formed on the cell array area of the substrate with an elongate pattern, in which multiple gate wirings are stacked and separated from each other with insulating films interposed therebetween; a gate insulating film formed on the side surface of the gate wiring stack body, in which an insulating charge storage layer is contained; a plurality of pillar-shaped semiconductor layers arranged in the elongated direction of the gate wiring stack body at a certain pitch, at least one side surfaces of which are opposed to the gate wiring stack body via the gate insulating film, other side surfaces thereof being in contact with a device isolating dielectric film, each the pillar-shaped semiconductor layer having the same conductivity type as the impurity diffusion layer and a lower impurity concentration than the impurity diffusion layer; and data lines formed to be in contact with the upper surfaces of the pillar-shaped semiconductor layers and intersect the gate wirings. according to another aspect of the present invention, there is provided a method of fabricating a semiconductor memory device including: forming a plurality of polycrystalline silicon films, which are stacked and separated from each other with insulating films interposed therebetween, in a cell array formation area of a semiconductor substrate; etching the stack structure of the polycrystalline silicon films and the insulating films to form a gate wiring stack body with an elongate pattern, in which a plurality of gate wirings are stacked via the insulating films; forming a gate insulating film on a first side surface of the gate wiring stack body, in which an insulating charge storage layer is formed; forming a plurality of pillar-shaped semiconductor layers with the same conductivity type as the impurity diffusion layer and a lower impurity concentration than the impurity diffusion layer, which are arranged in the elongated direction of the gate wiring stack body and opposed to the first side surface of the gate wiring stack body via the gate insulating film; forming a metal film on the second side surface of the gate wiring stack body, and annealing it to make the gate wirings silicides; and forming data lines to be in contact with the upper surfaces of the pillar-shaped semiconductor layers and intersect the gate wirings. brief description of the drawings fig. 1 is a plan view of a memory cell array in a nand-type flash memory in accordance with an embodiment of the present invention. fig. 2 is a sectional view taken along line i-i′ in fig. 1 . fig. 3 is a sectional view taken along line ii-ii′ in fig. 1 . fig. 4 is a sectional view taken along line iii-iii′ in fig. 1 . fig. 5 is an enlarged sectional view of one memory cell in fig. 2 . fig. 6 shows an equivalent circuit of the memory cell array. fig. 7 shows bias voltage relationships for explaining the erase operation of the flash memory. fig. 8 shows bias voltage relationships for explaining the read operation of the flash memory. fig. 9 shows bias voltage relationships for explaining the write operation of the flash memory. fig. 10 shows the step of depositing the gate wiring material film of the flash memory. fig. 11 shows the step of patterning the gate wiring material film. fig. 12 shows the step of forming the gate insulating film. fig. 13 shows the step of etching the gate insulating film. fig. 14 shows the step of forming an insulating film of one side surface of the gate wiring stack body. fig. 15 shows the step of forming a silicon layer serving as a memory cell activation layer. fig. 16 shows the step of etching the silicon layer to be remained on one side surface of the gate wiring stack body. fig. 17 shows the step of depositing an insulating film and planarizing it. fig. 18 shows a resist mask pattern used for etching the silicon layer. fig. 19 shows the step of insulating film etching and silicon etching with the resist mask. fig. 20 is the iii-iii′ sectional view showing the state that the silicon layer is divided into pillar-shaped silicon layers. fig. 21 shows the structure of drawing portions of the gate wirings. fig. 22 is a sectional view of the flash memory including the peripheral circuit area. fig. 23 is a plan view of a memory cell array in accordance with another embodiment. fig. 24 is a sectional view taken along line i-i′ in fig. 23 . fig. 25 is a plan view of a memory cell array in accordance with another embodiment. fig. 26 is a sectional view taken along line i-i′ in fig. 25 . fig. 27 is a plan view of a memory cell array in accordance with another embodiment. fig. 28 is a sectional view taken along line i-i′ in fig. 27 . fig. 29 is a plan view of a memory cell array in accordance with another embodiment. fig. 30 is a sectional view taken along line i-i′ in fig. 29 . fig. 31 is a sectional view taken along iii-iii′ in fig. 29 in case the bit lines are formed of a single layer. fig. 32 is a sectional view taken along iii-iii′ in fig. 29 in case the bit lines are formed of two layers. fig. 33 is a plan view of a memory cell array in accordance with another embodiment. fig. 34 is a sectional view taken along line i-i′ in fig. 33 . fig. 35 is a plan view of a memory cell array in accordance with another embodiment. fig. 36 is a sectional view taken along line i-i′ in fig. 35 . fig. 37 is a diagram for explaining the read bias condition in the cell array shown in fig. 25 . fig. 38 is a diagram for showing four-level data threshold distributions and the data bit assignment. fig. 39 is a sectional view for showing the step of stacking polycrystalline silicon films of a flash memory in accordance with another embodiment. fig. 40 is a sectional view for showing the step of patterning the polycrystalline silicon films. fig. 41 is a sectional view for showing the steps of: forming gate insulating film on the side surface of the gate wiring stack body; and forming the pillar-shaped silicon layers. fig. 42 is a sectional view for showing the step of etching the gate wiring stack body. fig. 43 is a sectional view for showing the salicide step of making the gate wirings of the gate wiring stack body and gate, source and drain of the peripheral transistor silicides. fig. 44 is a sectional view for showing the step of forming the interlayer dielectric film covering the cell array area and peripheral circuit area. fig. 45 is a sectional view for showing a nand cell unit structure, in which the lower side select gate transistor's gate insulating film has no charge storage layer. fig. 46 is a sectional view for showing a nand cell unit structure, in which the upper side select gate transistor's gate insulating film has no charge storage layer. fig. 47 is a sectional view for showing a nand cell unit structure, in which the upper and lower side select gate transistors' gate insulating film has no charge storage layer. fig. 48 is a sectional view for showing the step of forming the gate wiring stack body shown in fig. 45 . fig. 49 is a sectional view for showing the step of forming the gate insulating film 3 s without a charge storage layer. fig. 50 is a sectional view for showing the step of burying the mask material film. fig. 51 is a sectional view for showing the step of etching the gate insulating film 3 s. fig. 52 is a sectional view for showing the step of forming the gate insulating film with the charge storage layer. fig. 53 is a sectional view for showing the step of removing the mask material film to expose the substrate. fig. 54 is a sectional view for showing the steps of: forming a silicon layer; and crystallizing anneal thereof. fig. 55 is a sectional view for showing the step of forming contact diffusion layer. fig. 56 is a sectional view for showing the step of forming the interlayer dielectric film. fig. 57 is a sectional view for showing the step of forming the bit lines. fig. 58 is a sectional view for showing the step of burying the mask material film as followed the step shown in fig. 53 for forming the structure shown in fig. 47 . fig. 59 is a sectional view for showing the step of etching the gate insulating film 3 . fig. 60 is a sectional view for showing the step of forming the gate insulating film 3 d without a charge storage layer. fig. 61 is a sectional view for showing the step of removing the mask material film to expose the substrate. fig. 62 is a sectional view for showing the steps of: forming a silicon layer; and crystallizing anneal thereof. fig. 63 is a sectional view for showing the step of forming contact diffusion layer. fig. 64 is a sectional view for showing the step of forming the interlayer dielectric film. fig. 65 is a sectional view for showing the step of forming the bit lines. detailed description of the embodiments illustrative embodiments of this invention will be explained with reference to the accompanying drawings below. embodiment 1 fig. 1 is a plan view of a memory cell array of a nand-type flash memory in accordance with an embodiment, and figs. 2 , 3 and 4 are sectional views thereof taken along lines i-i′, ii-ii′ and iii-iii′ in fig. 1 , respectively. a plurality of gate wiring stack bodies 2 are formed on a silicon substrate 1 , each of which has multiple gate wirings 21 stacked and separated from each other with interlayer dielectric films 5 interposed therebetween. each of the gate wiring stack bodies 2 is patterned as elongated in x-direction in the x-y plane of the substrate 1 . the gate wirings 21 are formed of a metal film, the resistance of which is lower than that of a polycrystalline silicon film, for example, selected from tungsten (w), aluminum (al), cupper (cu), silicide thereof and the like. alternatively, the gate wirings 21 may be initially formed as polycrystalline silicon wirings, and then reformed as silicide wirings by a salicide (self aligned silicide) step. as a result, it is possible to form so low-resistive gate wirings as not been achieved when a polycrystalline silicon film is used. explaining in detail, in the stacked gate wirings 21 , the lowest and the uppermost ones serve as select gate lines (sgs and sgd), which are gates of the vertical select gate transistors; and four wirings disposed between them serve as word lines wl (wl 0 -wl 3 ), which are control gates of memory cells. the thickness of the gate wirings serving as the select gate lines sgs and sgd, i.e., gate length, is set to be larger than that of gate lines of memory cells (i.e., word lines). this is for making the cut-off property of the select gate transistors good. although, in this example, one nand cell unit is formed of four word lines, the present invention is not limited to this example. formed on one side surface of the gate wiring stack body 2 is a gate insulating film 3 , in which an insulating charge storage layer is formed. pillar-shaped silicon layers 4 , which serve as activation layers of memory cells, are formed to be opposite to the side surface of the gate wiring stack body 2 via the gate insulating film 3 . the silicon layers 4 are formed pillar-shaped with about the same height as the gate wiring stack bodies 2 , and arranged at a certain pitch in the elongated direction (i.e., x-direction) of the gate wiring stack bodies 2 . side surfaces of the pillar-shaped silicon layer 4 are in contact with device isolating dielectric film 6 except that opposite to the gate wiring stack body 2 . the pillar-shaped silicon layer 4 is n − -type one with a low impurity concentration, on the top surface of which an n + -type of diffusion layer 42 is formed for bit line contacting. on the bottom surface of the silicon layer 4 , another n + -type of diffusion layer 41 is formed due to impurity diffusion from the n + -type of diffusion layer 11 formed on the surface of the substrate 1 . the n + -type layer 11 is formed on the whole surface of the memory cell array area and it serves as a common source line of the cell array. as shown by a dotted line in fig. 2 , one gate wiring (word line) 21 and one pillar-type silicon layer 4 disposed opposite to it with the gate insulating film 3 interposed therebetween constitute an electrically rewritable and non-volatile memory cell, cell. this memory cell is a vertical cell with a gate length (i.e., channel length) defined by the thickness of the gate wiring 21 . multiple memory cells are stacked to constitute a nand cell unit (nand string). fig. 5 is an enlarged sectional view of a memory cell. the gate insulating film 3 is a laminated one, the medium layer 32 of which has a function of a charge storage layer. for example, this laminated film is a so-called ono film, which is formed of silicon oxide film 31 , silicon nitride film 32 and silicon oxide film 33 . note here that other insulating films may be used in place of the silicon nitride film 32 , and other insulating films may be used in place of the silicon oxide film 33 , which have dielectric coefficient higher than the silicon oxide film. this memory cell is conventionally referred to as a monos (metal oxide nitride oxide semiconductor)-type of cell. in this memory cell, since the entire gate insulating film including the charge storage layer is an insulator film, there is no need of using a process for separating the floating gates for every cell as different from the floating gate type memory cell. that is, the gate insulating film 3 may be formed over the side surface of the gate wiring stack body 2 , and it is not necessary to pattern it. as a result, the stacked structure of the vertical cells may be easily achieved. it is difficult in technique to selectively form source and drain diffusion layers of the memory cells to be stacked by ion implantation and the like. therefore, in this embodiment, source and drain diffusion layers are not formed in the n − -type of pillar-shaped silicon layer 4 except n + -type layers 41 and 42 formed on the bottom and top surfaces, respectively. in other words, the n − -type of silicon layer 4 is used as channel regions, source and drain regions as it is. for this reason, the threshold voltage of the select gate transistors may be negative, and a negative voltage may be used to turn off the select gate transistors as described later. the top surfaces of the nand cell units are covered by an insulating film 6 , on which data lines, i.e., bit lines 7 are formed. bit lines 7 are pattered to be elongated in y-direction and in contact with the upper diffusion layers 42 of the nand cell units. fig. 6 shows an equivalent circuit of the memory cell array arranged with nand cell units each having stacked vertical cells as described above. gate wirings 21 of the memory cells m 0 -m 3 serve as word lines wl 0 -wl 3 , respectively; and gate wirings 21 of the select gate transistors sg 1 and sg 2 serve as select gate lines sgd and sgs, respectively. n + -type diffusion layer 11 formed on the cell array area of the substrate 1 serves as the common source line cersrc. a set of nand cell units arranged in the direction of the word lines constitutes a block, which serves as an erase unit. the operations of the nand-type flash memory in accordance with this embodiment will be explained below. the memory cell array is initially set in an erase state (refer to as, for example, data “1” state) with a negative threshold voltage, and it will be written into such a state that memory cells are selectively set in a positive threshold state (refer to as data “0” state). this is a basic binary data storage scheme. setting more threshold levels, multi-level data storage may be performed. for example, setting three positive threshold voltages, it will be achieved a four-level storage. data erase is performed by a block. as shown in fig. 7 , with respect to a selected block, the select gate lines sgd and sgs, and bit lines bl are set in a floating state; all word lines are set at 0v; and a boosted and positive erase voltage vera is applied to the common source line celsrc. as a result, electrons stored in the charge storage layers in the selected block will be discharged, resulting in that the memory cells are erased in a state of a negative threshold voltage. in non-selected blocks, the select gate lines sgd, sgs, bit lines bl and word lines wl are set in a floating state. these floating nodes are boosted in potential by capacitive coupling, so that a large electric field is not applied between the charge storage layers and the silicon pillar layer, and data are not erased. further, the boosted potential of the non-selected block disposed adjacent to the selected block will not step-down in potential the pillar-shaped silicon layer in the selected block, and serve for keeping the potential of the pillar-shaped silicon layer in the selected block necessary for erasing. data read is performed, as shown in fig. 8 , under the condition that with respect to a selected block, select gate lines are applied with a positive voltage to sufficiently turn on the select gate transistors; a selected word line with 0v; and the remaining non-selected word lines with a positive read pass voltage vread, which turns off cells without regard to cell data. the common source line celsrc is set at 0v. the bit lines are initially precharged to a certain voltage vbl, and then set in a floating state. as a result, the bit lines will be discharged in accordance with selected cell data. therefore, detecting the bit line voltage after a certain bit line discharge operation, data will be read out. in the non-selected blocks, as shown in fig. 8 , select gate lines sgd and sgs are applied with a negative voltage, which keeps the select gate transistors off. as a result, the non-selected blocks are separated from the bit lines. data write is, as shown in fig. 9 , performed under the condition of that with respect to a selected block, the source line side select gate line sgs is applied with a negative voltage to keep the select gate transistor sg 2 off; the bit line side select gate line sgd with a positive voltage vsg to turn on the select gate transistor sg 1 ; a selected word line with a boosted and positive write voltage vpgm; and non-selected word lines with a write pass voltage (medium voltage) vm (<vpgm). applied to the bit lines are vss (=0v) in case of “0” write; and vdd in case of “1” write (i.e., write inhibiting) in accordance with write data. with these bit line voltages, in case of “0” write, selected nand cell channels are set at 0v while in case of “1” write, the sources of the bit line side select gate transistors are boosted to vsg-vth (vth is the threshold voltage of the select gate transistors), resulting in that the selected nand cell channels are set in a floating state. as a result, in the “0” write cell, electrons are injected into the charge storage layer, and the cell threshold voltage is made positive. by contrast, in the “1” write cell, the cell channel is boosted in potential by capacitive coupling. therefore, electron injection does not occur, thereby keeping the “1” write cell in the erase state (“1” data state) as it is. in non-selected blocks, applying 0v to all word lines; and applying 0v or a negative voltage to the select gate lines sgs and sgd with, the nand cell units are kept as separated from the bit lines. next, the fabrication steps of the flash memory in accordance with this embodiment will be explained with reference to figs. 10-20 below. figs. 10-17 and 19 are perspective views of the respective fabrication steps, in which i-i′ sectional views corresponding to that shown in fig. 2 are shown. on the silicon substrate 1 , n + -type diffusion layer 11 is formed on the whole cell array formation area. as shown in fig. 10 , after having formed an interlayer dielectric film 5 , a wiring material film 20 is formed thereon. repeatedly performing the same film formation, multiple gate wiring material films 20 are stacked as separated from each other with the interlayer dielectric films 5 . the gate wiring material film 20 is tungsten(w) film or silicide thereof (wsi) in this embodiment, but other high-melting point metals or silicide thereof may be used. following it, as shown in fig. 11 , vertically etch the stacked structure of the gate wiring material films by rie, and divide it into plural gate wiring stack bodies 2 separated from each other, each of which has plural gate wirings 21 stacked and a stripe pattern elongated in x-direction. this strip-shaped gate wiring stack body 2 is formed in such a state that gate wirings 21 and dielectric films 5 are alternately exposed on the side surfaces (x-z planes) thereof. next, as shown in fig. 12 , gate insulating film 3 is deposited with a good step-coverage deposition method in such a manner that it is formed on the side surfaces of the gate wiring stack bodies 2 with a constant thickness. as described above, the gate insulating film 3 has a stacked structure of silicon oxide film/silicon nitride film/silicon oxide film. the gate insulating film 3 is, as shown in fig. 13 , subjected to etch-back, and remained only on the side surfaces of each gate wiring stack body 2 . next, after having deposited and planarized insulating film 31 to be buried in the spaces between the gate wiring stack bodies 2 , as shown in fig. 14 , it is selectively etched by rie to expose only one side surface (on which activation layer is to be formed) of the gate wiring stack body 2 . following it, as shown in fig. 15 , amorphous silicon layer 40 is deposited and subjected to annealing treatment. as a result, the silicon layer 40 is crystallized due to solid-phase epitaxial growth by use of the silicon substrate 1 as a seed. in detail, the silicon layer 40 is n − -type layer with relatively low impurity concentration such as 10e19/cm 3 or less. in the crystallizing anneal process, impurities in the n + -type layer 11 formed on the surface of the substrate 1 are diffused into the silicon layer 40 , so that n + -type diffusion layer 41 is formed on the bottom of the silicon layer 40 . the diffusion layer 41 is formed in such a manner that upper surface thereof reaches the bottom surface of the lowest gate wiring 21 (i.e., select gate line sgs), thereby preventing the select gate transistor from being in a gate-offset state. if necessary for this purpose, annealing may be performed in addition to the crystallizing anneal process. then, as shown in fig. 16 , the silicon layer 40 is etched to be remained only on one side surface of the gate wiring stack body 2 . in this state, n-type impurity ions are implanted, and n + -type layers 42 are formed on the top surfaces of the silicon layers 40 formed on the side surfaces of the gate wiring stack bodies 2 and separated from each other, each of which serves as a bit line contact. next, as shown in fig. 17 , insulating film 32 is deposited and planarized. thereafter, the silicon layers 40 , which are elongated in x-direction at this stage, will be processed to become multiple pillar-shaped silicon layers arranged in x-direction at a certain pitch. for this purpose, as shown in fig. 18 , resist pattern 33 is formed on the planarized surface of the insulating film 32 , which has etching openings 33 a for dividing the silicon layer 40 into plural layers arranged at a certain pitch in the x-direction. with this resist pattern 33 , the insulating film 32 is etched so as to expose the silicon layer 40 at a first step, and then the exposed silicon layer 40 is etched so as to expose the silicon substrate 1 . fig. 19 shows such a state that windows 33 b are formed in the insulating film 32 corresponding to the openings 33 a of the resist pattern 33 . etching the silicon layer 40 via the windows 33 b, as shown in fig. 20 (iii-iii′ sectional view of fig. 1 ), pillar-shaped silicon layers 4 are dispersedly formed to be arranged along each gate wiring stack body 2 at a certain pitch. thereafter, as explained with reference to figs. 1 to 4 , insulating film 6 is further deposited; contact holes are formed therein; and bit lines 7 are formed to be in contact with n + -type layers 42 on the top surfaces of the pillar-shaped silicon layers 4 . as a result, the memory cell array formation will be completed. one side surface of each pillar-shaped silicon layer 4 is opposite to the gate wiring stack body 2 , and the remaining side surfaces are in contact with the device isolating film gate formed of insulating films 32 and 6 . fig. 21 shows a drawing structure of the stacked gate wirings 21 . as shown in fig. 21 , the extended portions of the gate wirings 21 from the cell array area edge are formed in such a state that the lower, the longer, and contact pugs 35 are buried in the interlayer insulating film 36 to be in contact with the end portions of the gate wirings 21 , respectively. as a result, the gate wirings 21 will be coupled to the corresponding metal wirings (not shown) to be formed on the insulating film 36 . according to this embodiment, the gate wiring stack body is formed with the steps of: alternately depositing gate wiring films and insulating films; and etching the stacked structure to be stripe-shaped. the gate material films exposed on the side surfaces of the gate wiring stack body are used as gate electrodes, on the side surface of which a gate insulating film including charge storage layer and an activation silicon layer are formed, and then the silicon layer is subjected to separation process to be formed as pillar-shaped silicon layers, each of which serves as a vertically stacked nand cell unit. according to the method shown in patent document 1, in which a pillar-shaped silicon layer is initially formed, and then select gate lines and word lines are formed to surround the silicon layer, the line/space formation process of the select gate lines and word lines is too complicated to realize the structure. by contrast, in this embodiment, after having formed the gate wiring stack body, the gate insulating film and the pillar-shaped silicon layer are formed. therefore, it is able to form the gate wiring stack body by alternately depositing the gate electrode material films and the insulating films on a plane semiconductor substrate. in other words, the gate wiring stack body may be easily formed with a precise size. further, in case the memory cells are vertically stacked, it is difficult in the process technology to form source/drain diffusion layers thereof or charge storage layers thereof for every memory cell. in consideration of this point, in this embodiment, n − -type silicon activation layer is used as sources, drains and channel regions of the vertically stacked memory cells as it is, resulting in that there is no need of performing selective ion implantation. in case the pillar-shaped silicon layer (i.e., channel body) is formed as p-type one, as shown in patent document 2, to make the channel body in contact with the p-type substrate without letting it be floating, it is necessary to selectively form the source diffusion layers. by contrast, in this embodiment, the pillar-shaped silicon layer is formed as n − -type one, and source/drain diffusion layers are not formed in the vertically stacked memory cells. therefore, n + -type diffusion layer is previously formed on the whole memory cell array area, and it serves as a common source line of the cell array. as a result, the potential of the channel bodies of all nand cell units is defined by the common source line. besides, the memory cell is formed to have a monos structure (i.e., the charge storage layer is insulating), in which it is unnecessary to form floating gate-type charge storage layers for every memory cell. as a result, vertically stacked memory cells may be formed with a good controllability. as described above, it is easy to form the vertically stacked structure of the vertical memory transistors, and possible to make the unit cell area of the cell array sufficiently smaller than that of the conventional nand-type flash memory. since the gate wiring is formed of a metal film, such as w or wsi film, with low resistivity, it is able to achieve a flash memory with a practical memory density and sufficiently low-resistive word lines and select gate lines. fig. 22 is a sectional view showing the nand-type flash memory including the peripheral circuit area. supposing that the silicon substrate 1 is p-type, on which n + -type diffusion layer 11 is formed as the common source line of the cell array, pmos transistor qp in the peripheral circuit is formed on n-type well 12 ; and nmos transistor qn on the p-type silicon substrate 1 . as a result, the peripheral circuit is formed as a cmos circuit. examples of memory cell arrays in accordance with other embodiments will be explained below. in the embodiments described below, parts corresponding to those in the embodiment 1 will be shown with the same reference symbols in the embodiment 1, and explanation thereof will be omitted. embodiment 2 figs. 23 and 24 are a plan view and i-i′ sectional view thereof, respectively, of a memory cell array in a nand-type flash memory in accordance with embodiment 2, which correspond to figs. 1 and 2 , respectively. in embodiment 1, pillar-shaped silicon layers 4 are disposed in relation with the gate wiring stack bodies 2 in such a manner that one array is opposite to one side surface of a gate wiring stack body; and the following one to the reverse side surface of the following gate wiring stack body. by contrast, in this embodiment, pillar-type silicon layers 4 are disposed opposite to the same side surfaces of the respective gate wiring stack bodies 2 . others are the same as in embodiment 1. that is, one side surface of the pillar-shaped silicon layer 4 is opposite to the gate wiring stack body 2 while the remaining three side surfaces are in contact with device isolating film; ii-ii′ and iii-iii′ sectional views of fig. 23 are identical with those shown in figs. 3 and 4 ; and fabrication processes are the same as in embodiment 1. therefore, according to this embodiment 2, the same effects as in embodiment 1 will be obtained. embodiment 3 fig. 25 is a plan view of a memory cell array in a nand-type flash memory in accordance with embodiment 3, which corresponds to fig. 1 in embodiment 1. fig. 26 is i-i′ sectional view of fig. 25 . ii-ii′ and iii-iii′ sectional views of fig. 25 are identical with those shown in figs. 3 and 4 ; and fabrication processes are the same as in embodiment 1. in embodiment 1, two arrays of pillar-shaped silicon layers 4 are disposed between two gate wiring stack bodies 2 to be driven with them. by contrast, in this embodiment 3, adjacent two gate wiring stack bodies share one array of pillar-shaped silicon layers 4 . in other words, in embodiments 1 and 2, one side surface of each pillar-shaped silicon layer 4 is opposite to the gate wiring stack body 2 and the remaining three side surfaces are in contact with the device isolating film, while in this embodiment 3, opposite side surfaces of the pillar-shaped silicon layer 4 are opposite to adjacent two gate wiring stack bodies 2 , respectively; and the remaining two side surfaces are in contact with the device isolating film. according to this embodiment, since two side surfaces of one pillar-shape silicon layer 4 are used, the same cell density as embodiment 1 will be obtained with the half number of the pillar-shaped silicon layers 4 in comparison with embodiment 1. that is, it is possible to achieve high integration of the memory cells. in case two nand cell units share one pillar-shaped silicon layer as channel bodies thereof, if the width of the pillar-shaped silicon layer is made smaller than a certain value, the interference between two nand cell units sharing the pillar-shape silicon layer will become larger. although the detail will be explained later, it may cause wasteful current in non-selected nand cell units in a read mode. a data read mode taking note of the above-described interference will be explained below with reference to figs. 37 and 38 . fig. 37 shows an equivalent circuit of two nand cell units sharing a pillar-shaped silicon layer 4 and a read bias condition thereof in a read mode. supposing that one memory cell stores four-level data, fig. 38 shows the data threshold distributions and the data bit assignment example. four-level data is defined by four data levels (threshold levels) l 0 , l 1 , l 2 and l 3 . the lowest level lo is a negative threshold state obtained by a collective erase while levels l 1 to l 3 are write states with positive threshold voltages. supposing that four-level data is expressed by (hb, lb), where hb is upper bit; and lb lower bit, the bit assignment is defined as follows. the lowest level l 0 is defined as data (1,1); following level l 1 is obtained by a lower bit write step, which selectively increases the threshold voltage of cells with data level (1,1), and defined as data (1,0); and levels l 2 and l 3 are obtained by a higher bit write step, which selectively increase the threshold voltages of cells with data levels (1,1) and (1,0), and defined as data (0,0) and (0,1), respectively. supposing that the above-described data write scheme is used, in case one of the two nand cell units shown in fig. 37 is selected while the other is non-selected, it is in need of avoiding the wasteful interference from the non-selected nand cell unit. for example, assume that there is a negative threshold cell with data (1,1) in the non-selected nand cell unit. in this case, even if a word line corresponding to the negative threshold cell is set at 0v, the channel is not made off. therefore, in the data read mode of the selected nand cell unit, a wasteful channel current flows through the on-cell in the non-selected nand cell unit in addition to the primary channel current. even if the select gate transistors in the non-selected nand cell unit are made off, it is impossible to avoid this phenomenon, and this leads to read error. particularly, in fig. 26 , in case the width d of the pillar-shaped silicon layer, i.e., the common channel body in the two nand cell units, is smaller than four times gate length l of each memory cell, the possibility of the above-described situation will become high. fig. 37 shows such a read bias condition that it is considered to avoid the interference described above. on the selected nand cell unit side, a word line corresponding to the selected cell (surrounded by a dotted line) is applied with read voltage r 0 (or r 1 , r 2 ); the remaining non-selected word lines are applied with pass voltage vread, which turns on cells without regard to cell data; and select gate lines are applied with vsg(on), which turns on the select gate transistors. the read voltages r 0 -r 2 are selected as shown in fig. 38 . that is, in case of reading the upper bit hb, read voltage r 1 , which is set between the data levels l 1 and l 2 , is used. in case of reading the lower bit lb when the upper bit hb is “1”, read voltage r 0 , which is set between the data levels l 0 and l 1 , is used. in case of reading the lower bit lb when the upper bit hb is “0”, read voltage r 2 , which is set between the data levels l 2 and l 3 , is used. as a result, cell current flows or not in the selected nand cell unit in accordance with that the selected cell is on or off. the cell current detection may be performed in such a way that the bit line is previously precharged, and then the sense amplifier detects whether the bit line is discharged or not. by contrast, in the non-selected nand cell units, all memory cells are set to be kept in a channel-off state without regard to cell data. that is, supposing that the memory cell's threshold voltage is vt; the common source line celsrc is set at vs; and the lower limit of the lowest data level l 0 is vtmin, all word lines are applied with vcg(off)=vtmin−δ+vss; and the select gate lines vsg(off)<vt+vs. the lower limit vtmin of the lowest data level l 0 is not judged when the data level l 0 is obtained with the collective erase operation. in addition, since over-erased cells are often generated, it is difficult to previously estimate the lower limit vtmin. to set the lower limit vtmin to be in a certain range, it is desirable to perform preliminary write with vtmin as a write-verify voltage after the collective erase. by use of this scheme, selecting the control voltage vcg(off) to be lower than the lower limit vtmin of data level l 0 by a certain level δ, it becomes possible to certainly make the channel of the non-selected nand cell unit off. adapting the read bias as described above, in case two nand cell units are formed as sharing a pillar-shaped silicon layer, it is possible to perform such a data read that the interference between the two nand cell units is removed or reduced. in case two nand cell units are formed to share a channel body, it is necessary to consider similarly in the case of not only the above-described four-level data storage but also a binary data storage scheme or other multi-level data storage schemes with more than four levels. that is, in case two nand cell units share a channel body, word lines in the non-selected nand cell unit side are biased so as to make the channel off without regard to cell data. as a result, it becomes possible to perform data read free from the interference between two nand cell units. embodiment 4 fig. 27 is a plan view of a memory cell array in accordance with embodiment 4, and fig. 28 is i-i′ sectional view of fig. 27 . ii-ii′ and iii-iii′ sectional views thereof are the same as figs. 3 and 4 , respectively; and the fabrication steps are the same as embodiment 1. in this embodiment, two arrays of the pillar-shaped silicon layers 4 are so disposed along each gate wiring stack body 2 as opposed to opposite side surfaces of the gate wiring stack body 2 via gate insulating films 3 . the two memory cells driven with a word line are disposed to share a bit line. in this case, two pillar-shaped silicon layers 4 sandwiching a gate wiring stack body 2 are not used as independent nand cell units, i.e., two memory cells sharing a bit line and a word line can not store data independently from each other. however, it becomes possible to improve the s/n ratio and data reliability because the signal charge quantity becomes large. this is effective particularly in case of using a multi-level data storage scheme. embodiment 5 fig. 29 is a plan view of a memory cell array in accordance with embodiment 5. as similar to embodiment 4 shown in fig. 27 , two arrays of the pillar-shaped silicon layers 4 are so disposed along each gate wiring stack body 2 as opposed to opposite side surfaces of the gate wiring stack body 2 via gate insulating films 3 . however, as different from embodiment 4, the two pillar-shaped silicon layers sandwiching a gate wiring stack body 2 are coupled to different bit lines 7 a and 7 b from each other. fig. 30 is i-i′ sectional view of fig. 29 . ii-ii′ sectional view thereof is basically the same as fig. 3 ; and the fabrication steps are the same as embodiment 1. as a result, although two pillar-shaped silicon layers sandwiching a gate wiring stack body 2 are driven with a common word line, these serve as different nand cell units for storing different data because these are coupled to different bit lines. bit lines 7 a and 7 b are formed by patterning a common conductive material film or formed with different conductive films. iii-iii′ sectional view shown in fig. 31 is the former case while that shown in fig. 32 is the latter case. embodiment 6 fig. 33 is a plan view of a memory cell array in accordance with embodiment 6. it is common to embodiment 4 shown in fig. 27 that adjacent two arrays of the pillar-shaped silicon layers 4 are opposed to opposite side surfaces of each gate wiring stack body 2 via the gate insulating films 3 . further, it is common to embodiment 3 shown in fig. 25 that adjacent two gate wiring stack bodies 2 are opposed to opposite side surfaces of each array of the pillar-shaped silicon layers 4 . two pillar-shaped silicon layers 4 sandwiching a gate wiring stack body 2 are coupled to a common bit line 7 . fig. 34 is i-i′ sectional view of fig. 33 . ii-ii′ and iii-iii′ sectional views of fig. 33 are the same as those in figs. 3 and 4 , respectively. the fabricating processes are the same as in embodiment 1. in this embodiment, two silicon layers 4 sandwiching a gate wiring stack body 2 are not used as independent nand cell units because two memory cells sharing a word line and a bit line can not store data independently of each other. however, it becomes possible to improve, particularly in case of multi-level storing, the s/n ratio and data reliability because the signal charge quantity becomes large. embodiment 7 fig. 35 is a plan view of a memory cell array in accordance with embodiment 7. the arrangement of the gate wiring stack bodies 2 and pillar-shaped silicon layers 4 is the same as that in embodiment 6 shown in fig. 33 , but it is different that two pillar-shaped silicon layers 4 opposed to opposite side surfaces of a gate wiring stack body 2 via the gate insulating films 3 are coupled to different bit lines 7 a and 7 b. as a result, although the two pillar-shaped silicon layers are driven simultaneously with a word line, these constitute independent nand cell units, which are able to store different data. bit lines 7 a and 7 b are formed of a conductive material film, or different conductive material films from each other. therefore, iii-iii′ sectional view of fig. 35 is the same as fig. 31 or fig. 33 . embodiment 8 in the above-described embodiments, w or wsi film is used as the stacked gate wirings, whereby low-resistive wirings may be achieved. by contrast, in case the gate wiring is formed of a polycrystalline film, the polycrystalline silicon wiring is preferably reformed as silicide wirings with a salicide (self aligned silicide) technology when the cell array formation has been about completed. the fabrication processes will be explained with reference to figs. 39 to 44 in accordance with such an embodiment 8. figs. 39 to 44 each shows the sectional view of the peripheral circuit area together with iii-iii′ sectional view of the cell array in embodiment 1. as shown in fig. 39 , a plurality of polycrystalline films, as gate electrode material films 20 , are stacked on the silicon substrate 1 in such a way that these are separated from each other with insulating films 5 . on the whole cell array area of the substrate 1 , n + -type diffusion layer 11 is formed like the above-described embodiments. on the peripheral circuit area, device isolating dielectric film 51 is buried with an sti (shallow trench isolation) method prior to the polycrystalline silicon stacking. as shown in fig. 40 , the polycrystalline silicon film stacked structure is etched to expose the cell array area of the substrate. as a result, a plurality of stripe-shaped gate wiring stack bodies 2 are formed as separated by grooves 52 . note here that the gate wiring stack bodies 2 at this stage are not separated perfectly as shown in fig. 11 in embodiment 1, but coupled two by two. thereafter, as shown in fig. 41 , gate insulating film 3 is formed on the side surface of the gate wiring stack bodies 2 with a charge storage layer formed therein; and then pillar-shaped silicon layers 4 are formed to be opposed to the side surface of the gate wiring stack bodies 2 via the gate insulating film 3 . a plurality of the pillar-shaped silicon layers 4 are arranged in perpendicular to the shown sectional view. in the bottom portions of the pillar-shaped silicon layers 4 , n + -type diffusion layers are formed in accordance with impurity diffusion from the substrate 1 ; and on the top portions of them, n + -type diffusion layers are formed by ion implantation. the above described processes from the step of forming the gate insulating film 3 to that of pillar-shaped silicon layers 4 are the same as in embodiment 1. thereafter, the cell array area is covered with interlayer insulating film 55 ; and formed thereon is silicon nitride film 56 a. by use of the silicon nitride film 56 a as a mask, the gate wiring stack body on the peripheral circuit area is removed, and peripheral transistors are formed as follows: polycrystalline silicon gate 63 is formed on the substrate 1 with a gate insulating film interposed therebetween; side wall insulating film is formed; and source/drain diffusion layers 54 are formed. following it, the silicon nitride film 56 a covering the cell array area is removed, and silicon nitride film 56 b is formed again, as shown in fig. 42 , to cover the whole surface. the silicon nitride film 56 b is patterned on the cell array area as a mask; and the gate wiring stack bodies 2 are etched to expose the substrate, whereby the final stack structure of the gate wirings 21 will be formed. in other words, grooves 57 are formed so as to divide each gate wiring stack body 2 into two pieces, in each of which becomes a bundle of word lines and select gate lines. all the while, the peripheral circuit area is kept in such a state that it is covered with the silicon nitride film 56 b. after having removed the silicon nitride film 56 b, as shown in fig. 43 , metal film 58 , such as co, ni or pd film, is formed by sputtering. although sputtering has poor step-coverage, it is not necessary more than that the metal film 58 is buried in the groove 57 formed between the gate wiring stack bodies 2 . even if voids are formed in the metal film 68 , there is no problem. annealing thereafter, metal penetrates into the polycrystalline silicon film 20 and interacts with it, so that silicide 59 is formed. in case metal film 58 is co or ni, silicide 59 hardly swells, so that it is formed without projecting itself from the side surface of the gate wirings 21 . particularly in case of co, it penetrates almost perfectly into the polycrystalline silicon film 20 and interacts with it, and the silicide 59 is formed within the polycrystalline silicon film 20 . at this salicide step, silicide 59 is also formed on gate electrode 53 , source and drain diffusion layers 54 in a self-aligned manner in the peripheral transistor. after the salicide step, un-reacted metal film 58 will be removed by wet etching. then, as shown in fig. 44 , interlayer dielectric film 60 is formed to cover the cell array area and the peripheral circuit area. following it, metal wirings such as bit lines are formed (not shown). according to this embodiment, stacked gate wirings (i.e., word lines and select gate lines) may be reformed as low-resistive wirings with the salicide technique. note here that in this embodiment, the salicide process has been adapted to not only the cell array area but also the peripheral circuit area. however, it is possible to use such options that the salicide process is not adapted to the peripheral circuit area, or the salicide process adapted to the peripheral circuit area is different from that adapted to the cell array area. embodiment 9 in the above-described embodiments, with respect to the vertically stacked nand cell unit, all memory cells and select gate transistors has a gate insulating film with a charge storage layer formed therein such as an ono film. however, to make the property of the nand cell unit more stabilized, it is desired that at least one of the upper and lower select gate transistors has such a gate insulating film that no charge storage layer is formed therein. figs. 45 to 47 are examples each showing the structure of one nand cell unit in accordance with embodiment 9. the portions corresponding to those in the above-described embodiments are designated with the same reference symbols as in the above-described embodiments, and the detail explanation will be omitted. fig. 45 shows such an example that the gate insulating film 3 s of the select gate transistor sg 2 disposed on the lower side, i.e., on the source line side, of the nand cell unit is formed as different from the gate insulating film 3 including the charge storage layer. fig. 46 shows another example, in which the gate insulating film 3 d of the select gate transistor sg 1 disposed on the upper side, i.e., on the bit line side, of the nand cell unit is formed as different from the gate insulating film 3 including the charge storage layer. fig. 47 shows still another example, in which the gate insulating films 3 d and 3 s of the select gate transistors sg 1 and sg 2 disposed on the both ends of the nand cell unit are formed as different from the gate insulating film 3 including the charge storage layer. the fabricating method of the nand cell unit shown in fig. 45 will be explained with reference to figs. 48 to 57 . what is explained here is for the cell array scheme shown in fig. 25 , in which two gate wiring stack bodies 2 share a pillar-shaped silicon layer 4 sandwiched therebetween. fig. 48 shows a state that the gate wiring stack bodies 2 with a plurality of wiring layers 21 stacked are patterned. so far, the fabricating processes are the same as in the above-described embodiments. thereafter, as shown in fig. 49 , gate insulating film 3 s, for example, silicon oxide film, in which no charge storage layer is formed, is formed. then, as shown in fig. 50 , mask material film 71 used for selectively etching the gate insulating film 3 s is deposited and etched-back, thereby being remained at the groove-bottom portion between the gate wiring stack bodies, i.e., at the formation portion of the lower side select gate transistor sg 2 . for example, in case the gate insulating film 3 s is sio 2 film, silicon nitride (sin) film is used as the mask material film 71 . alternatively, a polycrystalline silicon film may be used as the mask material film 71 because it is possible to select such an etching condition that the etching rate is lower than that of the silicon oxide film. following it, as shown in fig. 51 , by use of the mask material film 71 , the gate insulating film 3 s is etched and removed except the portion remained at the lower side select gate transistor. subsequently, as shown in fig. 52 , gate insulating film 3 including the charge storage layer is formed. then, removing the mask material film 71 , as shown in fig. 53 , the substrate surface between the gate wiring stack bodies 2 is exposed. thereafter, an amorphous silicon layer is deposited and subjected to crystallizing anneal, as shown in fig. 54 , n − -type silicon layer 4 is formed. on the bottom of the silicon layer 4 , n + -type diffusion layer 41 is formed in accordance with impurity diffusion from the substrate like in the above-described embodiments. following it, as shown in fig. 55 , diffusing impurities on the top portion of the silicon layer 4 , n + -type diffusion layer 42 is formed thereon. the silicon layer 4 is divided into pillar-shaped silicon layers arranged at a pitch in the elongated direction of the gate wiring stack bodies 2 . then, interlayer dielectric film 6 is formed as shown in fig. 56 ; and after having formed a contact hole, bit line 7 is formed as shown in fig. 57 as being in contact with the n + -type diffusion layer 42 . according to this embodiment, the operation of the lower side select gate transistor sg 2 in the nand cell unit is stabilized, and the property of the nand cell unit is stabilized. to form the structure shown in fig. 47 , in which both select gate transistors sg 1 and sg 2 have gate insulating films 3 d and 3 s with no charge storage layer, it is sufficient that after having formed the structure shown in fig. 53 , the steps shown in figs. 58 to 60 are adapted. that is, in the state shown in fig. 53 , mask material film 72 is, as shown in fig. 58 , deposited again and etched-back to be buried with such a height as to remain the gate insulating film 3 of the memory cells between the gate wiring stack bodies. in case the gate insulating film 3 is formed of an ono film, silicon nitride or polycrystalline silicon is used as the mask material film 72 like the mask material film 71 . then, as shown in fig. 59 , having etched and removed the gate insulating film 3 by use of the mask material film 72 as a mask, the gate insulating film 3 d with no charge storage layer formed therein, for example, a silicon oxide film, is formed as shown in fig. 60 . thereafter, etching the mask material film 72 , as shown in fig. 59 , the top surface of the substrate is exposed between the gate wiring stack bodies 2 . the steps shown in figs. 62 to 65 are the same as those shown in figs. 54 to 57 , i.e., forming the silicon layer as an activation layer; patterning it; forming contact diffusion layer 42 ; and forming bit lines 7 . as a result, both of the select gate transistors in the nand cell unit are stabilized in operation. to form the structure shown in fig. 46 , in which only the upper side select gate transistor has a gate insulating film with no charge storage layer formed therein, it is sufficient that after having formed the gate insulating film 3 with the charge storage layer formed therein, the processes shown in fig. 58 and the remaining drawings are adapted. this invention is not limited to the above-described embodiment. it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit, scope, and teaching of the invention.
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094-300-121-761-91X
|
DE
|
[
"US",
"WO",
"DE",
"EP"
] |
G06Q10/00
| 2002-08-05T00:00:00 |
2002
|
[
"G06"
] |
tool and method for configuring, designing or programming an installation
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the invention relates to a tool comprising a computer, a memory, input elements and a display. the control program that is stored in the memory and contains user prompting information and menus is converted into displays, each having two disparately organized navigation areas and a data area. the first navigation area facilitates an overview of the entire task. the second navigation area displays individual work steps in the sequence in which they are to be processed. a tool provided by the invention is preferably used for the purposes of configuring, designing or programming an installation, for example an installation in the field of drive engineering.
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1 .- 14 . (canceled) 15 . a tool for configuring, designing, or programming, the tool comprising: a storage unit for storing a control program; an operating unit for inputting operator commands; a computer; and a display for displaying a graphic user interface having a first navigation area, a second navigation area, and a data area, wherein the first navigation area is an area, in which the sub-tasks and work steps associated with a project can be displayed in a hierarchically organized manner, wherein the second navigation area is an area, in which individual work steps associated with the project can be displayed in their processing sequence, and wherein a required work step can be selected in the first navigation area and/or in the second navigation area. 16 . the tool according to claim 15 , wherein the first navigation area is an area with a tree structure. 17 . the tool according to claim 15 , wherein the first navigation area provides an overview of the project in a tree structure. 18 . the tool according to claim 16 , wherein the first navigation area provides an overview of the project in a tree structure. 19 . the tool according to claim 15 , wherein the elements displayed in the first navigation area are displayed in the form of an alphanumeric display. 20 . the tool according to claim 16 , wherein the elements displayed in the first navigation area are displayed in the form of an alphanumeric display. 21 . the tool according to claim 17 , wherein the elements displayed in the first navigation area are displayed in the form of an alphanumeric display. 22 . the tool according to claim 15 , wherein the elements displayed in the second navigation area are each displayed in alphanumeric and graphic form. 23 . the tool according to claim 16 , wherein the elements displayed in the second navigation area are each displayed in alphanumeric and graphic form. 24 . the tool according to claim 17 , wherein the elements displayed in the second navigation area are each displayed in alphanumeric and graphic form. 25 . the tool according to claim 15 , wherein once the required work step has been selected, data associated with said work step is displayed in the data area. 26 . the tool according to claim 15 , wherein once the required work step has been selected, the alphanumeric display in the first navigation area corresponding to the selected work step and the alphanumeric and graphic display in the second navigation area corresponding to the selected work step are visually marked. 27 . the tool according to claim 15 , wherein the tool is adapted for configuring, designing, or programming an installation or technical composition. 28 . the tool according to claim 22 , wherein the data displayed in the data area is displayed in the form of a list containing selectable list elements. 29 . the tool according to claim 28 , wherein a button is assigned to each selectable list element, which can be clicked on to superimpose a window corresponding to an assistant on the current display, the window containing help information or prompting the inputting of parameters. 30 . the tool according to claim 15 , wherein status indicators are provided in each of the navigation areas, the status indicators containing information about whether or not a work step has already been completed. 31 . the tool according to claim 30 , wherein the status indicators further contain information about whether or not the data selection made in a work step has resulted in a non-permitted status. 32 . a method for configuring, designing, and/or programming an installation, the method comprising: providing a graphic user interface displayed on a display, the graphic user interface having at least two navigation areas and a data area, wherein a first navigation area being an area in which the sub-tasks and work steps associated with a project can be displayed in a hierarchically organized manner and wherein a second navigation area being an area in which individual work steps are displayed in their processing sequence; selecting a work step by navigating in the first or in the second navigation area; visually marking display elements associated with the selected work step in the first and in the second navigation area; and displaying data associated with the selected work step in the data area. 33 . a digital storage medium comprising a control program adapted for interacting with a computer, an operator unit, and a display for performing the method according to claim 32.
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cross reference to related applications this application is the u.s. national stage of international application no. pct/de2003/002486, filed jul. 23, 2003 and claims the benefit thereof. the international application claims the benefits of german application no. 10235517.7 filed aug. 5, 2002, both applications are incorporated by reference herein in their entirety. field of the invention the invention relates to a tool. this can be used for example when configuring installations in the field of drive engineering. the invention also relates to a method for configuring an installation and a digital storage medium. a tool according to the invention can also be used in conjunction with the design or programming of an installation. background of the invention a plurality of sub-tasks has to be processed in the context of a configuration process, with work steps being assigned to each sub-task. to assist the user, it is already known that so-called assistants or wizards can be provided, which facilitate task processing for the user. these assistants are displayed in the form of a screen window on the display of the respective configuration tool and generally contain text information, which informs the user which data has to be input in the context of a work step and which form said data input has to take. such an assistant can comprise a plurality of text pages, which have to be called up by the user in sequence. a programming tool for configuring and managing a process control network including the use of spatial information is already known from de 101 02 205 a1. this programming tool is implemented using a programming workstation, which is linked to a local data network. an operator workstation, a laboratory workstation and controllers/multiplexers are also connected to the local data network. the controllers/multiplexers act as electrical interfaces between the workstations and a plurality of processes. the programming workstation has a processor, a display, a storage unit and user interface devices such as a keyboard, a light pen, etc. a control program is stored in the storage unit and executed using the processor in order to implement operations and functions of the process control environment. the programming tool is used to configure the process control network and to ensure that the process control network corresponds to a required standard protocol, for example the field bus protocol. screen presentations are thereby displayed on the display of the programming workstation, which either just display the logical links of a process or contain physical connections, which contain the spatial characteristics of the layout of an installation. the screen is divided into different areas, including for example a color bar menu area, a pictogram menu area, a template menu area and a diagram area. when designing a process control environment using logical links, a user activates a template from the template menu area and drags the active template to the required position inside the diagram area. a method and a graphic tool for configuring electrical installation components of a building are known from ep 1 134 864 a1. a device list is thereby provided in a screen window, which contains the devices to be configured. a space to be configured is represented by a specific, further screen window. devices are assigned to the space to be configured from the said device list. the devices assigned to the space are displayed in the window assigned to the space. the devices placed in the space screen window are then connected graphically to each other by means of electric circuits using assistants or wizards. a graphic user interface is known from u.s. pat. no. 6,005,566, with which the user is able to control the type of information associated with an object. different aspects of a selected object, for example a vehicle, are displayed in different fields of a display. the user is able to navigate within fields to select an item displayed there. us 2002/0003548 a1 discloses a method for controlling network devices via a user interface. icons for all the devices and/or services connected to the network are thereby displayed hierarchically. each of the said icons is also linked to functions of a respectively assigned device or service. a method and a device for presenting project planning and computer-assisted design are known from wo 01/03049 a1. an operator interface for example is displayed, having a project planning section, forward and back buttons and a design section. the individual tasks of a project are displayed in a tree structure in the project planning section. summary of the invention the object of the invention is to improve the user-friendliness of a tool for configuring, designing or programming an installation. this object is achieved by the claims. advantageous embodiments and developments will emerge from the dependent claims. the advantages of the invention relate in particular to the fact that two different, disparately organized navigation areas are available to the user at the same time. the first navigation area is particularly suited to providing a general overview of the current project or task. this is particularly advantageous, when the user resumes work after a break of any length. it also has advantages for a subsequent processor wishing to continue the work and for other people wishing to obtain an overview of the current status of the entire task. the second navigation area is particularly suited to the execution of the task itself, as the work steps to be carried out are displayed in their processing sequence in the second navigation area. this makes it significantly easier for the user to be able to execute the work steps they need to carry out in the predefined sequence. if the first navigation area has a tree structure, this gives the person observing the display a particularly good overview of the project in hand. if the second navigation area also contains pictorial or graphic elements, for example a representation of a motor and a power circuit, this assists in particular experienced operators in processing their tasks. the option of being able to select a required work step both in the first and in the second navigation areas takes into account the working practices of different user groups. marking the representations associated with the current work step in both navigation areas facilitates the user's overview of the work process as does provision of status indicators. brief description of the drawings further advantageous characteristics of the invention will emerge from the description which follows of an exemplary embodiment with reference to the figures, in which: fig. 1 shows a block diagram of a configuration tool according to the invention and figs. 2-8 show examples of the graphic user interfaces shown on the display. detailed description of the invention the invention relates to a tool, as can be used with all activities to be processed using a computer, which are to be processed in the form of a plurality of sub-tasks and work steps. the tool according to the invention is preferably a configuration, design or programming tool. the invention is described below by way of an example with reference to a configuration tool. the configuration tool shown in fig. 1 has a computer 1 , a storage unit 2 inserted into the computer, a keyboard 3 , a mouse 4 and a display 5 . the storage unit 2 is preferably a cd-rom. control signals and data that can be read using the computer and converted by it are stored on said storage unit and interact with the further components of the configuration tool shown in the fig such that a user is assisted with the processing of a configuration process. the stored data is displayed as a function of the progress of the configuration method on the display 5 , to give users an overview of the project in hand, give them information relating to the sequence of the sub-tasks and work steps to be processed, provide them with status information about the status of the configuration process and offer them objects for selection as a function of the current work step and also provide general information relating to the current work step as a function of the current work step. the display 5 is divided into a plurality of display areas. the display area 6 is a first navigation area. the sub-tasks and work steps associated with a project can be displayed in a hierarchically organized manner in this first navigation area. this takes place preferably using a tree structure, which gives the user a good overview of the entire project or—in the case of major projects—a good overview of a large part of the project. to save space the data displayed in the area 6 with the tree structure is preferably displayed in alphanumeric form, in particular in the form of keywords. this good overview of the entire project is particularly advantageous when the user resumes work after a break in the configuration process. said user quickly obtains information again about the current status of the configuration process from the display in the first navigation area 6 . the good overview of the entire project is also advantageous, when two or more people share the configuration work. each of these people is immediately informed about the current status of the configuration work when they resume configuration work. navigation in this first navigation area 6 also allows selection of a required work step. to this end the user positions a cursor or another pointer element on the alphanumeric representation corresponding to the required step using the cursor control keys on the keyboard 3 or using the mouse 4 and then selects this step by clicking on it. the result of this selection is that the data displayed in the second navigation area 7 , the data displayed in the data area 8 and the data displayed in the information field 9 change correspondingly. in particular a plurality of successive work steps are displayed in their processing sequence in the second navigation area 7 , one of these displayed steps being the step selected in the first navigation area 6 . if—as described above—a required work step is selected in the first navigation area 6 , to identify the selection made the wording corresponding to the selected step or the wording of the sub-task corresponding to the selected step in the first navigation area 6 and the wording associated with the selected step and/or the associated pictorial representation in the second navigation area 7 are visually marked. the display area 7 is—as mentioned above—a second navigation area. in this second navigation area individual work steps associated with the project can be displayed in their processing sequence. for example in fig. 1 a total of four work steps are represented in the second navigation area 7 by graphic and alphanumeric elements, which have to be processed in the sequence shown in the context of the configuration process. if the processing of a plurality of steps has been completed, it is possible to return to each of the steps already processed using the cursor control keys on the keyboard 3 or using the mouse 4 . this is done for example to check previously input or selected data once again. such navigation in the display area 7 also results in the displays in the first navigation area 6 , in the data area 8 and in the information area 9 changing as a function of the currently selected work step. in the first navigation area 6 the wording corresponding to the selected step or the wording corresponding to the current sub-task is visually marked to identify the selection made in the second navigation area 7 . data associated with the selected step is then displayed in the data area 8 . this display is preferably in the form of a table or list with a button assigned to each of the elements in said list. if one of these buttons is marked using the mouse or cursor control keys, an assistant or wizard opens in the form of a window, which is displayed over the data area 8 and either contains further information about the selected list element or requests the inputting of data relating to the selected list element. in the information field 9 general information relating to the configuration process, in particular the currently selected work step or currently selected sub-task is given in alphanumeric form, preferably in the form of complete sentences. when a selected work step has been processed, the representations associated with this step are assigned a completion marker in both navigation areas 6 and 7 , as set out in the description which follows of the further figures. figs. 2 to 8 show examples of graphic operator interfaces, as displayed in the various stages of a configuration process relating to electrical drive engineering on the display 5 . with all these representations a first navigation area 6 , a second navigation area 7 and a data area 8 are provided on the display. an information area or information field 9 is also provided on the display, in which general information relating to the configuration process is displayed. this general information relates in particular to the currently selected work step or the currently selected sub-task and is displayed in the form of complete sentences. the data displayed in the first navigation area 6 gradually forms a tree structure during the course of the configuration process, giving the user an overview of the entire project, which can comprise a plurality of sub-projects. the elements displayed in the second navigation area 7 include both alphanumeric components 7 b and graphic components 7 a . these display elements are associated with individual work steps and are displayed in their processing sequence. it can therefore be derived from the second navigation area 7 shown in fig. 2 that the work steps network, motor, power circuit, output options and input options have to be processed in the context of the configuration of a new drive. a status display 7 c is provided below these display elements 7 a and 7 b . this has a horizontal bar containing a plurality of circular marker elements, each marker element being assigned to one work step. the currently selected work step is marked by a triangular wedge 7 d , the tip of which points to the circular marker element assigned to the selected work step. in the representation according to fig. 2 the currently selected work step is the network. for example, the green check 7 e in the circular marker element of the work step network shows that this step has already been completed. network data associated with the currently selected work step, i.e. the work step network, is displayed in the data area 8 . in the exemplary embodiment shown this is the data “400 v, 50 hz, 3”. a button 8 b is also assigned to the displayed network data. clicking on this superimposes a window on the current display to display further information relating to the network data. the data displayed in the first navigation area 6 also has a status display. a green check 6 a is thus marked in a box associated with the currently selected work step network to signal to the user that this work step has already been completed. the arrow 6 b in the box assigned to the wording “new drive” means that the currently selected work step is associated with the configuration of a new drive. the following two sentences are displayed in the information field 9 : “there is just one network supply in each project. if you wish to configure devices for different network voltages, you must create a project for each network voltage.” these two sentences provide the user with general information about the currently selected work step. fig. 3 shows a display, as generated by the computer 1 running the control program after clicking on the word “motor” in the first navigation area 6 or the second navigation area 7 or by clicking on the graphic representation of the motor in the second navigation area 7 . the display according to fig. 3 is different from the display according to fig. 2 in that the triangular wedge 7 d now points to the circular marker element associated with the work step “motor” and that data associated with the work step “motor” is displayed in the data area 8 in the form of a list or table 8 a , with one button 8 b assigned to each of these items of data. general information relating to the selection of the motor is also displayed in the information area 9 . fig. 4 shows a display corresponding to fig. 3 , on which however—after clicking on the button 8 b in fig. 3 —a window corresponding to a motor assistant is superimposed on the display. this prompts the user to input further data relating to selection of the motor. the user has for example to select the load characteristic and specify the pole number. the user is provided with further information relating to the motor selection in the information field 9 . fig. 5 shows a display as generated by the computer 1 running the control program after clicking on the words “power circuit” in the first navigation area 6 or in the second navigation area 7 or by clicking on the graphic representation of the power circuit in the second navigation area 7 . the display according to fig. 5 is different from the display according to fig. 3 in that the triangular wedge 7 d now points to the circular marker element associated-with the work step “power circuit” and that data associated with the work step “power circuit” is displayed in the data area 8 in the form of a list or table 8 a , with one button 8 b assigned to each of these items of data. general information is also displayed in the information field 9 relating to selection of the power circuit. also to identify that the work step “motor” has already been processed, a green check 6 c is shown in the box associated with the wording “motor” in the first navigation area 6 and a green check 7 f is shown in the circular marker element associated with the wording “motor” in the second navigation area 7 . it can also be seen from the display of the first navigation area 6 that the tree structure gradually builds up during the course of the configuration process. if the user clicks on the button 8 b associated with the power circuit in the display according to fig. 5 , the computer 1 running the control program stored in the storage unit 2 generates a display according to fig. 6 . this has a window 10 superimposed on the further display, in which the user is prompted to select the power circuit. the user is also offered a selection of different power circuits in this window. the user is given further information relating to selection of the power circuit in the information field 9 . fig. 7 shows a display as displayed after completion of the configuration of a new drive system, when the user clicks on the power circuit. clicking on the power circuit is demonstrated by the positioning of the triangular wedge 7 d at the circular marker element associated with the work step “power circuit”. the green checks 7 e , 7 f , 7 g , 7 h and 7 i show that all the work steps relating to this drive system have already been completed. processing of all the work steps relating to the selected drive system is also indicated by the similarly green checks 6 a , 6 b , 6 c , 6 d , 6 e and 6 f in the first navigation area 6 . in one embodiment of the invention, if for example in the context of configuration in one work step a power circuit is selected, which is not compatible with components already selected in previous work steps, for example the supply network or a specific motor, all non-compatible components are identified by red checks so that the user can select other mutually compatible components. fig. 8 shows a display, in which it can be seen from the first navigation area 6 that a plurality of sub-projects are associated with the overall project to be configured. these are designated “drive system”, “drive system 1 ” and “drive system 2 ”. the sub-projects “drive system” and “drive system 1 ” have already been fully configured, as shown by the checks 6 a , . . . , 6 j in the first navigation area 6 . the triangular wedge 7 d in the second navigation area 7 , positioned at the circular marker element associated with the motor, indicates that the currently selected work step is the work step “motor”. the motor associated with the drive system 2 is selected in this work step. selection of a suitable motor is facilitated for the user by the table 8 a displayed in the data area 8 . the user can obtain further information about motors available for selection by clicking on the button 8 b and from the information in the information area 9 . the computer 1 thus runs the control program stored in the storage unit 2 , with which menus and dialog texts are also associated, in the form of representations that can be displayed on the display 5 . these each have two navigation areas 6 , 7 and a data area 8 . the two navigation areas are organized disparately. the first navigation area 6 provides a good overview of the entire project or at least a large part of it. selection of a required work step by navigating in the first navigation area 6 allows the information content of the second navigation area 7 and the data area 8 to the adapted to the selection made. individual work steps are shown in their processing sequence in the second navigation area 7 . this is particularly advantageous in the configuration phase itself. the user preferably also obtains information relating to the currently selected work step in an information area 9 of the display 5 , which is provided in addition to the navigation areas 6 and 7 and the data area 8 . as an alternative to selecting a required work step by navigating and clicking in the first navigation area 6 , the required work step can also be selected by navigating and clicking in the second navigation area 7 . the information content in the first navigation area 6 and the data area 8 is also adapted after such a selection. the second navigation area 7 is divided into individual command elements. a command element thereby maps a work step to be carried out by the user. all these command elements in the sequence to be observed by the user in the configuration process form the second navigation area, which is also referred to as the workflow navigation area. any of these command elements can be selected and then displays to the user the data associated with the respective work step in the data area or gives the user the option of inputting or changing data. this workflow navigation area 7 is processed from left to right and defines a sequence during the first processing operation. once all the work steps, which are selected by the user in sequence using the said command elements, have been processed, the entire task is closed or the configuration process is terminated. additional assistance can be obtained for the user by providing buttons “forward” and “back” buttons. these are used in particular to prompt those learning the system or first-time users in an optimum manner. if changes have to be made to already configured projects, the required work step can be selected using these “forward” and “back” buttons or by direct selection in the second navigation area 7 . the second navigation area 7 or workflow navigation area described above is supplemented by the first navigation area 6 with its tree structure. this shows the user the hierarchical structure of the work steps or elements to be processed, thereby facilitating a structured search. the tree structure of the first navigation area 6 provides a good overview of the entire configuration task. this is particularly helpful for new entire tasks and after fairly long breaks or even when another user wishes to continue an already started entire task. the currently selected work step is marked in both navigation areas. if the user starts to navigate in the second navigation area 7 , the marking is also displaced correspondingly in the first navigation area. the user thereby gets to know the hierarchical structure and can find their way about there easily. it is possible to move between the two navigation areas 6 and 7 at any time. the status indicators in both navigation areas show the user whether or not work steps have already been completed. it can also be indicated whether work steps need to be verified again or have become invalid. in the hierarchical view collative status information for entire hierarchical trees can provide the user with additional status information. this status information allows a quick overview of the progress of the entire task even during a change of processor. it is possible to stop configuration work at any time and continue it at any later time. the user is also assisted in task processing when the sequence of work steps is predefined. the user is not however bound by this sequence if changes should be made at a later stage. in one advantageous development of the invention, when a menu is offered the user is only able to click on or select those list elements, which are compatible with elements or devices that have already been selected.
|
094-383-823-816-205
|
TR
|
[
"US",
"WO",
"EP"
] |
G06F21/60,H01L23/00
| 2011-11-18T00:00:00 |
2011
|
[
"G06",
"H01"
] |
active shield with electrically configurable interconnections
|
introduced is an active shield method providing security to a security critical integrated circuit against some physical attacks like probing, manipulation and modification, while providing the ability to detect any physical modification made on the active shield itself. electrically controllable switching circuits are used to construct the upper layer conductive bit lines with electrically selectable different interconnection configurations. these bit lines arranged in a shielding pattern are used to carry a test data between a transmitter circuitry and a number of receiver circuitries which verify the integrity of the shielding lines to provide the security for the integrated circuit. by changing the selected interconnection configuration of the bit lines with a select signal produced by the transmitter, the self detection ability of the proposed active shield is provided as a countermeasure against the vulnerability to physical modification made on the active shield itself.
|
1 . an integrated circuit comprising an active shield said active shield comprising upper layer conductive lines ( 2 ) arranged in a shielding manner to cover at least a, part of a security critical circuit ( 3 ) arranged in lower layers of an integrated circuit ( 1 ); electrically controllable switching circuits arranged to select the connections of ones of said upper layer conductive lines ( 2 ) to other ones of said upper layer conductive lines ( 2 ) to form a multiplicity of data bit lines; internal data buses ( 12 ) arranged in lower lavers of the integrated circuit ( 1 ); at least one transmitter ( 7 ) and a multiplicity of receivers ( 8 ), wherein the transmitter ( 7 ) is arranged to transmit test data to the receivers ( 8 ) via both the said data bit lines and said internal data buses ( 12 ). the said at least one transmitter ( 7 ) comprises means for generating a. select signal ( 11 ) and means for transmitting the select signal ( 11 ) to the said receivers ( 8 ) and the said electrically controllable switching circuits ( 5 ) via a. data path arranged in lower lavers of the integrated circuit ( 1 ), and the said at least one transmitter ( 7 ) is arranged to change the value of the said select signal ( 11 ) in regular or random time intervals; the said electrically controllable switching circuits are arranged to select different ones of said upper layer conductive lines ( 2 ) for the different values of the said select signal ( 11 ) to change the interconnection configuration ( 9 , 10 ) of the said bit lines; the said receivers ( 8 ) comprises means for reordering the said bit lines according to the said interconnection configuration ( 9 , 10 ) selected by the said select signal ( 11 ) and, the said receivers ( 8 ) are configured to compare the test data received from the said bit lines with the actual test data received from the said internal data buses ( 12 ), in order to verify the integrity of the said upper layer conductive lines ( 2 ). 2 - 7 . (canceled)
|
technical field the invention is related to integrated circuits including security critical circuit components and integrated circuits processing or storing secret information. background art in security critical integrated circuits, some security countermeasures are implemented to provide safety of the critical information against some analysis and attack techniques aimed to obtain the information in an unauthorized way. active shield is a countermeasure providing security against some attacks depending on physically monitoring or manipulating the integrated circuit from outside. these attack techniques include probing the critical information by making connections to the metal lines of the integrated circuit, faulting the integrated circuit by forcing from these outside connections and changing the connections of the internal metal lines permanently by using fib (focused ion beam). in active shield method, the whole surface of the integrated circuit is covered by metal lines on the top metal layer. a transmitter circuitry which supplies a test data to the metal lines covering the whole chip and a number of receiver circuitries which compare the test data received from the top layer metal lines with the original test data received from the transmitter internally are added to integrated circuit. according to the result of the comparison, these receiver circuitries verify the integrity of the top layer metal lines. since any physical attack will disturb the integrity of the top layer metal lines by making them open or short circuit, the receiver circuitries do not receive the correct test data pattern from the top layer metal lines, thus detect the physical attack. it is believed that the references; us 2009/0024890 a1, us 2008/0244749 a1, us 2008/0150574 a1, us 2005/0092848 a1 and us 2003/0132777 a1 provide sufficient information on the background of the active shield method. in reference document us 2005/0092848 a1, a way of implementing the active shield method without requiring an additional metal layer is introduced and in reference documents us 2009/0024890 a1 and us 2008/0150574 a1, improvements are aimed to reduce the power consumption due to active shield. the reference us 2008/0244749 a1 introduces some improvements mainly on the detection circuitry part of the active shield method, not on the protection of the top metal layer shield itself. technical problem although being used in integrated circuits to detect any physical attack, active shield itself has still vulnerability against physical modification. since the top layer metal lines of the active shield have fixed interconnections, it is possible to make shortcut connections between the lines and remove the parts covering the whole integrated circuit or a part of it, to perform the actual attack without being detected by the active shield. some improvements can be made to decrease the vulnerability of the active shield to physical modification, like randomization of the connections of the top layer metal lines and increasing the number of receiver circuitries, however it is not possible to prevent the vulnerability completely. in reference document us 2003/013277 a1, a novel countermeasure against physical modification on the active shield is introduced. a capacitive measurement between the top layer metal lines of the active shield is performed along with the verification of the test data, to check whether the top layer metal lines are integral in their actual shapes. however, since the mentioned capacitive measurement between the top layer metal lines cannot be performed precisely, it is still possible for an attacker to perform partial physical modifications on the active shield while still satisfying sufficient capacitive coupling between the top layer metal lines. technical solution it is aimed to prevent the vulnerability caused by the fixed interconnections of the top layer metal lines by introducing a method using electrically configurable interconnections. using electrically configurable interconnections provides the opportunity to select from more than one interconnection scheme during the operation of the integrated circuit. this dynamic configurability of the invention introduces a precise self integrity checking mechanism to the active shield method. thus, it is prevented to bypass and remove the metal lines of the active shield by making fixed shortcut connections between them. best mode for carrying out the invention an integrated circuit ( 1 ) having an active shield according to the invention is illustrated in fig. 1 . a multiplicity of upper layer conductive lines ( 2 ), generally realized on top metal layer of the preferred technology, covers the whole surface of the integrated circuit ( 1 ) including the security critical circuit ( 3 ). the separate upper layer conductive lines ( 2 ) are connected by using lower layer conductive lines ( 4 ) and electrically controllable switching circuits ( 5 ), generally realized with multiplexers ( 6 ) as shown in fig. 3 , to construct the bit lines arranged in a shielding manner. these bit lines are used for the transmission of the test data between the transmitter ( 7 ) and the receivers ( 8 ). in fig. 1 , the number of separate bit lines is selected to be four and the number of receivers is selected to be two as an example. using electrically controllable switching circuits ( 5 ) within the interconnections of the bit lines makes it possible to select from different random interconnection configurations ( 9 and 10 ) according to a select signal ( 11 ) produced by the transmitter ( 7 ). the number of random interconnection configurations ( 9 and 10 ) is selected to be two as an example. the transmitter ( 7 ) transmits a test data, which is usually a random data, along with a select signal ( 11 ) used to determine which interconnection configuration ( 9 and 10 ) is selected by electrically controllable switching circuits ( 5 ). the receivers ( 8 ) receive the test data from the bit lines and reorder the bits of the data received according to the select signal ( 11 ) produced by the transmitter ( 7 ). the receivers ( 8 ) also receive the same test data from the transmitter ( 7 ) through internal data buses ( 12 ) arranged in lower layer conductive lines. then, the receivers ( 8 ) compare the test data received from the bit lines with the actual test data received from the internal data buses ( 12 ), thus verify the integrity of upper layer conductive lines ( 2 ) of the active shield. generally, the internal data buses ( 12 ) carrying the actual test data and the conductive lines carrying the select signal ( 11 ) from the transmitter ( 7 ) to the receivers ( 8 ), and the transmitter ( 7 ) and the receivers ( 8 ) themselves are arranged as a part of the integrated circuit ( 1 ) such as distributed within the whole layout and not easily recognizable for the sake of security. thanks to the electrically controllable switching circuits used to construct different interconnection configurations ( 9 and 10 ), the active shield according to the invention, verifies the test data received from the bit lines with the actual test data for detection of the physical attacks focused on the integrated circuit ( 1 ), while providing the ability to detect any fixed modification made on the upper layer conductive lines ( 2 ) aimed to bypass the shielding pattern and remove at least a part of it. in order to satisfy the latter purpose, the transmitter ( 7 ) changes the selected interconnection configuration ( 9 and 10 ) during the operation of the integrated circuit ( 1 ) by changing the select signal ( 11 ) regularly or randomly. thus, any fixed physical modification on the upper layer conductive lines ( 2 ) leads to an error in the verification of the test data. fig. 2 illustrates an active shield according to the invention of which upper layer conductive lines ( 2 ) are partly removed from the top of the security critical circuit ( 3 ) by making fixed shortcut connections ( 13 ). these shortcut connections between the transmitter ( 7 ) and one of the receivers ( 8 ) are arranged to preserve the integrity of the bit lines according to the first interconnection configuration ( 9 ). although the fixed shortcut connections ( 13 ) satisfy the correct transmission of the test data from the transmitter ( 7 ) to the receivers ( 8 ) when the first interconnection configuration ( 9 ) is selected, they do not satisfy the correct transmission of the test data when the second interconnection configuration ( 10 ) is selected. since the transmitter ( 7 ) changes the select signal ( 11 ) regularly or randomly during the operation of the integrated circuit ( 1 ), the receivers ( 8 ) verify the integrity of the upper layer conductive lines ( 2 ) for all of the interconnection configurations ( 9 and 10 ), thus the vulnerability of the active shield to physical modification is prevented. fig. 3 shows an exemplary embodiment of the electrically controllable switching circuits ( 5 ). four two-input multiplexers ( 6 ) are used to construct a part of the two different interconnection configurations ( 9 and 10 ) of four bit lines as an example. the select signal ( 11 ) determines in which order the inputs of the multiplexers ( 6 ) are connected to the outputs.
|
096-509-854-701-324
|
JP
|
[
"US"
] |
D21C5/02,D21B1/08,D21H11/14,D21F9/00
| 2017-12-28T00:00:00 |
2017
|
[
"D21"
] |
processing apparatus, sheet manufacturing apparatus, processing method, and sheet manufacturing method
|
a processing apparatus includes a powder material supply portion that supplies a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating, and a powder material removing portion that removes at least a portion of the powder material from the fiber-containing material supplied with the powder material. it is preferable that the processing apparatus include a defibrating portion that defibrates the fiber-containing material on an upstream side of the powder material supply portion.
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1 . a processing apparatus comprising: a powder material supply portion that supplies a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating; and a powder material removing portion that removes at least a portion of the powder material from the fiber-containing material supplied with the powder material. 2 . the processing apparatus according to claim 1 , further comprising: a defibrating portion that defibrates the fiber-containing material on an upstream side of the powder material supply portion. 3 . the processing apparatus according to claim 1 , wherein an average particle diameter of the second particle group is 2 times or more and 10,000 times or less an average particle diameter of the first particle group. 4 . the processing apparatus according to claim 1 , wherein an average particle diameter of the first particle group is 0.01 μm or more and 10 μm or less, and an average particle diameter of the second particle group is 5 μm or more and 1500 μm or less. 5 . the processing apparatus according to claim 1 , wherein the first particle and the second particle have different densities from each other. 6 . the processing apparatus according to claim 5 , wherein a density of the first particle is greater than a density of the second particle. 7 . the processing apparatus according to claim 1 , wherein a removal rate of the powder material in the powder material removing portion is 40% or more. 8 . a sheet manufacturing apparatus comprising: the processing apparatus according to claim 1 . 9 . a processing method comprising: supplying a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating; agitating the powder material and the fiber-containing material in a state where the powder material and the fiber-containing material are mixed; and removing at least a portion of the powder material from the fiber-containing material supplied with the powder material. 10 . the processing method according to claim 9 further comprising: manufacturing a sheet from the fiber-containing material from which the powder material is removed. 11 . a processing apparatus comprising: a powder material supply portion that supplies a powder material containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material containing a fiber during or after defibrating; and a powder material removing portion that removes at least a portion of the powder material from the fiber-containing material supplied with the powder material. 12 . the processing apparatus according to claim 11 , further comprising: a defibrating portion that defibrates the fiber-containing material on an upstream side of the powder material supply portion. 13 . the processing apparatus according to claim 11 , wherein both of the first particle and the second particle are formed of a material containing an organic material. 14 . the processing apparatus according to claim 11 , wherein both of the first particle and the second particle are formed of a material containing an inorganic material. 15 . the processing apparatus according to claim 11 , wherein one of the first particle and the second particle is formed of a material containing an organic material and the other is formed of a material containing an inorganic material. 16 . the processing apparatus according to claim 11 , wherein the first particle and the second particle have different average particle diameters from each other. 17 . the processing apparatus according to claim 11 , wherein the first particle and the second particle have different densities from each other. 18 . a sheet manufacturing apparatus comprising: the processing apparatus according to claim 11 . 19 . a processing method comprising: supplying a powder material containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material containing a fiber during or after defibrating; agitating the powder material and the fiber-containing material in a state where the powder material and the fiber-containing material are mixed; and removing at least a portion of the powder material from the fiber-containing material supplied with the powder material. 20 . the processing method according to claim 19 further comprising: manufacturing a sheet from the fiber-containing material from which the powder material is removed.
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background 1. technical field the present invention relates to a processing apparatus, a sheet manufacturing apparatus, a processing method, and a sheet manufacturing method. 2. related art in the related years, as environmental awareness rises, it is required not only to reduce the amount of paper (recording medium) used in a workplace but also to recycle the paper on the floor in the office. as a method for recycling the recording medium, for example, there is known a method of removing a recording layer formed by ink, toner or the like by ejecting a blast material onto the recording layer (printed portion) of a used recording medium which is made of a sheet of paper and printed (for example, refer to jp-a-2000-284657). the recording medium from which the recording layer is removed becomes a usable medium again. however, with the above method, there was a problem that it is impossible to sufficiently remove a foreign material (foreign material derived from constituent material of recording layer to be removed). in addition, even if a processing time is increased for the purpose of improving a removal rate of foreign material, there is a problem that the removal rate of foreign material can not be sufficiently improved and a processing efficiency is also lowered. summary an advantage of some aspects of the invention is to provide a processing apparatus, a sheet manufacturing apparatus, a processing method, and a sheet manufacturing method capable of efficiently removing a foreign material in a case where the foreign material is contained in a fiber-containing material. such an advantage is achieved by the following invention. according to an aspect of the invention, there is provided a processing apparatus including a powder material supply portion that supplies a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating; and a powder material removing portion that removes at least a portion of the powder material from the fiber-containing material supplied with the powder material. accordingly, it is possible to provide the processing apparatus capable of efficiently removing the foreign material in a case where the foreign material is contained in the fiber-containing material. it is preferable that the apparatus further include a defibrating portion that defibrates the fiber-containing material on an upstream side of the powder material supply portion. accordingly, it is possible to suitably perform deinking processing using a raw material which is not defibrated (for example, sheet-shaped raw material) even without preparing the defibrated material which is previously defibrated. in the apparatus, it is preferable that an average particle diameter of the second particle group be 2 times or more and 10,000 times or less an average particle diameter of the first particle group. accordingly, a synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably, and in a case where the foreign material is contained in the fiber-containing material, the removal efficiency of the foreign material can be made more excellent. in the apparatus, it is preferable that an average particle diameter of the first particle group be 0.01 μm or more and 10 μm or less, and an average particle diameter of the second particle group be 5 μm or more and 1500 μm or less. accordingly, the removal efficiency of the foreign material adhered to an outer surface of the fiber-containing material in an exposed state can be made more excellent, and the foreign material intruding a minute space such as a gap between the fibers forming the fiber-containing material can be more efficiently removed, and as a result, the removal efficiency of the foreign material as a whole of the powder material can be made more excellent. in the apparatus, it is preferable that the first particle and the second particle have different densities from each other. accordingly, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in the apparatus, it is preferable that a density of the first particle be greater than a density of the second particle. accordingly, in the deinking processing, the kinetic energy of the first particles (particles having a relatively small particle diameter) can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material intruding into a minute space such as a gap between fibers forming fiber-containing material) can be efficiently proceeded, and the kinetic energy of the second particles (particles having a relatively large particle diameter) can be more reliably prevented from being excessively increased. accordingly, the fibers forming the fiber-containing material can be more effectively prevented from being damaged (excessively shortening fiber length). in the apparatus, it is preferable that a removal rate of the powder material in the powder material removing portion be 40% or more. accordingly, the quality of the fiber-containing material after the deinking processing and the sheet manufactured using the fiber-containing material can be made more excellent. according to another aspect of the invention, there is provided a sheet manufacturing apparatus includes the processing apparatus of the aspect. accordingly, it is possible to efficiently remove the foreign material contained in the fiber-containing material and to manufacture the sheet from the material from which the foreign material is removed. according to still another aspect of the invention, there is provided a processing method including supplying a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating; agitating the powder material and the fiber-containing material in a state where the powder material and the fiber-containing material are mixed; and removing at least a portion of the powder material from the fiber-containing material supplied with the powder material. accordingly, it is possible to provide the processing method capable of efficiently removing the foreign material in a case where the foreign material is contained in the fiber-containing material. according to still another aspect of the invention, there is provided a sheet manufacturing method including supplying a powder material containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material containing a fiber during or after defibrating; agitating the powder material and the fiber-containing material in a state where the powder material and the fiber-containing material are mixed; and removing at least a portion of the powder material from the fiber-containing material supplied with the powder material, in which a sheet is manufactured from the fiber-containing material from which the powder material is removed. accordingly, it is possible to efficiently remove the foreign material contained in the fiber-containing material and to manufacture the sheet from the material from which the foreign material is removed. according to an application example of the invention, there is provided a processing apparatus including a powder material supply portion that supplies a powder material containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material containing a fiber during or after defibrating; and a powder material removing portion that removes at least a portion of the powder material from the fiber-containing material supplied with the powder material. brief description of the drawings the invention will be described with reference to the accompanying drawings, wherein like numbers reference like elements. fig. 1 is a schematic side view showing a first embodiment of a sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 2 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 1 . fig. 3 is an image diagram showing a state where a powder material (deinking agent) is mixed with a fiber-containing material in the sheet manufacturing apparatus shown in fig. 1 , and a foreign material is adsorbed by the powder material and separated. fig. 4 is a schematic side view showing a state where the mixed powder material (deinking agent) and the fiber-containing material are sieved and a web from which the powder material is removed is accumulated on a mesh belt in the sheet manufacturing apparatus shown in fig. 1 . fig. 5 is a schematic side view showing an upstream side of a second embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 6 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 5 . fig. 7 is a schematic side view showing an upstream side of a third embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 8 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 7 . fig. 9 is a schematic side view showing an upstream side of a fourth embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 10 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 9 . fig. 11 is a graph schematically showing an example of a particle size distribution of the powder material. description of exemplary embodiments hereinafter, preferred embodiments of the invention will be described in detail with reference to the accompanying drawings. first embodiment fig. 1 is a schematic side view showing a first embodiment of a sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 2 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 1 . fig. 3 is an image diagram showing a state where a powder material (deinking agent) is mixed with a fiber-containing material in the sheet manufacturing apparatus shown in fig. 1 , and a foreign material is adsorbed by the powder material and separated. fig. 4 is a schematic side view showing a state where the mixed powder material (deinking agent) and the fiber-containing material are sieved and a web from which the powder material is removed is accumulated on a mesh belt in the sheet manufacturing apparatus shown in fig. 1 . hereinafter, for convenience of description, an upper side may be referred to as “upper” or “upward”, a lower side may be referred to as “lower” or “downward”, a left side may be referred to as “left” or “upstream side”, and a right side in figs. 1 and 4 (the same applies to figs. 5, 7, and 9 ) may be referred to as “right” or “downstream side”. a processing apparatus 1 of the invention is provided with a powder material supply portion 25 that supplies a powder material rm containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material m 3 containing a fiber during or after defibrating, and a powder material removing portion 28 that removes at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm. in addition, a processing method of the invention is provided with a powder material supply step of supplying a powder material rm containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material m 3 containing a fiber during or after defibrating, an agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed, and a powder material removing step of removing at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm. this method is performed by the processing apparatus 1 . according to the invention as described above, as described later, even in a case where a foreign material cm derived from a recording material such as ink or toner (for example, a colorant, a binder resin, a charge control agent, or the like) is contained in the fiber-containing material m 3 , the foreign material cm can be efficiently removed from the fiber-containing material m 3 by the powder material (deinking agent) rm. that is, the foreign material cm can be removed (deinked) from the fiber-containing material m 3 with a high removal rate in short time processing. in addition, thereafter, the foreign material cm can also be removed with the powder material rm by the powder material removing portion 28 (powder material removing step). in particular, it is possible to remove the foreign material cm in a dry manner without requiring a large amount of water or large equipment. specifically, while the removal efficiency of foreign material cm adhered to an outer surface of the fiber-containing material m 3 in an exposed state is excellent, it is possible to efficiently remove the foreign material cm entering a minute space such as a gap between the fibers forming the fiber-containing material m 3 . in the invention, the average particle diameter refers to an average particle diameter based on the number. the average particle diameter of the powder refers to the number average value of the particle long diameter (diameter in the length direction of the particle) measured using a dry type particle size distribution meter and calculated by analysis using a static image analyzer (static image analysis apparatus: morphologi g3: manufactured by malvern). in addition, in the invention, “deinking” refers to removing (separating) foreign material derived from a recording material such as ink or toner. in addition, in the invention, “processing” refers to deinking processing on a paper material including a used paper. in the deinking processing in the related art, processing of dispersing the used paper in water, releasing the coloring agent mechanically and chemically (surfactants, alkaline chemicals, or the like), and removing the foreign material by a floating method, a screen washing method or the like is normally used. in the invention, deinking can be performed without requiring to soak the used paper in water. the deinking can be said to be a dry deinking technique. the sheet manufacturing apparatus 100 of the invention is provided with the processing apparatus 1 . in addition, a sheet manufacturing method of the invention is provided with a powder material supply step of supplying a powder material rm containing a first particle group consisting of a plurality of first particles, and a second particle group consisting of a plurality of second particles and having an average particle diameter larger than that of the first particle group, to a fiber-containing material m 3 containing a fiber during or after defibrating, an agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed, and a powder material removing step of removing at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm, and a sheet s is manufactured from the fiber-containing material m 3 from which the powder material rm is removed. this method is performed by the sheet manufacturing apparatus 100 . according to the invention as described above, the sheet s is further manufactured (reproduced) from the material from which the foreign material cm derived from the recording material such as ink, toner or the like (for example, a colorant, a binder resin, a charge control agent, or the like) is removed while enjoying the advantages of the above-described processing apparatus 1 (processing method). in particular, it is possible to manufacture the sheet s with high whiteness in a dry manner without requiring a large amount of water or large equipment. the sheet manufacturing apparatus 100 shown in fig. 1 is provided with a raw material supply portion 11 , a coarse crushing portion 12 , a defibrating portion 13 , a powder material supply portion 25 , a sorting portion 14 , a first web forming portion 15 , a subdividing portion 16 , a mixing portion 17 , a loosening portion 18 , a second web forming portion 19 , a sheet forming portion 20 , a cutting portion 21 , and a stock portion 22 . in addition, the sheet manufacturing apparatus 100 is provided with a humidifying portion 231 , a humidifying portion 232 , a humidifying portion 233 , and a humidifying portion 234 . the operation of each part of the sheet manufacturing apparatus 100 is controlled by a control unit (not shown). in addition, the sheet manufacturing apparatus 100 is provided with the processing apparatus 1 . in the embodiment, the processing apparatus 1 is configured to include the raw material supply portion 11 , the coarse crushing portion 12 , the defibrating portion 13 , the powder material supply portion 25 , the sorting portion 14 , and the first web forming portion 15 . as shown in fig. 2 , in the embodiment, the method for manufacturing a sheet includes a raw material supply step, a coarse crushing step, a defibrating step, a sorting step, a first web forming step, a dividing step, a mixing step, a loosening step, a second web forming step, a sheet forming step, and a cutting step. in addition, the powder material supply step is performed with the defibrating step, and the powder material removing step is performed with the first web formation step. in addition, an agitation step is provided between the powder material supply step and the sorting step. the sheet manufacturing apparatus 100 can sequentially perform these steps. in addition, among these steps, the steps performed by the processing apparatus 1 are the raw material supply step, the coarse crushing step, the defibrating step, the powder material supply step, the sorting step, the first web forming step, and the powder material removing step. hereinafter, the configuration of each part provided in the sheet manufacturing apparatus 100 will be described. the raw material supply portion 11 is a portion that performs the raw material supply step (refer to fig. 2 ) of supplying the raw material m 1 to the coarse crushing portion 12 . the raw material m 1 is, for example, a sheet-like material formed of a fiber-containing material containing a fiber (cellulose fiber). in addition, in the embodiment, although the raw material m 1 is the used paper, that is, a used sheet, it is not limited thereto, and it may be an unused sheet. the cellulose fiber may be any one as long as it is fibrous mainly formed of cellulose as a compound. the cellulose fiber is not limited as long as it is fibrous mainly formed of cellulose (narrowly defined cellulose) as a compound, and may contain hemicellulose and lignin in addition to cellulose and derivatives thereof. the coarse crushing portion 12 is a portion that performs the coarse crushing step (refer to fig. 2 ) of crushing the raw material m 1 supplied from the raw material supply portion 11 in the air (in air). the coarse crushing portion 12 has a pair of coarse crushing blades 121 and a chute (hopper) 122 . by rotating in a direction opposite to each other, the pair of coarse crushing blades 121 can coarsely crush, that is, cut the raw material m 1 therebetween into coarse crushed pieces m 2 . the shape and size of the coarse crushed piece m 2 are preferably suitable for defibrating processing in the defibrating portion 13 . for example, it is preferably a small piece having a side length of 100 mm or less, more preferably a small piece of 10 mm or more and 70 mm or less. the chute 122 is disposed below the pair of coarse crushing blades 121 , and has a funnel shape, for example. as a result, the chute 122 can receive the coarse crushed piece m 2 that is crushed and dropped by the coarse crushing blade 121 . in addition, above the chute 122 , the humidifying portion 231 is disposed adjacent to the pair of coarse crushing blades 121 . the humidifying portion 231 humidifies the coarse crushed piece m 2 in the chute 122 . the humidifying portion 231 has a filter (not shown) containing moisture, and is formed of a vaporization type (or warm air vaporization type) humidifier which supplies humidified air having increased humidity to the coarse crushed piece m 2 by allowing air to pass through the filter. by supplying the humidified air to the coarse crushed piece m 2 , it is possible to inhibit the adhesion of the coarse crushed piece m 2 to the chute 122 or the like due to static electricity. the chute 122 is connected to the defibrating portion 13 via a pipe (flow path) 241 . the coarse crushed piece m 2 collected in the chute 122 passes through the pipe 241 and is transported to the defibrating portion 13 . the defibrating portion 13 is provided on the upstream side of the powder material supply portion 25 and is a portion that performs the defibrating step (refer to fig. 2 ) of defibrating the coarse crushed piece m 2 (fiber-containing material containing fiber) in the air, that is, in a dry manner. by the defibrating processing at the defibrating portion 13 , the fiber-containing material m 3 as a defibrated material can be generated from the coarse crushed piece m 2 . in this manner, since the processing apparatus 1 is provided with the defibrating portion 13 , it is possible to suitably perform the deinking processing using the raw material m 1 which is not defibrated (for example, sheet-shaped raw material m 1 ) even without preparing the defibrated material which is previously defibrated (defibrated material defibrated from fiber-containing material). here, “to defibrate” refers to unravel the coarse crushed piece m 2 formed by binding a plurality of fibers to each fiber one by one. this unraveled material is the defibrated material (fiber-containing material) m 3 . the shape of the defibrated material m 3 is a linear shape or a belt shape. in addition, the defibrated material m 3 may exist in a state of being intertwined to form a lump, that is, in a state of forming a so-called “dama”. in the embodiment, for example, the defibrating portion 13 is formed of an impeller mill having a rotor rotating at high speed and a liner positioned on an outer periphery of the rotor. the coarse crushed piece m 2 flowing into the defibrating portion 13 is interposed between the rotor and the liner and is defibrated by a crushing and pulverizing defibrating action to be a fiber-containing material (defibrated material) m 3 . in addition, the defibrating portion 13 can generate a flow of air (air flow) from the coarse crushing portion 12 to the sorting portion 14 by the rotation of the rotor. as a result, the coarse crushed piece m 2 can be sucked from the pipe 241 to the defibrating portion 13 . in addition, after the defibrating processing, the defibrated material m 3 can be sent out to the sorting portion 14 via a pipe 242 . the powder material supply portion 25 is connected to the defibrating portion 13 having such a configuration. the powder material supply portion 25 is a portion for supplying the powder material rm containing the plurality of first particles and second particles having different average particle diameters from each other to the fiber-containing material (defibrated material) m 3 during defibrating. therefore, the powder material rm supplied from the powder material supply portion 25 to the defibrating portion 13 is mixed with the fiber-containing material (defibrated material) m 3 during defibrating. that is, in the embodiment, in the defibrating portion 13 , the powder material supply step of supplying the powder material rm to the fiber-containing material m 3 , and the agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed are performed with the defibrating step. in a case where a shearing force acts between the powder material rm and the fiber-containing material (defibrated material) m 3 and the foreign material cm adheres to the fiber-containing material (defibrated material) m 3 , the foreign material cm efficiently is removed. the configuration of the powder material supply portion 25 and the powder material rm will be described in detail later. in addition, the defibrating portion 13 is connected to the sorting portion 14 via the pipe (flow path) 242 . the defibrated material m 3 (fiber-containing material after defibrating) passes through the pipe 242 and is transported to the sorting portion 14 . in addition, a blower 261 is installed in the middle of the pipe 242 . the blower 261 is an air flow generating device that generates an air flow toward the sorting portion 14 . as a result, the delivery of the defibrated material m 3 to the sorting portion 14 is promoted. the sorting portion 14 performs the sorting step (refer to fig. 2 ) of sorting the defibrated material m 3 according to the length of the fiber. in the sorting portion 14 , the defibrated material m 3 is sorted into a first sorted object m 4 - 1 and a second sorted object m 4 - 2 larger than the first sorted object m 4 - 1 . the first sorted object m 4 - 1 has a size suitable for the subsequent manufacture of the sheet s. the second sorted object m 4 - 2 includes, for example, an insufficiently defibrated material, an excessively aggregated defibrated material, and the like. the sorting portion 14 has a drum portion 141 and a housing portion 142 that houses the drum portion 141 . the drum portion 141 is formed of a cylindrical mesh body and is a sieve that rotates about the central axis. the defibrated material m 3 flows into the drum portion 141 . as the drum portion 141 rotates, the defibrated material m 3 ′ smaller than a mesh opening is sorted as a first sorted object m 4 - 1 , and the defibrated material m 3 ′ larger than the mesh opening is sorted as a second sorted object m 4 - 2 . the first sorted object m 4 - 1 falls from the drum portion 141 . on the other hand, the second sorted object m 4 - 2 is sent out to a pipe (flow path) 243 connected to the drum portion 141 . the pipe 243 is connected to the pipe 241 on the side (downstream side) opposite to the drum portion 141 . the second sorted object m 4 - 2 passed through the pipe 243 joins the coarse crushed piece m 2 in the pipe 241 and flows into the defibrating portion 13 with the coarse crushed piece m 2 . as a result, the second sorted object m 4 - 2 is returned to the defibrating portion 13 and is subjected to the defibrating processing with the coarse crushed piece m 2 . in addition, the first sorted object m 4 - 1 from the drum portion 141 falls while dispersing in the air and heads toward the first web forming portion (separation portion) 15 located below the drum portion 141 . the first web forming portion 15 is a portion for performing the first web forming step (refer to fig. 2 ) of forming a first web m 5 from the first sorted object m 4 - 1 . the first web forming portion 15 has a mesh belt (separation belt) 151 , three stretching rollers 152 , and a suction portion (suction mechanism) 153 . the mesh belt 151 is an endless belt, and the first sorted object m 4 - 1 is accumulated. the mesh belt 151 is wrapped around three stretching rollers 152 . by rotationally driving the stretching roller 152 , the first sorted object m 4 - 1 on the mesh belt 151 is transported to the downstream side. the first sorted object m 4 - 1 is larger than the mesh opening of the mesh belt 151 . as a result, the first sorted object m 4 - 1 is restricted from passing through the mesh belt 151 , and thus can be accumulated on the mesh belt 151 . in addition, since the first sorted object m 4 - 1 is accumulated on the mesh belt 151 while being transported to the downstream side with the mesh belt 151 , the first sorted object m 4 - 1 is formed as a layered first web m 5 . in addition, in the first sorted object m 4 - 1 , the powder material rm described later in detail coexists. the powder material rm is smaller than the mesh opening of the mesh belt 151 . as a result, the powder material rm passes through the mesh belt 151 and fall further downward. the first web forming portion 15 constitutes a portion of the powder material removing portion 28 . in addition to the first web forming portion 15 , the powder material removing portion 28 is provided with a collecting portion 27 , a pipe 244 , a pipe 245 , and a blower 262 . the powder material removing portion 28 will be described in detail later. the suction portion 153 can suck air from below the mesh belt 151 . as a result, the powder material rm passing through the mesh belt 151 can be sucked with the air. in addition, the suction portion 153 is connected to the collecting portion 27 via the pipe (flow path) 244 . the powder material rm sucked by the suction portion 153 is collected by the collecting portion 27 . a pipe (flow path) 245 is further connected to the collecting portion 27 . in addition, a blower 262 is installed in the middle of the pipe 245 . by the operation of the blower 262 , suction force can be generated by the suction portion 153 . as a result, formation of the first web m 5 on the mesh belt 151 is promoted. the first web m 5 is obtained by removing the powder material rm. in addition, the powder material rm reach the collecting portion 27 after passing through the pipe 244 by operation of the blower 262 . the housing portion 142 is connected to the humidifying portion 232 . the humidifying portion 232 is formed of a vaporization type humidifier similar to the humidifying portion 231 . as a result, humidified air is supplied into the housing portion 142 . by this humidified air, it is possible to humidify the first sorted object m 4 - 1 , and thus it is possible to inhibit the first sorted object m 4 - 1 from adhering to an inner wall of the housing portion 142 due to electrostatic force. on the downstream side of the sorting portion 14 , the humidifying portion 235 is disposed. the humidifying portion 235 is formed of an ultrasonic humidifier for spraying water. as a result, moisture can be supplied to the first web m 5 , and thus the moisture content of the first web m 5 is adjusted. by this adjustment, the first web m 5 can be inhibited from adsorbing to the mesh belt 151 due to electrostatic force. as a result, the first web m 5 is easily separated from the mesh belt 151 at a position where the mesh belt 151 is folded back by the stretching roller 152 . on the downstream side of the humidifying portion 235 , the subdividing portion 16 is disposed. the subdividing portion 16 is a portion that performs the dividing step (refer to fig. 2 ) of dividing the first web m 5 separated from the mesh belt 151 . the subdividing portion 16 has a propeller 161 rotatably supported and a housing portion 162 housing the propeller 161 . by winding the first web m 5 around the rotating propeller 161 , it is possible to divide the first web m 5 . the divided first web m 5 becomes a subdivided body m 6 . in addition, the subdivided body m 6 descends within the housing portion 162 . the housing portion 162 is connected to the humidifying portion 233 . the humidifying portion 233 is formed of a vaporization type humidifier similar to the humidifying portion 231 . as a result, humidified air is supplied into the housing portion 162 . by this humidified air, it is also possible to prevent the subdivided body m 6 from adhering to the inner wall of the propeller 161 and the housing portion 162 due to electrostatic force. on the downstream side of the subdividing portion 16 , the mixing portion 17 is disposed. the mixing portion 17 is a portion that performs the mixing step (refer to fig. 2 ) of mixing the subdivided body m 6 and a binder p 1 . the mixing portion 17 includes a binder supply portion 171 , a pipe (flow path) 172 , and a blower 173 . the pipe 172 connects the housing portion 162 of the subdividing portion 16 and a housing portion 182 of the loosening portion 18 , and is a flow path through which a mixture m 7 of the subdivided body m 6 and the binder p 1 passes. the binder supply portion 171 is connected to the middle of the pipe 172 . the binder supply portion 171 has a screw feeder 174 . by rotationally driving the screw feeder 174 , it is possible to supply the binder p 1 as a powder to the pipe 172 . the binder p 1 supplied to the pipe 172 is mixed with the subdivided body m 6 to be the mixture m 7 . the binder p 1 bonds the fibers to each other in a later step. for example, a thermoplastic resin, a curable resin, or the like can be used, and a thermoplastic resin is preferably used. examples of thermoplastic resin include polyolefin such as as resin, abs resin, polyethylene, polypropylene, ethylene-vinyl acetate copolymer (eva), acrylic resins such as modified polyolefins, polymethyl methacrylate, polyester such as polyvinyl chloride, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyamides (nylon) such as nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66, liquid crystal polymers such as polyphenylene ether, polyacetal, polyether, polyphenylene oxide, polyether ether ketone, polycarbonate, polyphenylene sulfide, thermoplastic polyimide, polyetherimide, aromatic polyester, various thermoplastic elastomers such as styrene type, polyolefin type, polyvinyl chloride type, polyurethane type, polyester type, polyamide type, polybutadiene type, trans polyisoprene type, fluoro rubber type, chlorinated polyethylene type, and the like. one type or two or more types selected from these can be used in combination. preferably, as the thermoplastic resin, a polyester or a resin containing polyester is used. as a material supplied from the binder supply portion 171 , for example, a coloring agent for coloring the fiber, an aggregation inhibitor for inhibiting aggregation of the fiber or aggregation of the binder p 1 , a flame retardant for making the fiber less susceptible to burning, and the like may be included, in addition to the binder p 1 . in addition, the blower 173 is installed on the downstream side of the binder supply portion 171 in the pipe 172 . the blower 173 can generate the air flow towards the loosening portion 18 . with this air flow, the subdivided body m 6 and the binder p 1 can be agitated in the pipe 172 . as a result, the mixture m 7 can flow into the loosening portion 18 in a state where the subdivided body m 6 and the binder p 1 are uniformly dispersed. in addition, the subdivided body m 6 in the mixture m 7 is loosened in the process of passing through the inside of the pipe 172 , and becomes finer fibrous. the loosening portion 18 is a portion for performing the loosening step (refer to fig. 2 ) of loosening the mutually entangled fibers in the mixture m 7 . the loosening portion 18 has a drum portion 181 and a housing portion 182 for housing the drum portion 181 . the drum portion 181 is formed of a mesh body having a cylindrical shape and is a sieve rotating around the central axis. the mixture m 7 flows into the drum portion 181 . as the drum portion 181 rotates, fibers or the like smaller than the mesh opening of the mixture m 7 can pass through the drum portion 181 . at that time, the mixture m 7 is loosened. in addition, the mixture m 7 loosened by the drum portion 181 falls while dispersing in the air and heads toward the second web forming portion 19 located below the drum portion 181 . the second web forming portion 19 is a portion for performing the second web forming step (refer to fig. 2 ) of forming a second web m 8 from the mixture m 7 . the second web forming portion 19 includes a mesh belt (separation belt) 191 , a stretching roller 192 , and a suction portion (suction mechanism) 193 . the mesh belt 191 is an endless belt, and the mixture m 7 is accumulated. the mesh belt 191 is wrapped around four stretching rollers 192 . by rotationally driving the stretching roller 192 , the mixture m 7 on the mesh belt 191 is transported to the downstream side. in addition, most of the mixture m 7 on the mesh belt 191 is larger than the mesh opening of the mesh belt 191 . as a result, the mixture m 7 is restricted from passing through the mesh belt 191 , and thus can be accumulated on the mesh belt 191 . in addition, since the mixture m 7 is accumulated on the mesh belt 191 while being transported to the downstream side with the mesh belt 191 , the mixture m 7 is formed as the layered second web m 8 . the suction portion 193 can suck air from below the mesh belt 191 . as a result, the mixture m 7 can be sucked onto the mesh belt 191 , and thus the accumulation of the mixture m 7 is promoted on the mesh belt 191 . a pipe (flow path) 246 is connected to the suction portion 193 . in addition, a blower 263 is installed in the middle of the pipe 246 . by the operation of the blower 263 , suction force can be generated by the suction portion 193 . the housing portion 182 is connected to the humidifying portion 234 . the humidifying portion 234 is formed of a vaporization type humidifier similar to the humidifying portion 231 . as a result, humidified air is supplied into the housing portion 182 . by this humidified air, it is possible to humidify the interior of the housing portion 182 , and thus it is possible to inhibit the mixture m 7 from adhering to the inner wall of the housing portion 182 due to electrostatic force. on the downstream side of the loosening portion 18 , the humidifying portion 236 is disposed. the humidifying portion 236 is formed of an ultrasonic humidifier similar to the humidifying portion 235 . as a result, moisture can be supplied to the second web m 8 , and thus the moisture content of the second web m 8 is adjusted. by this adjustment, the second web m 8 can be inhibited from adsorbing onto the mesh belt 191 due to electrostatic force. as a result, the second web m 8 is easily separated from the mesh belt 191 at a position where the mesh belt 191 is folded back by the stretching roller 192 . on the downstream side of the second web forming portion 19 , the sheet forming portion 20 is disposed. the sheet forming portion 20 is a portion for performing the sheet forming step (refer to fig. 2 ) of forming the sheet s from the second web m 8 . the sheet forming portion 20 includes a pressurizing portion 201 and a heating portion 202 . the pressurizing portion 201 has a pair of calender rollers 203 , and can apply pressure without heating the second web m 8 therebetween. as a result, the density of the second web m 8 is increased. the second web m 8 is transported toward the heating portion 202 . one of the pair of calender rollers 203 is a main driving roller driven by the operation of a motor (not shown), and the other is a driven roller. the heating portion 202 has a pair of heating rollers 204 , and can apply pressure while heating the second web m 8 therebetween. with this heating and pressurization, in the second web m 8 , the binder p 1 is melted, and the fibers are bonded to each other via the molten binder p 1 . as a result, the sheet s is formed. the sheet s is transported toward the cutting portion 21 . one of the pair of heating rollers 204 is a main driving roller driven by operation of a motor (not shown), and the other is a driven roller. on the downstream side of the sheet forming portion 20 , the cutting portion 21 is disposed. the cutting portion 21 is a portion that performs the cutting step (refer to fig. 2 ) of cutting the sheet s. the cutting portion 21 includes a first cutter 211 and a second cutter 212 . the first cutter 211 cuts the sheet s in a direction intersecting with the transport direction of the sheet s. the second cutter 212 cuts the sheet s in a direction parallel to the transport direction of the sheet s on the downstream side of the first cutter 211 . by cutting the first cutter 211 and the second cutter 212 as described above, a sheet s having a desired size can be obtained. the sheet s is further transported to the downstream side and accumulated in the stock portion 22 . incidentally, as described above, the powder material supply portion 25 is connected to the defibrating portion 13 (refer to fig. 1 ). the powder material supply portion 25 is a portion that performs the powder material supply step (refer to fig. 2 ) of supplying the powder material rm to the defibrated material m 3 during defibrating in the defibrating portion 13 . in the embodiment, with respect to the defibrated material m 3 , the powder material supply step is also performed while performing the defibrating step in the air. in fig. 1 , although the powder material supply portion 25 is shown connected to the center of the defibrating portion 13 , the powder material supply portion 25 may supply the powder material rm to the defibrating portion 13 , so that it is not necessarily limited to this configuration. for example, the powder material supply portion 25 may be configured to be connected to the pipe 241 on the upstream side of the defibrating portion 13 , and to transport the powder material rm to the defibrating portion 13 with the coarse crushed piece m 2 transported from the chute 122 . in the embodiment, the raw material m 1 is a used paper that is printed and used. therefore, as shown in fig. 3 , the defibrated material m 3 contains the foreign material cm (for example, a colorant, a binder resin, a charge control agent, or the like) derived from the recording material such as ink or toner. the powder material rm supplied from the powder material supply portion 25 to the defibrating portion 13 has a function of adsorbing the foreign material cm contained in the defibrated material m 3 (fiber). the powder material rm supplied from the powder material supply portion 25 to the defibrating portion 13 is mixed with the fiber-containing material (defibrated material) m 3 during defibrating, so that a shearing force acts between the powder material rm and the fiber-containing material (defibrated material) m 3 . as a result, as shown in fig. 3 , the adsorption function included in the powder material rm is effectively exhibited, and the foreign material cm moves to the powder material rm to be efficiently removed (separated) from the defibrated material m 3 . the powder material supply portion 25 includes a storage portion 251 . the storage portion 251 is a tank that stores the powder material rm. in a case where the powder material rm is empty, the storage portion 251 exchanges the powder material rm with a new one in which the powder material rm is sufficiently stored, or adds (replenishes) the powder material rm. the powder material supply portion 25 is connected (or installed) to the defibrating portion 13 between the powder material supply portion 25 and the storage portion 251 , and includes an ejecting portion 252 for ejecting the powder material rm toward the defibrated material m 3 in the defibrating portion 13 . the ejecting portion 252 is formed of a pipe 253 and a blower 254 . the powder material supply portion 25 may be installed inside the defibrating portion 13 or may be installed integrally with the defibrating portion 13 . the pipe 253 connects the storage portion 251 and the defibrating portion 13 . the powder material rm can pass through the pipe 253 from the storage portion 251 toward the defibrating portion 13 . the blower 254 is installed in the middle of the pipe 253 in the longitudinal direction. the blower 254 can generate an air flow towards the defibrating portion 13 . as a result, the powder material rm passes through the inside of the pipe 253 and is ejected into the defibrating portion 13 . some of the ejected powder materials rm collide with the foreign material cm adhering to the defibrated material m 3 and come into contact therewith. this powder material rm can adsorb the foreign material cm and transfer the foreign material cm from the defibrated material m 3 . as a result, it is possible to efficiently remove the foreign material cm from the defibrated material m 3 . in addition, by the ejecting of the powder material rm, the defibrated material m 3 is in contact with the powder material rm while being agitated. as a result, the contact between the foreign material cm adhering to the defibrated material m 3 and the powder material rm is also promoted, and thus it is possible to sufficiently remove the foreign material cm from the defibrated material m 3 . the supply amount of the powder material rm with respect to 100 parts by mass of the defibrated material m 3 is not particularly limited, and it is preferably 10 parts by mass or more and 100,000 parts by mass or less, more preferably 30 parts by mass or more and 50,000 parts by mass or less, and still more preferably 100 parts by mass or more and 10,000 parts by mass or less. as a result, the foreign material cm contained in the defibrated material m 3 can be more efficiently removed while suppressing the usage amount of the powder material rm. in addition, separation and removal of the powder material rm (powder material rm′) from the defibrated material m 3 subjected to the deinking processing can be performed more easily and more reliably. the velocity (ejection velocity) of the powder material rm ejected into the defibrating portion 13 is appropriately set, for example, depending on the constituent material and size of the powder material rm. as shown in fig. 1 , the sheet manufacturing apparatus 100 (processing apparatus 1 ) is provided with the powder material removing portion 28 . the powder material removing portion 28 is a portion for performing the powder material removing step (refer to fig. 2 ) of removing the powder material rm from the defibrated material m 3 supplied with the powder material rm with the foreign material cm. in the embodiment, the powder material removing step is also performed on the defibrated material m 3 while performing the first web forming step. in the configuration shown in fig. 1 , the powder material removing portion 28 is provided with the first web forming portion 15 , the collecting portion 27 , the pipe 244 , the pipe 245 , and the blower 262 . above the first web forming portion 15 , as described above, the defibrated material m 3 is sorted into the first sorted object m 4 - 1 and the second sorted object m 4 - 2 by the sorting portion 14 . as shown in fig. 4 , in the first sorted object m 4 - 1 , the powder material rm adsorbing the foreign material cm (hereinafter, this powder material rm may be referred to as “powder material rm′”) coexists. the first sorted object m 4 - 1 may contain the powder material rm not adsorbing the foreign material cm. the first sorted object m 4 - 1 falls onto the mesh belt 151 of the first web forming portion 15 with the powder material (deinking agent) rm′. the powder material removing portion 28 separates and removes the powder material rm by using the difference in size between the powder material rm and the defibrated material m 3 (fiber). that is, the powder material removing portion 28 is provided with the mesh belt 151 (mesh body) having a mesh opening of a size that allows the powder material rm (powder material rm′) to pass through and regulates the passage of the fiber of the first sorted object m 4 - 1 (defibrated material m 3 ). as a result, as shown in fig. 4 , the first sorted object m 4 - 1 accumulates on the mesh belt 151 and is formed as the first web m 5 . on the other hand, the powder material rm (powder material rm′) passes through the mesh belt 151 by the suction force of the suction portion 153 , and thereafter passes through the suction portion 153 and the pipe 244 in turn, and is collected by the collecting portion 27 . as a result, the powder material rm (powder material rm′) is efficiently removed from the first web m 5 (defibrated material m 3 ). the first web m 5 is transferred to the subsequent step and finally becomes the sheet s. the mesh opening of the mesh belt 151 is set to a value larger than the second particle of the powder material rm. the powder material rm collected in the collecting portion 27 includes the powder material rm adsorbing the foreign material cm, that is, the powder material rm′ and the powder material rm not adsorbing the foreign material cm. in addition, in the powder material removing portion 28 , the entire amount of the supplied powder material rm may be removed (separated), or a portion of the supplied powder material rm may be removed. that is, a portion of the supplied powder material rm (containing powder material rm′) may remain in the defibrated material m 3 after the deinking processing. in this case, the removal rate of the powder material rm in the powder material removing portion 28 (ratio of mass of removed powder material rm to mass of supplied powder material rm) is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. as a result, the quality of the defibrated material m 3 after the deinking processing and the sheet s manufactured using the defibrated material m 3 can be made more excellent. in addition, the removal rate of the first particle group and the second particle group forming the powder material rm in the powder material removing portion 28 may be the same as or different from each other. specifically, for example, the removal rate of the second particle group in the powder material removing portion 28 may be higher or lower than the removal rate of the first particle group in the powder material removing portion 28 , and is preferably higher than the removal rate of the first particle group in the powder material removing portion 28 . in the embodiment, the powder material rm containing the first particle and the second particle is removed at once by the powder material removing portion 28 , and the invention is not limited thereto. the first particle and the second particle of the powder material rm may be divided into a plurality of stages and removed. in this case, each removal may be performed by a method suitable for the particle diameter and composition of each of the first particle and the second particle. for example, the removal of the first particle having a small particle diameter may be performed by an electrostatic adsorption method or the like in a previous step or a subsequent step of the powder material removing portion 28 . as a result, it is possible to further increase the removal rate of the first particle having a small particle diameter which is less susceptible to the suction force than the second particle. as described above, in the sheet manufacturing apparatus 100 (processing apparatus 1 ), even in a case where the foreign material cm is contained in used paper as a raw material for recycling the sheet. the foreign material cm is removed by the powder material rm supplied from the powder material supply portion 25 and thereafter the foreign material cm can be removed with the powder material rm by the powder material removing portion 28 . as a result, the sheet s to be manufactured is a high-quality sheet from which the foreign materials cm which can be impurities are removed during recycling. hereinafter, the powder material rm according to the invention will be described in detail. fig. 11 is a graph schematically showing an example of a particle size distribution of the powder material. the powder material rm includes the first particle group consisting of the plurality of first particles and the second particle group consisting of the plurality of second particles and having an average particle diameter larger than that of the first particle group (refer to fig. 11 ). by using such a powder material, it is possible to efficiently remove the foreign material cm intruding into a minute space such as a gap between the fibers forming the defibrated material m 3 , while making removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 excellent. as a result, the foreign materials cm can be removed (deinked) from the defibrated material m 3 with a high removal rate in short time processing. on the other hand, satisfactory results can not be obtained unless the above conditions are satisfied. for example, in a case where the powder material is formed of a single particle group having a relatively small average particle diameter, the time required for removing the foreign material from the defibrated material is long, and it is impossible to sufficiently remove the foreign material by short time processing. in addition, the foreign material once removed from the defibrated material is likely to reattach to the defibrated material. in addition, although it is also conceivable to increase the amount of the powder material used for the defibrated material to prevent the above problem, in such a case, the cost for processing the defibrated material increases, and it is difficult to sufficiently remove the powder material from the defibrated material after the processing. accordingly, the content of the powder material in the defibrated material after the processing can not be sufficiently lowered and there is a problem that the properties of the defibrated material after the processing and the properties of the sheet manufactured using the defibrated material are deteriorated. in addition, in a case where the powder material is formed of a single particle group having a relatively large average particle diameter, the removal rate of the foreign material can be relatively increased in a relatively short time from the start of the processing using the powder material, whereas even if the processing time is increased, the removal rate of the foreign material can not be effectively improved. more specifically, it is difficult to remove the foreign material intruding a minute space such as a gap between fibers forming the defibrated material. in addition, in a case where the processing time using the powder material is increased, a phenomenon in which the foreign material intruding into such a minute space is woven into a further narrow space (deep portion) occurs, and it is increasingly difficult to remove the foreign material. the powder material rm can be suitably prepared by mixing the separately prepared first particle group and the second particle group. the average particle diameter of the first particle group and the average particle diameter of the second particle group may be obtained from the particle size distribution of each particle group before mixing. the peak particle diameter on the small particle diameter side in the particle size distribution of the powder material rm may be the average particle diameter of the first particle group, and the peak particle diameter on the large particle diameter side in the particle size distribution of the powder material rm may be the average particle diameter of the second particle group (refer to fig. 11 ). the average particle diameter of the second particle group may be larger than the average particle diameter of the first particle group, and there is a preferable range for the degree of divergence between the particle diameters of both. that is, the average particle diameter of the second particle group is preferably two times or more and 10,000 times or less, more preferably 3 times or more and 1,000 times or less, and still more preferably 5 times or more and 100 times or less the average particle diameter of the first particle group. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering of the powder material rm (in particular, scattering which is difficult to recover) at the time of deinking processing or the like. on the other hand, if the divergence between the average particle diameter of the first particle group and the average particle diameter of the second particle group is too small, there is a possibility that the above effect due to the difference in particle diameter may not be fully exhibited. in addition, if the divergence between the average particle diameter of the first particle group and the average particle diameter of the second particle group is too large, the removal rate of the powder material rm in the powder material removing portion 28 decreases or the configuration of the powder material removing portion 28 needs to be complicated in order to increase the removal rate. the average particle diameter of the first particle group may be smaller than the average particle diameter of the second particle group, and the average particle diameter is preferably 0.01 μm or more and 10 μm or less, more preferably 0.05 μm or more and 7.0 μm or less, and still more preferably 0.1 μm or more and 5.0 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm (in particular, first particle) during the deinking processing or the like. the minimum particle diameter of the first particle group is preferably 0.01 μm or more and 3.0 μm or less, more preferably 0.02 μm or more and 2.5 μm or less, and still more preferably 0.03 μm or more and 2.0 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm (in particular, first particle) during the deinking processing or the like. the maximum particle diameter of the first particle group is preferably 0.1 μm or more and 100 μm or less, more preferably 0.2 μm or more and 70 μm or less, and still more preferably 0.3 μm or more and 50 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the average value of the aspect ratios of the first particles forming the first particle group is preferably 1.0 or more and 5.0 or less, more preferably 1.05 or more and 4.9 or less, and still more preferably 1.1 or more and 4.8 or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the content rate of the first particles in the powder material rm is preferably from 10% by volume or more and 90% by volume or less, more preferably 20% by volume or more and 80% by volume or less, and still more preferably 30% by volume or more and 70% by volume or less. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in addition, the average particle diameter of the second particle group may be larger than the average particle diameter of the first particle group, and the average particle diameter is preferably 5 μm or more and 1500 μm or less, more preferably 7 μm or more and 1,400 μm or less, and still more preferably 10 μm or more and 1,200 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the minimum particle diameter of the second particle group is preferably 0.5 μm or more and 1,000 μm or less, more preferably 0.7 μm or more and 850 μm or less, and still more preferably 1 μm or more and 800 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the maximum particle diameter of the second particle group is preferably 5 μm or more and 3,000 μm or less, more preferably 10 μm or more and 2,000 μm or less, and still more preferably 15 μm or more and 1,500 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the average value of the aspect ratios of the second particles forming the second particle group is preferably 1.0 or more and 50 or less, more preferably 1.05 or more and 30 or less, and still more preferably 1.1 or more and 20 or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. when the average value of the aspect ratios of the first particles forming the first particle group is a 1 and the average value of the aspect ratios of the second particles forming the second particle group is a 2 , it is preferable that the relationship of 0.1≤a 2 /a 1 ≤50 be satisfied, it is more preferable that the relationship of 0.5≤a 2 /a 1 ≤30 be satisfied, and it is still more preferable that the relationship of 0.8≤a 2 /a 1 ≤15 be satisfied. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. the content rate of the second particles in the powder material rm is preferably from 10% by volume or more and 90% by volume or less, more preferably 20% by volume or more and 80% by volume or less, and still more preferably 30% by volume or more and 70% by volume or less. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. when the content ratio of the first particles in the powder material rm is x 1 (% by volume) and the content rate of the second particles in the powder material rm is x 2 (% by volume), it is preferable that the relationship of 0.01≤x 1 /x 2 ≤10.0 be satisfied, it is more preferable that the relationship of 0.01≤x 1 /x 2 ≤5.0 be satisfied, and it is still more preferable that the relationship of 0.15 x 1 /x 2 ≤2.33 be satisfied. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. for example, the first particle and the second particle may have the same density, and it is preferable that the first particle and the second particle have mutually different densities from each other. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in the specification, unless otherwise specified, density refers to true specific gravity. in a case where the density of the first particle is different from the density of the second particle, the density of the first particle may be smaller than the density of the second particle, and is preferably greater than the density of the second particle. as a result, in the deinking processing, the kinetic energy of the first particles (particles having a relatively small particle diameter) can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded, and the kinetic energy of the second particles (particles having a relatively large particle diameter) can be more reliably prevented from being excessively increased. accordingly, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged (excessively shortening fiber length). in particular, when the density of the first particles is ρ 1 [g/cm 3 ] and the density of the second particles is ρ 2 [g/cm 3 ], it is preferable that the relationship of 0.2 ρ 1 /ρ 2 ≤15 be satisfied, it is more preferable that the relationship of 0.3 ρ 1 /ρ 2 ≤10 be satisfied, and it is still more preferable that the relationship of 0.5 ρ 1 /ρ 2 ≤5 be satisfied. as a result, in the deinking processing, the kinetic energy of the first particles (particles having a relatively small particle diameter) can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded, and the kinetic energy of the second particles (particles having a relatively large particle diameter) can be more reliably prevented from being excessively increased. accordingly, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged (excessively shortening fiber length). the density of the first particles is preferably 1.3 g/cm 3 or more and 10.0 g/cm 3 or less, more preferably 1.8 g/cm 3 or more and 8.0 g/cm 3 or less, and still more preferably 2.5 g/cm 3 or more and 5.0 g/cm 3 or less. as a result, in the deinking processing, the kinetic energy of the first particles can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded. accordingly, the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the density of the second particles is preferably 0.3 g/cm 3 or more and 8.0 g/cm 3 or less, more preferably 0.6 g/cm 3 or more and 6.2 g/cm 3 or less, and still more preferably 0.8 g/cm 3 or more and 4.8 g/cm 3 or less. as a result, in the deinking processing, the kinetic energy of the second particles can be more reliably prevented from being excessively increased, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, the constituent particles of the powder material rm may be, for example, a porous body or may have minute unevenness on the surface. the average particle diameter of the powder material rm as a whole is preferably 2.6 μm or more and 255 μm or less, more preferably 5.1 μm or more and 153 μm or less, and still more preferably 10.2 μm or more and 120 μm or less. as a result, the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm during the deinking processing or the like. in addition, the ratio (r/l) of the average particle diameter (r) of the powder material rm to the average length (l) of the particles forming the defibrated material m 3 is preferably 0.001 or more and 10 or less, more preferably 0.003 or more and 9 or less, and still more preferably 0.005 or more and 8 or less. as a result, in the deinking processing, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the ratio (ρ p /ρ f ) of the average value (ρ p ) of the density of the particles forming the powder material rm to the average value (ρ f ) of the density of the fiber forming the defibrated material m 3 is 0.2 or more and 10 or less, more preferably 0.4 or more and 4.5 or less, and still more preferably 0.5 or more and 3.5 or less. as a result, in the deinking processing, the defibrated material m 3 and the powder material rm can be more suitably mixed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the first particles and the second particles forming the powder material rm may have the same composition as or may have different compositions from each other. the composition of the powder material rm (first particle and second particle) is not particularly limited, and examples of the constituent material of the powder material rm include various resin materials such as various thermoplastic resins and various thermosetting resins, cellulose type materials such as cellulose, cellulose-modified materials (for example, methylcellulose, carboxymethylcellulose and salts thereof (for example, sodium salt and the like)), a material having a sugar chain structure such as starch, alginic acid, and chitosan, glass, calcium carbonate, metal compounds such as titanium oxide and alumina, and plant materials such as a crushed outer shell of the seed of the plant (seeds of walnut, peach, apricot, and the like), and a crushed actual shell of the plant fruit (dried corn grain, dried wheat endosperm, and the like). for example, both of the first particle and the second particle may be formed of a resin material, or the first particle may be formed of a cellulose-based material and the second particle may be formed of a metal compound. examples of thermoplastic resin include polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, a liquid crystal polymer such as modified polyolefin, polyamide (example: nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), thermoplastic polyimide, aromatic polyester, various thermoplastic elastomers such as polyphenylene oxide, polyphenylene sulfide, polycarbonate, polymethyl methacrylate, polyether, polyether ether ketone, polyether imide, polyacetal, styrene type, polyolefin type, polyvinyl chloride type, polyurethane type, polyester type, polyamide type, polybutadiene type, trans polyisoprene type, fluoro rubber type, chlorinated polyethylene type, or copolymers mainly containing these, blends, polymer alloys. examples of thermosetting resin include an epoxy resin, a phenol resin, a urea resin, a melamine resin, polyester (unsaturated polyester) resin, polyimide resin, silicone resin, polyurethane resin, and the like. in particular, the powder material rm preferably contains a substance having at least one of a hydroxyl group and a carboxyl group. this substance may contain two or more types as exemplified below. for example, the substance may contain a compound having a hydroxyl group and having no carboxyl group, and a compound having a carboxyl group and having no hydroxyl group. in a case where the powder material rm contains the substance, so that the foreign material cm is contained in the defibrated material m 3 , the foreign material cm can be removed more efficiently. such excellent effects can be obtained for the following reasons. that is, in general, a recording material such as ink or toner used for a recording medium such as paper is designed so as to have excellent affinity and adhesion to cellulose fiber serving as the main material of the recording medium. on the other hand, the cellulose fiber contains a polymer material containing β-glucose having a large number of hydroxyl groups in the molecule as a constituent monomer, and is a highly hydrophilic material. the powder material rm supplies such a fiber-containing material containing cellulose fiber to the defibrated material m 3 which is defibrated. when the powder material rm contains a highly hydrophilic substance having at least one of a hydroxyl group and a carboxyl group, the powder material rm exhibits a polarity (hydrophilicity) similar to that of the cellulose fiber. therefore, such a powder material rm has high affinity with the foreign material cm derived from a recording material such as ink and toner, and in a case where the powder material rm comes into contact with the defibrated material containing the foreign material cm, it is possible to effectively adsorb the foreign material cm, and to efficiently remove the foreign material cm from the defibrated material m 3 . in addition, even in a case where such a powder material rm remains in the defibrated material m 3 after the deinking processing, normally, it is possible to sufficiently reduce adverse effects on the defibrated material m 3 after the deinking processing and the sheet s manufactured by using the defibrated material m 3 . in addition, in some cases, it is possible to obtain an effect such that the sheet s to be manufactured can be made more excellent in paper strength, affinity to a recording material such as ink, toner, or the like. when the powder material rm contains a substance having at least one of a hydroxyl group and a carboxyl group, by the electrostatic interaction with foreign material cm, it is possible to adsorb the foreign material cm contained in the defibrated material m 3 from the fiber (cellulose fiber). as a result, the foreign material cm contained in the defibrated material m 3 can be more efficiently removed. in particular, when the powder material rm is supplied so as to collide with the defibrated material m 3 , by the electrostatic interaction, collision between the foreign material cm contained in the defibrated material m 3 and the powder material rm is likely to occur. accordingly, the removal efficiency of foreign material cm contained in the defibrated material m 3 can be made more excellent. in addition, it is possible to more effectively prevent unintended aggregation of constituent particles of the powder material rm due to electrical repulsion between particles forming the powder material rm. in addition, in a case where a relatively small amount of the powder material rm is contained in the defibrated material m 3 after the deinking processing (for example, 0.01% by mass or more and 0.5% by mass or less), the sheet s to be manufactured by using the defibrated material m 3 can be made more excellent in paper strength, affinity to a recording material such as ink, toner, or the like. in a case where the powder material rm contains the substance (substance having at least one of a hydroxyl group and a carboxyl group), the substance is preferably solid at ordinary temperature (25° c.) and has preferably a hydrophilic material. as a result, the foreign material cm contained in the defibrated material m 3 can be more efficiently removed. in addition, separation and removal of the powder material rm (powder material rm′) from the defibrated material m 3 subjected to the deinking processing can be performed more easily and more reliably. the degree of hydrophilicity of the substance is not particularly limited, and it is preferable that the solubility in water at 25° c. be 1 g/100 gh 2 o or more, or the contact angle of water be 90° or less. as a result, the above-described effect is more remarkably exhibited. the solubility of the substance in water at 25° c. is preferably 1.0 g/100gh 2 o or more, more preferably 2.0 g/100gh 2 o or more and 70 g/100gh 2 o or more, and still preferably 3.0 g/100gh 2 o or more and 50 g/100gh 2 o or less. as a result, the above-described effect is more remarkably exhibited. in addition, the contact angle of water with respect to the substance at 25° c. is preferably 90° or less, more preferably 60° or less, and still more preferably 45° or less. as a result, the above-described effect is more remarkably exhibited. in a case where the powder material rm contains a substance having at least one of a hydroxyl group and a carboxyl group, the substance may be a low molecular weight material, and is preferably a polymer material. as a result, an adsorption property of the foreign material cm can be made more excellent. in addition, separation and removal of the powder material rm (powder material rm′) from the defibrated material m 3 subjected to the deinking processing can be performed more easily and more reliably. the weight average molecular weight of the polymer material is preferably 2,000 or more and 3,000,000 or less, more preferably 5,000 or more and 2,000,000 or less, and still more preferably 10,000 or more and 1,000,000 or less. as a result, the above-described effect is more remarkably exhibited. the substance may contain both such a polymeric material and a low molecular weight material. the polymeric material forming the powder material rm is preferably one having a sugar chain structure. in general, the compound having a sugar chain structure has a high hydroxyl group ratio (ratio of the number of hydroxyl groups to the molecular weight) in the molecule, can improve the hydrophilicity of the powder material rm as a whole, and can make the adsorption property of foreign material cm as a whole of the powder material rm higher. examples of the polymer material having a sugar chain structure include cellulose, a cellulose-modified material (for example, methyl cellulose, carboxymethyl cellulose or a salt thereof (for example, sodium salt and the like)), starch, alginic acid, chitosan, and the like. among these, it is preferable to contain at least one of cellulose and a cellulose-modified material, and it is more preferable to contain a salt of carboxymethyl cellulose. in such a material, the adsorption ability of the foreign material cm is particularly high, and the foreign material cm can be removed more efficiently. in addition, such a material is relatively inexpensive and easy to obtain. in addition, in a case where a relatively small amount of the powder material rm is contained in the defibrated material m 3 after the deinking processing (for example, 0.01% by mass or more and 0.5% by mass or less), the sheet s to be manufactured by using the defibrated material m 3 can be made more excellent in paper strength, affinity to a recording material such as ink, toner, or the like. as the powder material rm, paper powder may be used. as the polymer material, a synthetic resin material may be used. as a result, the adsorption property of the foreign material cm can be made more excellent. in addition, separation and removal of the powder material rm (powder material rm′) from the defibrated material m 3 subjected to the deinking processing can be performed more easily and more reliably. examples of the synthetic resin material include polyvinyl alcohol (pva), poly (meth) acrylic acid, polymer containing monomer having a terminal oh group as a constituent component (for example, poly (meth) acrylic resin containing monomer components such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate), and the like. in a case where the powder material rm contains a substance having at least one of a hydroxyl group and a carboxyl group, the powder material rm may contain components (other components) other than the above-described substances (substance having at least one hydroxyl group and carboxyl group). in such a case, the content of the substance (substance having at least one of a hydroxyl group and a carboxyl group) in the powder material rm is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. as a result, the above-described effect is more remarkably exhibited. in a case where only one of the first particle and the second particle is formed of the substance (substance having at least one of a hydroxyl group and a carboxyl group), it is preferable that the second particle be formed of the substance (substance having at least one of a hydroxyl group and a carboxyl group) and the first particle be formed of a material other than the substance (substance having at least one of a hydroxyl group and a carboxyl group). as a result, the interaction between the first particle intruding a minute space such as a gap between the fibers forming the defibrated material m 3 and the fiber (cellulose fiber) is too strong, while effectively preventing the first particle from being unintentionally remaining (being remaining at a relatively high rate) in the defibrated material m 3 after the deinking processing without being removed, the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. second embodiment fig. 5 is a schematic side view showing an upstream side of a second embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 6 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 5 . hereinafter, a second embodiment of the processing apparatus, sheet manufacturing apparatus, processing method, and sheet manufacturing method of the invention will be described with reference to these drawings. the differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted. this embodiment is the same as the first embodiment except that the arrangement position of the powder material supply portion is different and accordingly the timing of performing the powder material supply step is different from these of the first embodiment. as shown in fig. 5 , the sheet manufacturing apparatus 100 (processing apparatus 1 ) is provided with the pipe (flow path) 242 connected to the defibrating portion 13 and through which the fiber-containing material (defibrated material) m 3 passes. the powder material supply portion 25 performs the powder material supply step of supplying the powder material rm to the fiber-containing material (defibrated material) m 3 after defibrating after the defibrating step (refer to fig. 6 ). the powder material supply portion 25 is connected to the downstream side of the blower 261 of the pipe (flow path) 242 , and has the ejecting portion 252 for ejecting the powder material rm into the pipe (flow path) 242 . as a result, it is possible to supply and mix the powder material rm to the defibrated material m 3 sufficiently defibrated. by such supply and mixing, the powder material rm spreads to every corner of the defibrated material m 3 , and as a result collides with and comes into contact the foreign material cm. as a result, the foreign material cm is sufficiently adsorbed to the powder material rm, and the foreign material cm can be more reliably removed from the defibrated material m 3 . third embodiment fig. 7 is a schematic side view showing an upstream side of a third embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 8 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 7 . hereinafter, a third embodiment of the processing apparatus, sheet manufacturing apparatus, processing method, and sheet manufacturing method of the invention will be described with reference to these drawings. the differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted. this embodiment is the same as the first embodiment except that the arrangement position of the powder material removing portion and the configuration of the powder material removing portion are different from these of the first embodiment. as shown in fig. 7 , in the embodiment, the powder material removing portion 28 is disposed in the middle of the pipe 242 and on the downstream side of the blower 261 . as a result, the powder material removing step in the powder material removing portion 28 is performed after the defibrating step (refer to fig. 8 ). the powder material removing portion 28 separates and removes the powder material rm (powder material rm′) by utilizing a difference (density difference) in density (specific gravity) between the defibrated material m 3 and the powder material rm (powder material rm′). that is, the powder material removing portion 28 is configured to remove the powder material rm (powder material rm′) by centrifugal separation, and includes a centrifugal separating portion 281 , a pipe 282 , and a collecting portion 283 . the centrifugal separating portion 281 and the collecting portion 283 are connected to each other via the pipe 282 . the centrifugal separating portion 281 is disposed and connected in the middle of the pipe 242 . the defibrated material m 3 and the powder material rm (powder material rm′) passed through the pipe 242 collectively flow into the centrifugal separating portion 281 . the powder material rm flowing into the centrifugal separating portion 281 includes the powder material rm adsorbed by the foreign material cm, that is, the powder material rm′, and the powder material rm not adsorbed by the foreign material cm. by centrifugal separation in the centrifugal separating portion 281 , these materials are divided into the defibrated material m 3 that flows further down the pipe 242 toward the sorting portion 14 , and the powder material rm (powder material rm′) that flows toward the pipe 282 . the powder material rm (powder material rm′) directed to the pipe 282 passes through the pipe 282 with the foreign material cm and is collected by the collecting portion 283 . even with such a powder material removing portion 28 , it is possible to efficiently remove the foreign material cm from the defibrated material m 3 with the powder material rm. fourth embodiment fig. 9 is a schematic side view showing an upstream side of a fourth embodiment of the sheet manufacturing apparatus (including processing apparatus of the invention) of the invention. fig. 10 is a flow chart sequentially showing steps performed by the sheet manufacturing apparatus shown in fig. 9 . hereinafter, a fourth embodiment of the processing apparatus, sheet manufacturing apparatus, processing method, and sheet manufacturing method of the invention will be described with reference to these drawings. the differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted. this embodiment is the same as the third embodiment except that the arrangement position of the powder material supply portion is different from that of the third embodiment, and an agitating portion 247 for agitating a mixture of the defibrated material m 3 and the powder material rm is provided at a portion on the downstream side of the defibrating portion 13 and the powder material supply portion 25 , and on the upstream side of the powder material removing portion 28 . as shown in fig. 9 , in the embodiment, the powder material supply portion 25 is connected between the defibrating portion 13 and the cyclone type powder material removing portion 28 (centrifugal separating portion 281 ), so that the powdered material rm is supplied to the defibrated material m 3 which is defibrated from the defibrating portion 13 and discharged. as a result, the powder material supply step in the powder material supply portion 25 is performed after the defibrating step, and the powder material removing step is performed after the powder material supply step (refer to fig. 10 ). although the arrangement position of the powder material supply portion 25 is on the upstream side of the powder material removing portion 28 , it is preferably further on the upstream side of the blower 261 . the agitating portion 247 has a chamber provided on the downstream side of the defibrating portion 13 , and a rotary blade rotating in the chamber. as a result, the defibrated material m 3 and the powder material rm can be efficiently mixed and agitated, and the opportunity for collision between the powder material rm and the foreign material cm is increased, and thus adsorption of the foreign material cm can be promoted. the space inside the chamber is an agitating space for mixing and agitating the defibrated material m 3 and the deinking agent rm. when the defibrated material m 3 and the deinking agent rm are supplied to the agitating space, these are mixed and agitated by the rotation of the rotary blade. as a result, the defibrated material m 3 collides with the deinking agent rm efficiently, and removal of the foreign material cm from the defibrated material m 3 is promoted. furthermore, the speed at which the powder material rm passes through the pipe 242 increases by the action of the blower 261 . as a result, the opportunity for the powder material rm to collide with the defibrated material m 3 increases and as a result it also comes in contact with the foreign material cm adhering to the defibrated material m 3 and adsorption of the foreign material cm is promoted. the powder material rm (powder material rm′) adsorbed the foreign material cm is removed by the powder material removing portion 28 . hereinbefore, although preferred embodiments of the invention are described, the invention is not limited thereto. for example, each part forming the processing apparatus and the sheet manufacturing apparatus can be replaced with any configuration capable of exhibiting the same function. in addition, any components may be added. in addition, the processing apparatus, the sheet manufacturing apparatus, the processing method, and the sheet manufacturing method of the invention may be any combination of two or more configurations (features) of the above embodiments. in addition, in the above-described embodiment, a case where the powder material removing portion separates the deinking agent and the defibrated material by utilizing one of the differences in the density and the difference in size described, and the powder material removing portion may separate by utilizing both the differences in the density between the deinking agent and the defibrated material, and the difference in size between the deinking agent and the fibrillated material. in addition, in the invention, the powder material may contain at least one particle which does not belong to any of the first particle group and the second particle group. in addition, in the above-described embodiment, although the removal of foreign material from the defibrated material is typically described by adsorption, the foreign material may be removed by a mechanism other than adsorption. for example, by causing the powder material to collide with the defibrated material, the foreign material may be separated without adsorption to the powder material (particle) to remove the foreign material from the defibrated material. in addition, the contact between the fiber-containing material and the powder material is not limited to that performed by the above-described configuration, and may be performed by an air flow agitating, for example. in addition, in the above-described third and fourth embodiment, a case where the powder material removing portion is provided with the cyclone type centrifugal separating portion is described, an apparatus having a mesh (sieve) may be adopted instead of the centrifugal separating portion. examples next, specific examples of the invention will be described. [1] preparation of powder material (deinking agent) example 1 first, calcium carbonate powder having an average particle diameter of 5 μm, a minimum particle diameter of 1 μm, and a maximum particle diameter of 10 μm was prepared as a first particle group. the average value of the aspect ratios of the particles (first particles) forming the first particle group was 1.3. on the other hand, a commercially available powdered carboxymethyl cellulose sodium salt (manufactured by wako pure chemical industries, ltd.) was prepared. the powdery sodium salt of carboxymethyl cellulose was subjected to classification processing using a classification device to obtain a plurality of fractions. among these, a fraction having an average particle diameter of 120 μm, a minimum particle diameter of 25 μm, and a maximum particle diameter of 150 μm was defined as a second particle group. the average value of the aspect ratios of the particles (second particles) forming the second particle group was 15. the first particle group and the second particle group as described above were mixed at a volume ratio of 1:10 to obtain a powder material (deinking agent) as a mixed powder. examples 2 to 10 a powder material (deinking agent) as a mixed powder was obtained in the same manner as in example 1 except that the conditions (constituent materials, material particle size distribution) of the first particle group and the second particle group are set as shown in table 1, and the mixing ratio of the first particle group and the second particle group was changed as shown in table 1. in the powder material (deinking agent) according to each of the above-described examples, the average particle diameter of the powder material as a whole was 1 μm or more and 100 μm or less in any case. in addition, regarding those containing the particle group containing particles formed of sodium salt of carboxymethyl cellulose (cmc-na) of the powder material (deinking agent) according to each of the above examples, the weight average molecular weight of the cmc-na was 10,000 or more and 1,000,000 or less in any case. in addition, the cmc-na contained in the powder material (deinking agent) according to the example had solubility in water at 25° c. of 3.0 g/100gh 2 o or more and 50 g/100gh 2 o less, or the contact angle of water was 45° or less in any case. comparative example 1 a powder material (deinking agent) was obtained in the same manner as in example 1 except that the fraction having an average particle diameter of 15 μm, a minimum particle diameter of 1 and a maximum particle diameter of 25 μm was used as it was as a powder material (deinking agent) among the powders of sodium salt of carboxymethyl cellulose fractionated in the same manner as in example 1. that is, the powder material (deinking agent) according to this comparative example is formed of a single particle group. comparative example 2 a powder material (deinking agent) was obtained in the same manner as in example 1 except that the fraction having an average particle diameter of 120 μm, a minimum particle diameter of 25 μm, and a maximum particle diameter of 150 μm was used as it was as a powder material (deinking agent) among the powders of sodium salt of carboxymethyl cellulose fractionated in the same manner as in example 1. that is, the powder material (deinking agent) according to this comparative example is formed of a single particle group. the conditions of the powder materials (deinking agent) according to each example and each comparative example are summarizes in table 1. table 1first particle groupaverageminimummaximumsecondparticleparticleparticlecontentparticle groupconstituentdiameterdiameterdiameteraspectdensity[% byconstituentmaterial[μm][μm][μm]ratios[g/cm 3 ]mass]materialexample 1caco 351101.32.9318.6cmc-naexample 2caco 351101.32.9318.6naclexample 3caco 351101.32.9318.6starchexample 4caco 351101.32.9318.6polyacrylic acidexample 5caco 351101.32.9318.6methylcelluloseexample 6caco 351101.32.9318.6nylonexample 7caco 351101.32.9318.6aluminaexample 8caco 30.150.050.31.32.9318.6cmc-naexample 9tio 20.210.10.31.14.311.4cmc-naexample 10talc52501.12.79.6cmc-nacomparativecmc-na151251.21.634.4—example 1comparative———————cmc-naexample 2second particle groupaverageminimummaximumparticleparticleparticlecontentdiameterdiameterdiameteraspectdensity[% by[μm][μm][μm]ratios[g/cm 3 ]mass]example 112025150151.634.4example 2120085014001.12.1652.8example 330101001.51.442.9example 4100302501.71.241.7example 51002500121.631.3example 6103181.21.145.5example 75045531.23.5449.7example 812025150151.634.4example 912025150151.634.4example 1012025150151.634.4comparative——————example 1comparative12025150151.634.4example 2 [2] deinking processing and manufacture of sheet using the powder materials (deinking agent) prepared in each of the above examples and comparative examples, the following processing (deinking processing) and manufacture of a sheet were performed. first, the sheet manufacturing apparatus having the configuration shown in fig. 1 was prepared, and commercially available copy paper was subjected to monochrome printing of 10% duty on one side with an ink jet printer (px-m7050ft manufactured by seiko epson corporation) was prepared as a raw material. the mesh opening of the mesh belt (mesh body) included in the first web forming portion of the powder material removing portion of the sheet manufacturing apparatus was 600 μm. next, the above raw material was supplied to the raw material supply portion of the sheet manufacturing apparatus, the sheet manufacturing apparatus was operated, and the raw material was subjected to processing such as crushing, defibrating, deinking and the like to produce a sheet. at this time, the supply amount of the powder material (deinking agent) to 100 parts by mass of the fiber-containing material (defibrated material) was 100 parts by mass. the manufacturing conditions of the sheets were the same in each of the examples and the comparative examples except that the type of the powder material (deinking agent) was changed. in each of the above embodiments, the ratio (r/l) of the average particle diameter (r) of the powder material as a whole to the average length (l) of the fiber forming the defibrated material to be subjected to the deinking processing was 0.001 or more and 10 or less in any case. in addition, in each of the above examples, the ratio (ρ p /ρ f ) of the average value (ρ p ) of the density of the particles forming the powder material to the average value (ρ f ) of the density of the fiber forming the defibrated material to be subjected to the deinking processing was 0.2 or more and 10 or less in any case. [3] evaluation [3-1] coloring of defibrated material after deinking processing (remaining foreign material) for each of the examples and each of the comparative examples, a portion of the first web formed in the first web forming portion was taken out and observed with a digital microscope (vhx-5000 manufactured by keyence corporation). compared with the state of the first web in a case where the processing was performed in the same manner as above except that the powder material (deinking agent) was not used, the remaining state of the foreign material derived from the recording material (ink) was evaluated according to the following criteria. a: no remaining foreign material is observed. b: almost no remaining foreign material is observed. c: remaining foreign material is slightly observed. d: remaining foreign material is observed. e: remaining foreign material is significantly observed. these results are summarized in table 2. table 2remaining foreign materialexample 1aexample 2dexample 3bexample 4bexample 5cexample 6cexample 7bexample 8dexample 9dexample 10ccomparative example 1ecomparative example 2e as is apparent from table 2, excellent results were obtained in the invention. that is, in the invention, the powder material (deinking agent) efficiently adsorbed the foreign material contained in the defibrated material, and the foreign material could be efficiently removed. in addition, in the invention, the whiteness of the manufactured sheet was excellent, and unintended coloring or unintended color unevenness due to remaining foreign material was not observed. in addition, in the invention, separability between the defibrated material subjected to the deinking treatment and the powder material (deinking agent) was also excellent. in each of the above examples, the removal rate of the powder material in the powder material removing portion was 90% or more in any case, and the removal rate of the second particle was higher than the removal rate of the first particle. on the contrary, satisfactory results were not obtained in the comparative example. in addition, deinking processing and sheet manufacture were performed in the same manner as described above except that the supply amount of the powder material (deinking agent) to 100 parts by mass of the defibrated material was variously changed in the range of 10 parts by mass or more and 100,000 parts by mass or less, and the same evaluation as above was performed, and the same results as described above were obtained. in addition, the deinking processing and the sheet manufacture were performed in the same manner as described above except the apparatus used for the deinking processing and the sheet manufacture was changed to the one having the construction shown in fig. 5 , the one having the construction shown in fig. 7 , and the one shown in fig. 9 . hereinafter, preferred embodiments of the invention will be described in detail with reference to the same drawings used in the first to fourth embodiments. in addition, also in the embodiment of the invention, the same operation as that of the first to the fourth embodiments is applied and similar drawings ( figs. 1 to 10 ) are applied, so duplicate explanation will be omitted. therefore, it is assumed that the first to fourth embodiments are similarly applied to an application not described below. also in the embodiment, “deinking” and “processing” are the same as those in the first embodiment. fifth embodiment a processing apparatus 1 of the invention is provided with a powder material supply portion 25 that supplies a powder material rm containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material m 3 containing a fiber during or after defibrating, and a powder material removing portion 28 that removes at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm. in addition, a processing method of the invention is provided with a powder material supply step of supplying a powder material rm containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material m 3 containing a fiber during or after defibrating, an agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed, and a powder material removing step of removing at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm. this method is performed by the processing apparatus 1 . according to the invention as described above, as described later, even in a case where a foreign material cm derived from a recording material such as ink or toner (for example, a colorant, a binder resin, a charge control agent, or the like) is contained in the fiber-containing material m 3 , the foreign material cm can be efficiently removed from the fiber-containing material m 3 by the powder material (deinking agent) rm. that is, the foreign material cm can be removed (deinked) from the fiber-containing material m 3 with a high removal rate in short time processing. in addition, thereafter, the foreign material cm can also be removed with the powder material rm by the powder material removing portion 28 (powder material removing step). in particular, it is possible to remove the foreign material cm in a dry manner without requiring a large amount of water or large equipment. in addition, the first particle and the second particle are terms indicating the relative relationship between these, and the powder material may contain three or more types of particles formed of different materials from each other. however, in a case where the powder material contains three or more types of particles formed of different materials from each other, it is preferable that one of the two types of particles having the highest content ratio in the powder material be the first particle and the other one be the second particle. the sheet manufacturing apparatus 100 of the invention is provided with the processing apparatus 1 . in addition, a sheet manufacturing method of the invention is provided with a powder material supply step of supplying a powder material rm containing a first particle and a second particle having a different composition from that of the first particle, to the fiber-containing material m 3 containing a fiber during or after defibrating, an agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed, and a powder material removing step of removing at least a portion of the powder material rm from the fiber-containing material m 3 supplied with the powder material rm, and the sheet s is manufactured from the fiber-containing material m 3 from which the powder material rm is removed. this method is performed by the sheet manufacturing apparatus 100 . according to the invention as described above, the sheet s is further manufactured (reproduced) from the material from which the foreign material cm derived from the recording material such as ink, toner or the like (for example, a colorant, a binder resin, a charge control agent, or the like) is removed while enjoying the advantages of the above-described processing apparatus 1 (processing method). in particular, it is possible to manufacture the sheet s with high whiteness in a dry manner without requiring a large amount of water or large equipment. the powder material supply portion 25 is connected to the defibrating portion 13 of the configuration of the sheet manufacturing apparatus 100 in the embodiment. the powder material supply portion 25 is a portion for supplying the powder material rm containing a first particle and a second particle having a different composition from that of the first particle to the fiber-containing material (defibrated material) m 3 during defibrating. therefore, the powder material rm supplied from the powder material supply portion 25 to the defibrating portion 13 is mixed with the fiber-containing material (defibrated material) m 3 during defibrating. that is, in the embodiment, in the defibrating portion 13 , the powder material supply step of supplying the powder material rm to the fiber-containing material m 3 , and the agitating step of agitating the powder material and the fiber-containing material in a state where the powder material rm and the fiber-containing material m 3 are mixed are performed with the defibrating step. in a case where a shearing force acts between the powder material rm and the fiber-containing material (defibrated material) m 3 and the foreign material cm adheres to the fiber-containing material (defibrated material) m 3 , the foreign material cm efficiently is removed. the configuration of the powder material supply portion 25 and the powder material rm are the same as these of the first embodiment. in the embodiment, the powder material rm containing the first particle and the second particle is removed at once by the powder material removing portion 28 , and the invention is not limited thereto. the first particle and the second particle of the powder material rm may be divided into a plurality of stages and removed. in this case, each removal may be performed by a method suitable for the particle composition of each of the first particle and the second particle. for example, the removal of the first particle, which is easier to charge than the second particle, may be performed by an electrostatic adsorption method or the like in a previous step or a subsequent step of the powder material removing portion 28 . as a result, the removal rate of the powder material rm as a whole can be more efficiently increased. the powder material rm contains the first particle and the second particle, and the first particle and the second particle have different compositions from each other. by using such a powder material rm, it is possible to remove the foreign material cm contained in the fiber-containing material m 3 , and to improve the removal efficiency of the foreign material as a whole by a mechanism corresponding to each of the first particle and the second particle. in addition, the foreign material cm can be removed (deinked) from the fiber-containing material m 3 with a high removal rate in short time processing. in addition, as compared with a case of using a single type of particles, it is possible to efficiently remove the foreign material cm while suppressing damage to the fiber-containing material m 3 (for example, excessive cutting of fiber during deinking, or the like). the powder material rm may contain at least one of the first particle and the second particle respectively, and normally, contains a plurality of first particles and a plurality of second particles. the powder material rm can be suitably prepared by mixing the separately prepared first particles (in particular, first particle group including a plurality of first particles) and the second particles (in particular, second particle group including a plurality of second particles). at least one of the first particle and the second particle may contain plural types of components. in a case where at least one of the first particle and the second particle contains plural types of components, even if components common to each other are contained, these particles have different compositions from each other as long as the contents of at least one of the plurality of types of components are different from each other. examples of the constituent material of the powder material rm (first particle and second particle) include a composite material of an inorganic material and an organic material, in addition to various inorganic materials and various organic materials. examples of the inorganic material forming the powder material rm include various metallic materials such as iron and stainless steel, metal compounds such as sodium chloride, aluminum sulfate, calcium carbonate, titanium oxide, alumina and the like (ionic substance, metal oxide, metal nitride, metal carbide, and the like), various types of glass, various ores such as talc, dry ice, and the like. in particular, calcium carbonate is preferable as the inorganic material forming the powder material rm. in a case where the foreign material cm is contained in the defibrated material m 3 as the powder material rm contains calcium carbonate, the foreign material cm can be removed more efficiently. it is considered that such excellent effects can be obtained for the following reasons. that is, in calcium carbonate, the fiber forming the defibrated material m 3 has fine unevenness on the surface, and there is a problem that foreign material is likely to adhere to and remain in the recessed portion. calcium carbonate has a feature that it is suitably crushed by impact during the deinking processing and easily comes into contact with the foreign material in the recessed portion. in addition, in a case of using calcium carbonate, a new surface having excellent adsorption ability is exposed by crushing during the deinking processing as described above, and thus it is possible to prevent or suppress a decrease in adsorption ability with time of the powder material rm during the deinking processing. in a case where dry ice is used as the inorganic material forming the powder material rm, at least a portion of the dry ice normally sublimes during the deinking processing, and thus it is possible to reduce the amount of the powder material rm collected by the powder material removing portion 28 . examples of the organic material forming the powder material rm include various resin materials such as various thermoplastic resins and various thermosetting resins, natural resin such as rosin, cellulose type materials such as cellulose, cellulose-modified materials (for example, methylcellulose, carboxymethylcellulose and salts thereof (for example, sodium salt and the like)), a material having a sugar chain structure such as starch, alginic acid, and chitosan, plant materials such as a crushed outer shell of the seed of the plant (seeds of walnut, peach, apricot, and the like), and a crushed actual shell of the plant fruit (dried corn grain, dried wheat endosperm, and the like), and various sizing agents such as rosin type sizing agent, alkyl ketene dimer type sizing agent, alkenyl succinic acid type anhydride type sizing agent. examples of thermoplastic resin include polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, a liquid crystal polymer such as modified polyolefin, polyamide (example: nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), thermoplastic polyimide, aromatic polyester, various thermoplastic elastomers such as polyphenylene oxide, polyphenylene sulfide, polycarbonate, polymethyl methacrylate, polyether, polyether ether ketone, polyether imide, polyacetal, styrene type, polyolefin type, polyvinyl chloride type, polyurethane type, polyester type, polyamide type, polybutadiene type, trans polyisoprene type, fluoro rubber type, chlorinated polyethylene type, or copolymers mainly containing these, blends, polymer alloys. examples of thermosetting resin include an epoxy resin, a phenol resin, a urea resin, a melamine resin, polyester (unsaturated polyester) resin, polyimide resin, silicone resin, polyurethane resin, and the like. in addition, as the organic material forming the powder material rm, for example, a hydrophilic polymer used as a gel material such as polyacrylic acid salt (for example, sodium salt), polyacrylamide or the like may be used. in particular, as the organic material forming the powder material rm, a substance having at least one of a hydroxyl group and a carboxyl group is preferable. in a case where the foreign material cm is contained in the defibrated material m 3 as the powder material rm contains the substance, the foreign material cm can be removed more efficiently. it is considered that such excellent effects can be obtained for the following reasons. that is, in general, a recording material such as ink or toner used for a recording medium such as paper is designed so as to have excellent affinity and adhesion to cellulose fiber, which is the main material of the recording medium. on the other hand, the cellulose fiber contains a polymer material containing β-glucose having a large number of hydroxyl groups in the molecule as a constituent monomer, and is a highly hydrophilic material. a substance having at least one of hydroxyl group and carboxyl group is also highly hydrophilic and exhibits polarity (hydrophilicity) similar to that of cellulose fiber. therefore, the substance having at least one of a hydroxyl group and a carboxyl group has a high affinity with the foreign material cm derived from a recording material such as ink and toner, and can effectively adsorb the foreign material cm in a case where the substance comes in contact with the defibrated material m 3 containing the foreign material cm. as a result, the foreign material cm contained in the defibrated material m 3 can be more efficiently removed. in addition, if the powder material rm contains the material, when the powder material rm is supplied so as to collide with the defibrated material m 3 , by the electrostatic interaction, collision between the foreign material cm contained in the defibrated material m 3 and the powder material rm is likely to occur, and the removal efficiency of the foreign material cm contained in the defibrated material m 3 can be made particularly excellent. in addition, even in a case where the substance remains in the defibrated material m 3 after the deinking processing, normally, adverse influence on the defibrated material m 3 after the deinking processing and the sheet s manufactured using the same is sufficiently small. in addition, in some cases, it is possible to obtain an effect such that the sheet s to be manufactured can be made more excellent in paper strength, affinity to a recording material such as ink, toner, or the like. the substance contains various compounds such as a polymeric material and a low-molecular material, and preferably has a sugar chain structure. a compound having a sugar chain structure is normally a material having a high ratio of hydroxyl groups in the molecule (ratio of the number of hydroxyl groups to the molecular weight) and particularly high hydrophilicity. therefore, it is particularly advantageous in improving the adsorption property of foreign material cm. examples of the polymeric material having a sugar chain structure include cellulose, a cellulose-modified material (for example, methylcellulose, carboxymethylcellulose or a salt thereof (for example, sodium salt and the like)), starch, alginic acid, chitosan, and the like. among these, it is preferable to contain at least one of cellulose and a cellulose-modified material, and it is more preferable to contain a salt of carboxymethyl cellulose. when the salt of carboxymethyl cellulose is used, the above-described effect is more remarkably exhibited. in addition, the salt of carboxymethyl cellulose has appropriate conductivity, it is unlikely to charge during deinking processing, and the effect of neutralizing is exhibited. as a result, it is possible to more effectively prevent occurrence of problems such as constituent particles of the powder material clinging to the fiber, and causing it difficult to separate from the fiber during the deinking processing. the powder material rm may contain paper dust. hereinafter, the combination of the constituent material of the first particle and the constituent material of the second particle will be described. in a case where both of the first particle and the second particle are formed of a material containing an organic material, the following effects can be obtained. that is, many organic materials have a feature that is easily charged by friction. therefore, by using a plurality of types of organic materials in combination (using in combination as constituent material of first particle and constituent material of second particle), the foreign material cm contained in the fiber-containing material m 3 can be effectively removed by electrical adsorption, and the removal efficiency of the foreign material cm as a whole can be further improved. in addition, the foreign material cm can be removed (deinked) from the fiber-containing material m 3 with a high removal rate in short time processing. in a case where both of the first particle and the second particle are formed of a material containing an organic material, for example, one of the first particles and the second particles may be formed of a material containing a salt of carboxymethyl cellulose and the other may be formed of a material containing a polyamide. as a result, the function possessed by the salt of carboxymethyl cellulose as described above can be more effectively exhibited while exhibiting the superior charging property possessed by the polyamide. the frequency of contact and separation opportunities between the fiber forming the fiber-containing material m 3 and the powder material rm increases, and the removal ability of the foreign material cm as a whole of the powder material rm can be made particularly excellent. in addition, in a case where both of the first particle and the second particle are formed of a material containing an organic material, one of the first particle and the second particle may be formed of a material containing a salt of carboxymethyl cellulose and the other of the first particle and the second particle may be formed of a material containing polyacrylamide. as a result, the function possessed by the salt of carboxymethyl cellulose as described above can be more effectively exhibited while exhibiting the superior charging property possessed by the polyamide. the frequency of contact and separation opportunities between the fiber forming the fiber-containing material m 3 and the powder material rm increases, and the removal ability of the foreign material cm as a whole of the powder material rm can be made particularly excellent. in addition, in a case where both of the first particle and the second particle are formed of a material containing an organic material, one of the first particle and the second particle may be formed of a material containing a salt of carboxymethyl cellulose, and the other may be formed of a material containing a polyacrylate (for example, sodium salt or the like). polyacrylate is normally a material with high crystallinity, and the solid is likely to form angular portions on the surface. therefore, by using as a constituent material of the powder material rm, the removal efficiency of the foreign material cm from the fiber-containing material m 3 can be made more excellent. on the other hand, in a case where a polyacrylic acid salt is used alone, the fiber forming the fiber-containing material m 3 is likely to be damaged, and when used in combination with a salt of carboxymethyl cellulose, it is possible to sufficiently exhibit the effect of using the polyacrylic acid salt while appropriately protecting the fiber. as a result, the removal efficiency of the foreign materials cm from the fiber-containing material m 3 can be made more excellent while suitably protecting the fiber forming the fiber-containing material m 3 from damage in the deinking processing. in addition, in a case where both of the first particle and the second particle are formed of a material containing an organic material, one of the first particle and the second particle may be formed of a material containing a salt of carboxymethyl cellulose, and the other may be formed of a material containing at least one of a salt of carboxymethyl cellulose having a molecular weight different from that of the carboxymethyl cellulose salt and a starch. amorphous carboxymethyl cellulose has a feature of deformability (elastic deformation) at the time of pressure application. therefore, when colliding with the fiber, the foreign material cm entering the fiber recessed portion can be removed by deforming according to the unevenness shape of the fiber surface. however, by having deformability at the time of fiber collision, the time of adhesion to the fiber after collision increases and the fiber and particle can not be rapidly separated from each other. therefore, by using a high molecular weight carboxymethyl cellulose salt or starch which is not easily elastically deformed for the first particle, the second particle is rapidly separated from the collided fiber and the opportunity of contact between the particle and the fiber can be increased. as a result, an effect of further improving the effect of removing the foreign materials cm on the fiber surface can be obtained. in addition, in a case where both of the first particle and the second particle are formed of a material containing an inorganic material, the following effects can be obtained. that is, many inorganic materials have high specific gravity and high hardness. therefore, it is possible to increase the collision energy at the time of collision with the fiber-containing material m 3 in the deinking processing and to improve the removal efficiency of the foreign material cm from the fiber-containing material m 3 . in addition, the foreign material cm can be removed (deinked) from the fiber-containing material m 3 with a high removal rate in short time processing. in a case where both of the first particle and the second particle are formed of a material containing an inorganic material, for example, one of the first particles and the second particles may be formed of a material containing calcium carbonate and the other may be formed of a material containing titanium oxide. as a result, the function possessed by the calcium carbonate as described above can be more effectively exhibited while exhibiting the characteristic of titanium oxide having high specific gravity and high hardness, and the removal ability of the foreign material cm as a whole of the powder material rm can be made particularly excellent. in addition, in a case where both of the first particle and the second particle are formed of a material containing an inorganic material, for example, one of the first particles and the second particles may be formed of a material containing calcium carbonate and the other may be formed of a material containing alumina. as a result, the function possessed by the calcium carbonate as described above can be more effectively exhibited while exhibiting the characteristic of alumina having high specific gravity and high hardness, and the removal ability of the foreign material cm as a whole of the powder material rm can be made particularly excellent. in addition, in a case where both of the first particle and the second particle are formed of a material containing an inorganic material, for example, one of the first particles and the second particles may be formed of a material containing calcium carbonate and the other may be formed of a material containing talc. talc is a highly disintegratable mineral and produces a plurality of smaller diameter particles upon contact with the fiber. therefore, when colliding with the fiber, it is possible to adsorb the foreign material cm entered the recessed portion on the fiber surface. however, fine particles entered the fiber recessed portion are unlikely to separate from the fiber due to van der waals force or the like. therefore, the calcium carbonate of the second particle collides with the fiber and pushes out the fine talc particles and foreign material cm entered the fiber recessed portion out of the fiber recessed portion. as a result, an effect of further improving the removal effect of foreign material cm on the fiber surface can be obtained. in addition, in a case where one of the first particle and the second particle is formed of a material containing an organic material and the other is formed of a material containing an inorganic material, the following effects can be obtained. that is, in general, a feature possessed by the organic material that the organic material is likely to be charged by friction and can effectively remove the foreign material cm contained in the fiber-containing material m 3 by electrical adsorption is exhibited. in general, a feature possessed by the inorganic material that the inorganic material has a high specific gravity and a high hardness, can increase the collision energy at the time of collision with the fiber-containing material m 3 in the deinking processing, and can effectively remove the foreign materials cm from the fiber-containing material m 3 , is exhibited. therefore, the effect of removing the foreign material cm as a whole of the powder material rm can be made more excellent. in a case where one of the first particle and the second particle is formed of a material containing an organic material and the other is formed of a material containing an inorganic material, for example, one of the first particle and the second particle may be formed of a material containing a salt of carboxymethyl cellulose and the other may be formed of a material containing alumina. alumina is normally likely to form angular portions on the surface. therefore, by using the alumina as a constituent material of the powder material rm, the removal efficiency of the foreign material cm from the fiber-containing material m 3 can be made more excellent. on the other hand, in a case where alumina is used alone, the fiber forming the fiber-containing material m 3 is likely to be damaged, and when used in combination with a salt of carboxymethyl cellulose, it is possible to sufficiently exhibit the effect of using the alumina while appropriately protecting the fiber. as a result, the removal efficiency of the foreign materials cm from the fiber-containing material m 3 can be made more excellent while suitably protecting the fiber forming the fiber-containing material m 3 from damage in the deinking processing. in addition, in a case where one of the first particle and the second particle is formed of a material containing an organic material and the other is formed of a material containing an inorganic material, one of the first particle and the second particle may be formed of a material containing a salt of carboxymethyl cellulose and the other may be formed of a material containing calcium carbonate. as a result, the effect of using the salt of carboxymethyl cellulose as described above and the effect of using calcium carbonate act synergistically, and the removal ability of foreign material cm as a whole powder material rm can be made particularly excellent. it is preferable that the first particle and the second particle have different average particle diameters from each other. as a result, while making removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 more excellent, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be efficiently removed. as a result, the removal efficiency of foreign material cm from the defibrated material m 3 can be made particularly excellent. in the following description, it is assumed that the average particle diameter of the second particles is larger than the average particle diameter of the first particles. the average particle diameter of the first particle group consisting of a plurality of first particles and the average particle diameter of the second particle group consisting of a plurality of second particles may be obtained from the particle size distribution of each particle group before mixing. the peak particle diameter on the small particle diameter side in the particle size distribution of the powder material rm may be the average particle diameter of the first particle group, and the peak particle diameter on the large particle diameter side in the particle size distribution of the powder material rm may be the average particle diameter of the second particle group (refer to fig. 11 ). in the specification, the average particle diameter refers to an average particle diameter based on the number unless otherwise specified. the average particle diameter of the powder refers to the number average value of the particle long diameter (diameter in the length direction of the particle) measured using a dry type particle size distribution meter and calculated by analysis using a static image analyzer (static image analysis apparatus: morphologi g3: manufactured by malvern). the average particle diameter of the second particle group is preferably larger than the average particle diameter of the first particle group, and in particular, there is a preferable range for the degree of divergence between the particle diameters of both. that is, the average particle diameter of the second particle group is preferably two times or more and 10,000 times or less, more preferably 3 times or more and 1,000 times or less, and still more preferably 5 times or more and 100 times or less the average particle diameter of the first particle group. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm during the deinking processing or the like. the average particle diameter of the first particle group is preferably 0.01 μm or more and 10 μm or less, more preferably 0.05 μm or more and 7.0 μm or less, and still more preferably 0.1 μm or more and 5.0 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm (in particular, first particle) during the deinking processing or the like. the minimum particle diameter of the first particle group is preferably 0.01 μm or more and 3.0 μm or less, more preferably 0.02 μm or more and 2.5 μm or less, and still more preferably 0.03 μm or more and 2.0 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm (in particular, first particle) during the deinking processing or the like. the maximum particle diameter of the first particle group is preferably 0.1 μm or more and 100 μm or less, more preferably 0.2 μm or more and 70 μm or less, and still more preferably 0.3 μm or more and 50 μm or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the average value of the aspect ratios of the first particles forming the first particle group is preferably 1.0 or more and 5.0 or less, more preferably 1.05 or more and 4.9 or less, and still more preferably 1.1 or more and 4.8 or less. as a result, the foreign material cm intruding a minute space such as a gap between the fibers forming the defibrated material m 3 can be more efficiently removed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the content rate of the first particles in the powder material rm is preferably from 10% by volume or more and 90% by volume or less, more preferably 20% by volume or more and 80% by volume or less, and still more preferably 30% by volume or more and 70% by volume or less. as a result, the synergistic effect due to containing the first particle group and the second particle group that satisfy the relationship of the particle diameter as described above is exhibited more remarkably. in addition, the average particle diameter of the second particle group is preferably 5 μm or more and 1500 or less, more preferably 7 μm or more and 1,400 μm or less, and still more preferably 10 μm or more and 1,200 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the minimum particle diameter of the second particle group is preferably 0.5 μm or more and 1,000 μm or less, more preferably 0.7 μm or more and 850 μm or less, and still more preferably 1 μm or more and 800 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the maximum particle diameter of the second particle group is preferably 5 μm or more and 3,000 μm or less, more preferably 10 μm or more and 2,000 μm or less, and still more preferably 15 μm or more and 1,500 μm or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the average value of the aspect ratios of the second particles forming the second particle group is preferably 1.0 or more and 50 or less, more preferably 1.05 or more and 30 or less, and still more preferably 1.1 or more and 20 or less. as a result, the removal efficiency of the foreign material cm adhering in a state of being exposed on the outer surface of the defibrated material m 3 can be made more excellent, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. when the average value of the aspect ratios of the first particles forming the first particle group is a 1 and the average value of the aspect ratios of the second particles forming the second particle group is a 2 , it is preferable that the relationship of 0.1≤a 2 /a 1 ≤50 be satisfied, it is more preferable that the relationship of 0.5≤a 2 /a 1 ≤30 be satisfied, and it is still more preferable that the relationship of 0.8≤a 2 /a 1 ≤15 be satisfied. the synergistic effect due to containing the first particle group and the second particle group that satisfy the relationship of the particle diameter as described above is exhibited more remarkably. the average particle diameter of the powder material rm as a whole is preferably 2.6 μm or more and 255 μm or less, more preferably 5.1 μm or more and 153 μm or less, and still more preferably 10.2 μm or more and 120 μm or less. as a result, the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. in addition, it is possible to effectively prevent from containing excessively minute particles, and to more effectively prevent unintended scattering (in particular, scattering which is difficult to recover) of the powder material rm during the deinking processing or the like. in addition, the ratio (r/l) of the average particle diameter (r) of the powder material rm to the average length (l) of the particles forming the defibrated material m 3 is preferably 0.001 or more and 10 or less, more preferably 0.003 or more and 9 or less, and still more preferably 0.005 or more and 8 or less. as a result, in the deinking processing, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the content rate of the second particles in the powder material rm is preferably from 10% by volume or more and 90% by volume or less, more preferably 20% by volume or more and 80% by volume or less, and still more preferably 30% by volume or more and 70% by volume or less. as a result, the synergistic effect due to containing the first particle group and the second particle group that satisfy the relationship of the particle diameter as described above is exhibited more remarkably. when the content ratio of the first particles in the powder material rm is x 1 (% by volume) and the content rate of the second particles in the powder material rm is x 2 (% by volume), it is preferable that the relationship of 0.01≤x 1 /x 2 ≤10.0 be satisfied, it is more preferable that the relationship of 0.01≤x 1 /x 2 ≤5.0 be satisfied, and it is still more preferable that the relationship of 0.15≤x 1 /x 2 ≤2.33 be satisfied. as a result, the synergistic effect due to containing the first particle group and the second particle group that satisfy the relationship of the particle diameter as described above is exhibited more remarkably. for example, the first particle and the second particle may have the same density, and it is preferable that the first particle and the second particle have mutually different densities from each other. as a result, the synergistic effect due to containing the first particle group and the second particle group is exhibited more remarkably. in the specification, unless otherwise specified, density refers to true specific gravity. in a case where the density of the first particle is different from the density of the second particle, the density of the first particle may be smaller than the density of the second particle, and is preferably greater than the density of the second particle. as a result, in the deinking processing, the kinetic energy of the first particles (particles having a relatively small particle diameter) can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded, and the kinetic energy of the second particles (particles having a relatively large particle diameter) can be more reliably prevented from being excessively increased. accordingly, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged (excessively shortening fiber length). in particular, when the density of the first particles is ρ 1 [g/cm 3 ] and the density of the second particles is ρ 2 [g/cm 3 ], it is preferable that the relationship of 0.2≤ρ 1 /ρ 2 ≤15 be satisfied, it is more preferable that the relationship of 0.3≤ρ 1 /ρ 2 ≤10 be satisfied, and it is still more preferable that the relationship of 0.5≤ρ 1 /ρ 2 ≤5 be satisfied. as a result, in the deinking processing, the kinetic energy of the first particles (particles having a relatively small particle diameter) can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded, and the kinetic energy of the second particles (particles having a relatively large particle diameter) can be more reliably prevented from being excessively increased. accordingly, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged (excessively shortening fiber length). the density of the first particles is preferably 1.3 g/cm 3 or more and 10.0 g/cm 3 or less, more preferably 1.8 g/cm 3 or more and 8.0 g/cm 3 or less, and still more preferably 2.5 g/cm 3 or more and 5.0 g/cm 3 or less. as a result, in the deinking processing, the kinetic energy of the first particles can be sufficiently increased, the deinking processing with the first particles (in particular, removal of foreign material cm intruding into a minute space such as a gap between fibers forming defibrated material m 3 ) can be efficiently proceeded. accordingly, the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the density of the second particles is preferably 0.3 g/cm 3 or more and 8.0 g/cm 3 or less, more preferably 0.6 g/cm 3 or more and 6.2 g/cm 3 or less, and still more preferably 0.8 g/cm 3 or more and 4.8 g/cm 3 or less. as a result, in the deinking processing, the kinetic energy of the second particles can be more reliably prevented from being excessively increased, the fiber forming the defibrated material m 3 can be more effectively prevented from being damaged, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. the ratio (ρ p /ρ f ) of the average value (ρ p ) of the density of the particles forming the powder material rm to the average value (ρ f ) of the density of the fiber forming the defibrated material m 3 is 0.2 or more and 10 or less, more preferably 0.4 or more and 4.5 or less, and still more preferably 0.5 or more and 3.5 or less. as a result, in the deinking processing, the defibrated material m 3 and the powder material rm can be more suitably mixed, and the removal efficiency of the foreign material cm as a whole of the powder material rm can be made more excellent. examples next, specific examples of the invention will be described. [1] preparation of powder material (deinking agent) example 11 first, calcium carbonate powder having an average particle diameter of 5 μm, a minimum particle diameter of 1 μm, and a maximum particle diameter of 10 μm was prepared as a first particle group. the average value of the aspect ratios of the particles (first particles) forming the first particle group was 1.3. on the other hand, a commercially available powdered carboxymethyl cellulose sodium salt (manufactured by wako pure chemical industries, ltd.) was prepared. the powdery sodium salt of carboxymethyl cellulose was subjected to classification processing using a classification device to obtain a plurality of fractions. among these, a fraction having an average particle diameter of 120 μm, a minimum particle diameter of 25 μm, and a maximum particle diameter of 150 μm was defined as a second particle group. the average value of the aspect ratios of the particles (second particles) forming the second particle group was 15. the first particle group and the second particle group as described above were mixed at a volume ratio of 1:9 to obtain a powder material (deinking agent) as a mixed powder. examples 12 to 38 a powder material (deinking agent) as a mixed powder was obtained in the same manner as in example 11 except that the conditions (constituent materials, material particle size distribution) of the first particle group and the second particle group are set as shown in tables 3 and 4, and the mixing ratio of the first particle group and the second particle group was changed as shown in tables 3 and 4. regarding those containing the particle group containing particles formed of sodium salt of carboxymethyl cellulose (cmc-na) of the powder material (deinking agent) according to each of the above examples, the cmc-na had solubility at 25° c. in water of 3.0 g/100gh 2 o or more and 50 g/100gh 2 o less, or the contact angle of water was 45° or less in any case. comparative example 3 a powder material (deinking agent) was obtained in the same manner as in example 11 except that the fraction having an average particle diameter of 120 μm, a minimum particle diameter of 25 μm, and a maximum particle diameter of 150 μm was used as it was as a powder material (deinking agent) among the powders of sodium salt of carboxymethyl cellulose fractionated in the same manner as in example 11. comparative examples 4 and 5 a powder material (deinking agent) was obtained in the same manner as in comparative example 3 except that the conditions of the particles forming the powder material were changed as shown in table 4. the conditions of the powder materials (deinking agent) according to each example and each comparative example are summarizes in tables 3 and 4. in the table, the sodium salt of carboxymethyl cellulose is indicated as “cmc-na”. in addition, in each of the sodium salts of carboxymethyl cellulose not showing the molecular weight in the table, the weight average molecular weight was approximately 3,000. table 3first particleaverageminimummaximumparticleparticleparticlecontentconstituentdiameterdiameterdiameteraspectdensity[% bysecond particlematerial[μm][μm][μm]ratios[g/cm 3 ]mass]constituent materialexample 11caco 351101.32.9310.1cmc-naexample 12tio 20.210.10.31.14.311.1cmc-naexample 13talc52501.12.719.0cmc-naexample 14alumina54.55.31.23.543.4cmc-naexample 15caco 351101.32.939.3polyamideexample 16caco 351101.32.9310.9starchexample 17caco 351101.32.939.3polyacrylic acid naexample 18caco 351101.32.939.3polyacrylamideexample 19alumina54.55.31.23.5410.0polyamideexample 20alumina54.55.31.23.5411.8starchexample 21alumina54.55.31.23.5410.0polyacrylic acid naexample 22alumina54.55.31.23.5410.0polyacrylamideexample 23tio 20.210.10.31.14.311.1cmc-naexample 24tio 20.210.10.31.14.310.2polyamideexample 25tio 20.210.10.31.14.312.0starchexample 26tio 20.210.10.31.14.310.2polyacrylic acid naexample 27tio 20.210.10.31.14.310.2polyacrylamidesecond particleaverageminimummaximumaverage particleparticleparticleparticlecontentdiameter as adiameterdiameterdiameteraspectdensity[% bywhole of powder[μm][μm][μm]ratios[g/cm 3 ]mass]material [μm]example 1112025150151.689.9108.4example 1212025150151.688.9106.7example 1312025150151.681.098.1example 1412025150151.696.6116.1example 15105151.11.1490.79.5example 1630101001.51.489.127.3example 17100302501.71.290.791.2example 1850302501.71.1990.745.8example 19105151.11.1490.09.5example 2030101001.51.488.227.1example 21100302501.71.290.090.5example 2250302501.71.1990.045.5example 2312025150151.688.9106.7example 24105151.11.1489.89.0example 2530101001.51.488.026.4example 26100302501.71.289.889.8example 2750302501.71.1989.844.9 table 4first particleaverageminimummaximumsecondparticleparticleparticlecontentparticlediameterdiameterdiameteraspectdensity[% byconstituentconstituent material[μm][μm][μm]ratios[g/cm 3 ]mass]materialexample 28cmc-na12025150151.610.9cmc-na(mw8000)(mw3000)example 29polyamide10.521.21.1410.9cmc-naexample 30polyester1.20.531.31.3810.9cmc-naexample 31starch31101.51.49.2cmc-naexample 32polyacrylic acid na53251.71.210.9cmc-naexample 33methylcellulose5220121.610.9cmc-naexample 34rosin525041.0810.9cmc-naexample 35polyacrylamide31201.21.1910.9cmc-naexample 36tio 20.210.10.31.14.311.0caco 3example 37talc52501.12.718.9caco 3example 38alumina54.55.31.23.543.3caco 3comparativecmc-na12025150151.6100—example 3comparativecaco 351101.32.93100—example 4comparativetio 20.210.10.31.14.3100—example 5second particleaverageminimummaximumaverage particleparticleparticleparticlecontentdiameter as adiameterdiameterdiameteraspectdensity[% bywhole of powder[μm][μm][μm]ratios[g/cm 3 ]mass]material [μm]example 2812025150151.689.1120example 2912025150151.689.1107.0example 3012025150151.689.1107.1example 3112025150151.690.8109.2example 3212025150151.689.1107.5example 3312025150151.689.1107.5example 3412025150151.689.1107.5example 3512025150151.689.1107.3example 3651101.32.9389.04.5example 37205451.32.9381.117.2example 38101201.32.9396.79.8comparative——————120example 3comparative——————5example 4comparative——————0.21example 5 [2] deinking processing and manufacture of sheet using the powder materials (deinking agent) prepared in each of the above examples and comparative examples, the following processing (deinking processing) and manufacture of a sheet were performed. first, the sheet manufacturing apparatus having the configuration shown in fig. 1 was prepared, and commercially available copy paper was subjected to monochrome printing of 10% duty on one side with an ink jet printer (px-m7050ft manufactured by seiko epson corporation) was prepared as a raw material. the mesh opening of the mesh belt (mesh body) included in the first web forming portion of the powder material removing portion of the sheet manufacturing apparatus was 600 μm. next, the above raw material was supplied to the raw material supply portion of the sheet manufacturing apparatus, the sheet manufacturing apparatus was operated, and the raw material was subjected to processing such as crushing, defibrating, deinking and the like to produce a sheet. at this time, the supply amount of the powder material (deinking agent) to 100 parts by mass of the fiber-containing material (defibrated material) was 100 parts by mass. the manufacturing conditions of the sheets were the same in each of the examples and the comparative examples except that the type of the powder material (deinking agent) was changed. in each of the above embodiments, the ratio (r/l) of the average particle diameter (r) of the powder material as a whole to the average length (l) of the fiber forming the defibrated material to be subjected to the deinking processing was 0.001 or more and 10 or less in any case. in addition, in each of the above examples, the ratio (ρ p /ρ f ) of the average value (ρ p ) of the density of the particles forming the powder material to the average value (ρ f ) of the density of the fiber forming the defibrated material to be subjected to the deinking processing was 0.2 or more and 10 or less in any case. [3] evaluation [3-1] coloring of defibrated material after deinking processing (remaining foreign material) for each of the examples and each of the comparative examples, a portion of the first web formed in the first web forming portion was taken out and observed with a digital microscope (vhx-5000 manufactured by keyence corporation). compared with the state of the first web in a case where the processing was performed in the same manner as above except that the powder material (deinking agent) was not used, the remaining state of the foreign material derived from the recording material (ink) was evaluated according to the following criteria. a: no remaining foreign material is observed. b: almost no remaining foreign material is observed. c: remaining foreign material is slightly observed. d: remaining foreign material is observed. e: remaining foreign material is significantly observed. these results are summarized in tables 5 and 6. table 5remaining foreign materialexample 11bexample 12cexample 13cexample 14bexample 15cexample 16cexample 17cexample 18cexample 19bexample 20bexample 21bexample 22bexample 23bexample 24cexample 25cexample 26cexample 27c table 6remaining foreign materialexample 28bexample 29aexample 30cexample 31bexample 32bexample 33cexample 34cexample 35aexample 36bexample 37bexample 38bcomparative example 3ecomparative example 4ecomparative example 5e as is apparent from tables 5 and 6, excellent results were obtained in the invention. that is, in the invention, the powder material (deinking agent) efficiently removed the foreign material contained in the defibrated material. in addition, in the invention, the whiteness of the manufactured sheet was excellent, and unintended coloring or unintended color unevenness due to remaining foreign material was not observed. in addition, in the invention, separability between the defibrated material subjected to the deinking treatment and the powder material (deinking agent) was also excellent. in each of the above examples, the removal rate of the powder material in the powder material removing portion was 90% or more in any case, and the removal rate of the second particle was higher than the removal rate of the first particle. on the contrary, satisfactory results were not obtained in the comparative example. in addition, deinking processing and sheet manufacture were performed in the same manner as described above except that the supply amount of the powder material (deinking agent) to 100 parts by mass of the defibrated material was variously changed in the range of 10 parts by mass or more and 100,000 parts by mass or less, and the same evaluation as above was performed, and the same results as described above were obtained. in addition, the deinking processing and the sheet manufacture were performed in the same manner as described above except the apparatus used for the deinking processing and the sheet manufacture was changed to the one having the construction shown in fig. 5 , the one having the construction shown in fig. 7 , and the one shown in fig. 9 . the entire disclosure of japanese patent applications no. 2017-254973, filed dec. 28, 2017, and no. 2018-032223, filed feb. 26, 2018, are expressly incorporated by reference herein.
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096-708-801-211-315
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US
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[
"US"
] |
G06F1/16
| 1987-04-24T00:00:00 |
1987
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[
"G06"
] |
portable computer system and stand for use therewith
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there is disclosed a portable computer system including a computer, a power supply for the computer and a plate assembly which provides a support for the power supply external to the computer and a foot for disposing the computer in a desired position. the plate assembly includes a first plate to which the computer is attached, a second plate to which the power supply is attached and a hinge coupling the first and second plates together. the hinge allows the plates to be in substantial planar alignment or at an angle to each other to permit the second plate to function as a foot for the computer.
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1. a portable computer system, comprising: a computer; a power supply for said computer; a plate assembly comprising: a first plate, a second plate, bracket means, said computer being attached to said first plate by said bracket means, said power supply being attached to said second plate, and hinge means for coupling said first plate to said second plate such that said first plate and said second plate may be placed in substantial planar alignment with each other or may be disposed such that said second plate functions as a foot for said computer assembly, said hinge means serving to retain said first and second plates in a desired position. 2. an assembly in accordance with claim 1, wherein: said second plate comprises a first portion to which said hinge means is attached, and a second portion disposed at a right angle to said first portion. 3. an assembly in accordance with claim 1 wherein: said hinge means comprises a friction hinge. 4. a portable computer system, comprising: a computer; a power supply for said computer; a plate assembly comprising: a first plate, a second plate, bracket means, said computer being attached to said first plate by said bracket means, said power supply being attached to said second plate, and hinge means for coupling said first plate to said second plate such that said first plate and said second plate may be placed in substantial planar alignment with each other or may be disposed such that said second plate functions as a foot for said computer assembly, said hinge means serving to retain said first and second plates in a desired position; a tripod; and tripod coupling means carried by said first plate for coupling said assembly to said tripod. 5. an assembly in accordance with claim 4, wherein: said tripod coupling means comprises a pipe flange affixed to said first plate and a tripod post screwed into said flange. 6. an assembly in accordance with claim 4 wherein: said tripod mounting means comprises a straight coupling attached to said first plate and adapted to receive a tripod post; and a tripod post having one end adapted to engage said straight coupling and its other end adapted to be supported by said tripod. 7. an assembly in accordance with claim 4 wherein: said hinge means comprises a friction hinge.
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background of the invention this invention pertains to a portable computer system and to a stand for use with a computer. honeywell inc. has developed a portable computer system which is used as a diagnostic tool for testing and maintenance of complex systems. this system, which is referred to as mentor, has been reported in usa today, feb. 17, 1986; the denver post, apr. 5, 1986, section c, page 1-c; high technology, april, 1986, page 9; and business week, feb. 10, 1986, page 93. the mentor system utilizes a lap type personal computer which is used to read remotely acquired sensor data from hvac equipment. the computer is used to analyze the data and to compare it to a data base to determine whether system degradation has occurred or the problem exists. one feature of the mentor system is that the computer may be mounted on a tripod. most specifically the computer and its power supply are in a carrying case along with a power supply. originally, the carrying case itself which contained the computer and power supply was mounted to a tripod. this original arrangement proved to be unstable and have poor heat disapation for the computer and power supply, and thus lead to a high failure rate. the invention described herein eliminates these problems. summary of the invention in accordance with the principles of the invention a lap type computer is mounted on top of a first plate and the power supply for the computer is mounted on top of a second plate. the first and second plates are connected together by means of friction hinges. when the computer is to be stored, the two plates are disposed in planar alignment with each other. when it is desired to operate the computer, it is removed from its carrying case and the second plate is swung down so that it is at an angle to the first plate preferably an angle in the order of 90 degrees. with this arrangement the computer is placed at a convenient operating angle for the operator. additionally the power supply is less likely to overheat since air currents can now move along the power supply to dissipate heat. further in accordance with the principles of the invention the second plate includes two portions at right angles to each other so that when the computer is in its operating position one portion of the second plate forms a rear foot for the computer. still further in accordance with the principals of the invention the first plate has affixed thereto a pipe flange or a straight coupling to which a tripod post may be connected. the resulting structure may then be supported on a tripod. with the structure on a tripod the second plate is swung down so that it is at an angle to the first plate so that air currents can more freely circulate around the power supply and dissipate any heat. brief description of the drawing the invention will be understood from a reading of the following detailed description in conjunction with the drawing in which: fig. 1 is a side view of an assembly in accordance with the invention; fig. 2 is a perspective view of the assembly of fig. 1 mounted on a tripod; fig. 3 is a top view of the plate assembly in accordance with the invention having the power supply mounted thereon; fig. 4 is a side view of the assembly of fig. 3; fig. 5 is a bottom view of the assembly of fig. 3; fig. 6 is a front end view of the assembly of fig. 3; fig. 7 is a perspective view of one of the brackets used in conjunction with the plates of figs. 3-6; and fig. 8 is a side view of an alternate embodiment of the plate assembly. detailed description as shown in figs. 1 and 2 a computer 1 and a power supply 2 are attached to a plate assembly 3. the computer 1 is attached to the plate assembly 3 by means of brackets 9. the plate assembly 3 includes two plates which are coupled together by means of friction hinges so that the two plates may be placed in the position shown in figs. 1 and 2 when the computer is to be used. when the computer is to be stored then the two plates are disposed in the same plane. by means of this plate assembly the power supply is positioned such that air currents may freely flow around the power supply to dissipate any heat. additionally as shown in fig. 1 the plates provide a positioning arrangement for the computer assembly such that the computer when set on a table or desk top is placed in a convenient operating position. where operating space is limited the computer assembly may be placed on a tripod 5 as shown in fig. 2. turning now to figs. 3-6 the plate assembly will be described in greater detail. in figs. 3-6 the power supply 2 is shown attached to the plate assembly. the plate assembly 3 includes a first plate 6 and a second plate 7. as most clearly seen in figs. 4 and 5 the first plate 6 includes notches 8 which capture screws that are attached to brackets 9. as most clearly shown in figs. 1 and 2, the brackets 9 engage grooves on the computer 1. the second plate 7 includes a first portion 10 and a second portion 11, the second portion 11 being disposed at right angles to the first portion 10. as more clearly shown in fig. 4 the power supply 2 is fastened to the second plate 7 by means of screws. the first plate 6 is connected to the second plate 7 by means of two tension adjustable friction hinges 12, 13. the friction hinges 12, 13 are of a type commercially available and permits the two plates 6 and 7 to be moved relative to one another to a desired position. more specifically, plate 10 is chosen to be of such a length that when the computer assembly is placed on a desk top, the keyboard is at a correct ergonomic angle. a pipe flange 14 may be affixed to the first plate 6 so that the computer assembly may be mounted on a tripod. the pipe flange 14 includes an internally threaded portion adapted to receive a tripod post 15 as shown in fig. 6 which in turn may be supported by a tripod. alternately the first plate 6 may have a straight coupling welded thereto for receiving a tripod post. fig. 8 illustrates such an arrangement with a straight coupling 19. as shown in fig. 7 the bracket 9 are of straight forward design and are of some what a u shape. the bracket includes a first portion 16 and second and third portions 17 and 18 which are at right angles to the first portion 16. portion 17 is dimensioned to engage a grove on the computer 1. portion 18 includes a tapped hole to receive the screw which will engage in a notch 8 on plate 6. the computer 1 is a commercially available computer and details of the computer itself do not form any part of the present invention. likewise the power supply 2 is of conventional design and may be a commercially available power supply. details of the power supply 2 likewise do not form any part of the present invention. the computer system described above is particularly useful for acquiring data from remote hvac equipment and displaying the acquired information in various formats. the computer system in particular may have a data base such that the computer can determine from the acquired data if system degradation has occurred, dynamically determine when the service is needed and diagnose problems from the acquired data. this system is particular useful as a portable chiller/cooler maintenance system.
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097-309-100-640-019
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US
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[
"US"
] |
G06F17/00
| 2012-07-06T00:00:00 |
2012
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[
"G06"
] |
recording information for a web manufacturing process
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a web manufacturing process includes recording, onto an excess trim region of a web that is a subject of the web manufacturing process, information relating to a processing stage of the web manufacturing process.
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1 . (canceled) 2 . the method of claim 6 , further comprising performing, by a second processing stage that is downstream of the first processing stage, the corrective action. 3 . the method of claim 2 , wherein performing the corrective action comprises adjusting at least one parameter of the second processing stage based on the recorded information. 4 . the method of claim 6 , wherein recording the information comprises recording a barcode. 5 . the method of claim 4 , wherein recording the barcode comprises recording a non-directional barcode that is recognizable by a reader in both traveling directions of the web. 6 . a method of a web manufacturing process, comprising: recording, onto an excess trim region of a web that is a subject of the web manufacturing process, information relating to a first processing stage of the web manufacturing process; determining, based on reading the recorded information, a corrective action to take with respect to an issue indicated by the recorded information; and receiving parameter data from a sensor associated with the first processing stage, wherein the recorded information is based on the parameter data, and where the parameter data includes a measured parameter that relates to manufacturing processing performed by the first processing stage. 7 . the method of claim 6 , wherein the issue is a quality issue associated with a portion of the web, and wherein the corrective action compensates for the quality issue. 8 . the method of claim 7 , further comprising: identifying, based on the recorded information, a location of the portion of the web that has the quality issue. 9 . the method of claim 6 , wherein recording the information comprises repeatedly recording information relating to the measured parameter associated with the first processing stage at multiple positions in the excess trim region. 10 . a web manufacturing system comprising: web manufacturing infrastructure having a plurality of processing stages to apply corresponding manufacturing processes on a web, wherein a first of the plurality of processing stages is to record information relating to a quality issue onto an excess trim region of the web, wherein the first processing stage is to further record parameter data onto the excess trim region of the web, where the parameter data relates to a parameter of a manufacturing processing performed by the first processing stage, the parameter measured by a sensor of the first processing stage, and wherein a second of the plurality of processing stages is to perform a corrective action in response to the recorded information to address the quality issue. 11 . the web manufacturing system of claim 10 , wherein the second processing stage is downstream of the first processing stage. 12 . the web manufacturing system of claim 10 , wherein the corrective action includes modifying a parameter relating to a manufacturing process performed by the second processing stage. 13 . the web manufacturing system of claim 10 , wherein the corrective action includes culling a portion of the web having the quality issue. 14 . the web manufacturing system of claim 10 , further comprising a storage medium to store parameter data measured by sensors of the plurality of processing stages. 15 . the web manufacturing system of claim 10 , wherein the first processing stage has a printer to record the information relating to the quality issue onto the excess trim region of the web. 16 . (canceled) 17 . the web manufacturing system of claim 10 , wherein the recorded information includes a first version to be read when the web travels in a first direction, and a mirrored version of the first version to be read when the web travels in a second, opposite direction. 18 . a web manufacturing processing stage comprising: a sensor to measure parameter data relating to at least one parameter of a manufacturing process to be performed by the web manufacturing processing stage with respect to a web; and a printer to record, onto an excess trim region of the web, information relating to the measured parameter data and information pertaining to a quality issue associated with the web. 19 . the web manufacturing processing stage of claim 18 , further comprising a reader to read recorded information in the excess trim region of the web. 20 . the web manufacturing processing stage of claim 19 , further comprising a mechanism to apply a corrective action based on the read recorded information. 21 . the web manufacturing system of claim 10 , wherein the recorded information comprises a barcode recognizable by a barcode reader of the second processing stage in both traveling directions of the web. 22 . the web manufacturing processing stage of claim 18 , wherein the recorded information relating to the measured parameter and the recorded information pertaining to the quality issue comprise a barcode readable by a machine reader in both traveling directions of the web.
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background a web manufacturing process refers to a process of making target products on a web. target products can include finished goods or intermediate goods used for subsequent operations. a “web” can include a sheet-like or long-wound roll substrate that is continuously processed by one or multiple stages of a web manufacturing infrastructure used in the web manufacturing process or a unit operation. examples of a web include a roll of paper or other material that can be processed to form a target finished paper (such as photo paper onto which images can be printed), sheet metal or other material onto which solar cells or other elements can be formed, a substrate onto which organic light-emitting diodes (oleds) or other components can be formed, and so forth. the various stages of a web manufacturing infrastructure can apply respective different manufacturing processes with respect to the web. brief description of the drawings some embodiments are described with respect to the following figures: fig. 1 illustrates an example arrangement for a web manufacturing process, according to some implementations; fig. 2 is a schematic diagram of a web having excess trim regions onto which manufacturing process-related information can be recorded digitally or otherwise, in accordance with some implementations; fig. 3 is a schematic diagram of an example type of non-directional recorded information that can be recorded onto a web, in accordance with some implementations; fig. 4 is a block diagram of an example arrangement that includes a processing stage and an associated control portion, according to some implementations; fig. 5 is a block diagram of an example arrangement that includes multiple processing stages and associated control portions, sensors, readers, and printers, according to some implementations; and fig. 6 is a flow diagram of a web manufacturing process, according to some implementations. detailed description a benefit of using a web manufacturing process is process continuity, since webs can be continuously processed by at least a combination of some processing stages of a web manufacturing infrastructure, which can increase manufacturing throughput and reduce manufacturing cost. a web can refer to any underlying structure on which manufacturing processes can be applied continuously by corresponding processing stages of the web manufacturing infrastructure. as used here, manufacturing processes can also refer to processes for building a web, or alternatively, can refer to unit operations that are performed with respect to a web. for example, a manufacturer of a web can supply the web to a downstream entity, which can in turn apply a further operation or operations, referred to as unit operation(s), on the web (such as to further finish the web and so forth). the underlying structure can be subsequently converted to another form, such as a sheet-like substrate or a roll that can be fed through the web manufacturing infrastructure for processing by corresponding processing stages. examples of a sheet-like substrate or roll can include foil, metal, paper, film, textile, plastic, and so forth. example manufacturing processes that can be applied on a web include material deposition, coating, plating, printing, patterning, laminating, curing, converting, and so forth. quality control can be challenging in a web manufacturing process. the quality of target products resulting from the web manufacturing process can be based on various factors, such as quality of the incoming web, quality of other input materials, consistency of the various manufacturing processes applied on the web, process control of manufacturing-related parameters during the web manufacturing process, and so forth. with some example web manufacturing processes, when a quality issue is detected, it can be difficult to take efficient corrective action to address the quality issue as it happens, and it can also be difficult to identify a root cause of the quality issue concurrently with the occurrence of the quality issue. a quality issue can refer to a defect associated with target products of the web manufacturing process, where the target products can include finished goods or intermediate goods that are to be further processed or used. a quality issue can also refer to any other condition that may cause an output of a web manufacturing process to be less than optimal or outside of predefined specifications, such as an output that has characteristics outside predefined thresholds or other specifications. in some cases, a defect can be manually identified by a human inspector, or alternatively, identified by an automated defect detection/inspection system, or other image processing system. in response to the identified defect, a defect map can be generated to show where on a web the defect starts and ends. the defect map can use measurements from a length measurement device (e.g. a yardage meter) that measures a length of the web that has been processed by the web manufacturing infrastructure. however, such a defect map can be inaccurate, since it relies upon proper calibration of the length measurement device as well as the skill of an operator. if the defect map is inaccurate, then that can result in increasing the likelihood of manufacturing a relatively large amount of defective products. an inaccurate defect map may also lead to an increase in wasted web material when conforming materials are incorrectly culled. for example, the inaccurate defect map may lead to culling of a non-defective portion of the web, while a defective portion of the web is left un-culled. in accordance with some implementations, to allow for more accurate identification of portions of a web associated with defects or other quality issues, techniques or mechanisms are able to physically record information relating to the web manufacturing process and process parameter information onto the web itself at correct positions corresponding to the quality issues. the recorded information can include information regarding a detected quality issue, such as presence of a defect or other condition that is outside predefined threshold(s) or specifications. alternatively or additionally, recorded information can include information relating to a process parameter (or parameters) associated with a particular processing stage of the web manufacturing infrastructure. the particular processing stage can have sensor(s) to measure the parameter(s), and the measured parameter value(s) can be recorded onto the web for later retrieval, analysis, and downstream action plan determination. the information relating to the web manufacturing process can be recorded onto an excess trim region of the web. an “excess trim region” refers to a region of the web on which manufacturing processes are not to be applied, or if applied would not be conforming, since manufacturing tolerances may not allow for reliable manufacturing of target products in the excess trim regions. also, the excess trim regions of the web are intended to be slit or cut from the remainder of the web where the target products are provided, at or near the conclusion of the web manufacturing process. the recorded information on the web can be used for various purposes. for example, the recorded information can be used by the web manufacturing infrastructure to take a corrective action to address a quality issue. for example, the corrective action can include culling a defective portion of a web. culling can involve cutting the defective portion of the web, with the remaining portions of the web spliced together after the defective portion is removed. another example of a corrective action is to have a downstream processing stage modify its operating parameter in response to recorded information (on the web) indicating a quality issue being present in an upstream processing stage (note that the recorded information was recorded onto the web by the upstream processing stage). the modified behavior of the downstream processing stage can include any one or combination of the following: the downstream processing stage can modify at least one of its parameters (e.g. temperature, pressure, flow rate, time, speed, etc.) to cause manufacturing processing performed by the downstream processing stage to vary from its normal behavior; the downstream processing stage can be controlled to skip application of its manufacturing processing in response to detecting a defective portion of the web, to avoid the possibility of rejecting of a higher value-added material. note that it would be a wasted step to perform the manufacturing processing since the defective web portion would be culled later anyway. in other examples, the downstream processing stage can perform other modified processes. alternatively, the recorded information can be used to perform root cause analysis to identify the root cause of a quality issue. once the root cause is identified, a corrective action can be taken to address the root cause. performing a corrective action based on information recorded onto the web provides the system with an integrated closed-loop control capability. examples of information relating to a defect that can be recorded onto a web include any one or combination of the following: defect start point, defect type, defect size, defect location across the web, defect width across the web, defect description, frequency of defect per area, defect start and end points, and so forth. in other examples, other types of information relating to a defect or other quality issue can be recorded. in the ensuing discussion, reference is made to detecting defects on a web and recording information relating to such defects onto the web. note, however, in other examples, information recorded onto a web can relate to other types of process control quality issues, such as detected variations of measured parameters with respect to predefined thresholds or ranges, conditions that may cause target products of the web manufacturing process to have characteristics that are outside of predefined thresholds, and so forth. examples of information relating to parameters that can be recorded onto a web can include any one or combination of the following: an instantaneous web velocity, material flow rate, process temperature, material viscosity, color, clarity, type of material, coating weight, web tension, web temperature, web thickness, machine room temperature, machine room pressure, machine room humidity, outside temperature, outside pressure, outside humidity, power usage, and so forth. although various example parameters are listed above, it is noted that in other examples, other relevant alternative parameters can be recorded onto the web. in general, there can be several classes of parameters. one class of parameters include parameters that can indicate disruptive events, such as slugs in a coating on the web, breaks in the web, equipment malfunction, and so forth, which can have an instantaneous negative effect on the finished product quality. another class of parameters include parameters that can lead to undesirable quality issues over time, such as parameters relating to oven temperatures, moisture content, ambient room conditions, and so forth. fig. 1 illustrates an example system for a web manufacturing process. a web 102 is shown provided through a web manufacturing infrastructure 100 that has multiple processing stages (e.g. stage 1, stage 2, and stage n, where n≧2). the web 102 is provided from an input component 104 , which can be a source material core onto which the web 102 is initially wound. the web 102 , after processing by the processing stages of the web manufacturing infrastructure 100 , is provided to an output component 106 , which can be a receiving core onto which the processed web 102 is wound. during manufacturing, the web 102 is continuously moved from the input component 104 to the output component 106 , or as a contiguous web going through in one pass. in the example arrangement of fig. 1 , each of the processing stages has a sensor (or multiple sensors), and a printer (or other type of recording device). in accordance with some implementations, the printer at each processing stage can be used to print (or otherwise record) certain information (as discussed further below) onto the web 102 (and more specifically onto an excess trim region of the web 102 ). in some examples, the information printed onto the web 102 can be visible or invisible to the human eye. the sensor(s) at each processing stage can be used to detect corresponding process parameter(s) at the corresponding processing stage. the sensor(s) at each of processing stages 2 through n can further include a reader (e.g. an optical reader or other type of reader) to read recorded information on the web. note that each of the subsequent processing stages 2 through n is considered a downstream processing stage with respect to processing stage 1, which may have printed certain information onto the web 102 . information relating to a quality issue and/or a manufacturing process parameter that can be recorded onto the web 102 can include encoded information, where encoded information refers to data that has been translated by an encoding function. in some examples, the encoding function can translate input information into a barcode or information according to another format. a barcode can include a combination of bars for encoding information. alternatively, the barcode can be a matrix barcode or a two-dimensional barcode, such as a qr (quick response) code. details regarding some implementations of a barcode that can be recorded onto the web 102 are discussed further below. by recording information pertaining to the web manufacturing process onto the web 102 , information associated with specific quality issues can be provided at corresponding portions of the web 102 associated with the quality issues. in this manner, the location of a portion of the web 102 that has the quality issue can be accurately pinpointed, such that appropriate corrective action can be taken with respect to the web portion having the quality issue. by recording information relating to the web manufacturing process onto the web 102 , reliance does not have to be made on generating a defect map or other like data structure based on measurements taken by a length measurement device. as noted above, if the length measurement device is not properly calibrated, then the defect map (or other like data structure) may not be accurate, which may lead to imprecise corrective actions being taken. it is also noted that information can be recorded onto the web 102 even in the absence of a quality issue associated with a manufacturing processing applied by a processing stage. for example, useful information relating to one or multiple process parameters measured by one or multiple sensors of a given processing stage can also be recorded onto the web 102 , regardless of whether or not a quality issue was detected. information (including parameter measurements and recorded information read from the web) obtained by the sensor(s) of each processing stage can be communicated to a process machine controller 108 (hereinafter referred to simply as “controller”). although the controller 108 is depicted as being separate from the processing stages, it is noted that, in some examples, certain portions of the controller 108 can reside in the processing stages, such as in the form of control circuits, processors, and so forth. the controller 108 can process received information, and based on the received information, can perform corresponding control actions. for example, if the controller 108 determines that a quality issue is present at processing stage 1 in fig. 1 , the controller 108 can cause processing stage 1 to record information relating to the quality issue onto the web 102 , as discussed above. in some implementations, in response to detecting the quality issue at processing stage 1, the controller 108 can also cause processing stage 1 to take corrective action, such as to remove a portion of the web 102 that has the quality issue. in other implementations, instead of performing the corrective action at processing stage 1, the corrective action can be performed at a downstream processing stage (such as any of processing stages 2 through n), based on recorded information on the web 102 read by the downstream processing stage. using the recorded information read from the web 102 , the downstream processing stage can pinpoint and remove or otherwise compensate for the indicated quality issue, if possible. for example, the downstream processing stage can modify at least one parameter relating to the manufacturing processing applied by the downstream processing stage, to compensate for the quality issue at processing stage 1. alternatively, another corrective action that can be taken by the downstream processing stage is to cull a portion of the web 102 that has the quality issue. alternatively, the controller 108 can, instead of determining a corrective action to take, identify a root cause of the quality issue, such that the web manufacturing infrastructure 100 can be adjusted to prevent the quality issue from occurring in the future. using techniques or mechanisms according to some implementations, quality issue removal and/or tracking is improved. moreover, web material waste is reduced since locations of defects can be more accurately pinpointed. in addition, root cause determination can be improved and the time involved in diagnosing issues can be reduced. in addition to recording information onto the web, the same information can also be communicated to the controller 108 for storage in a storage module 110 , which can be implemented with one or multiple storage devices. digitally storing the information allows for electronic access of the information for various purposes, such as for root cause determination or for corrective action determination. the information stored in the storage module 110 can also be used for other types of analysis, such as product development, environmental impact assessment, yield optimization, scrap minimization, and so forth. in accordance with some implementations, as noted above, information recorded onto the web 102 is recorded onto an excess trim region of the web 102 . in some examples, as shown in fig. 2 , there can be two excess trim regions 202 and 204 on the two side portions of the web 102 . in other examples, excess trim regions can be provided elsewhere on the web 102 . since target products are not intended to be manufactured in the excess trim regions of the web 102 , such excess trim regions can be used for recording the various information discussed above, including quality issue information and process parameter information. as shown in fig. 2 , recorded information in the excess trim region 202 is represented as 206 , while recorded information in the excess trim region 204 is represented as 208 . the recorded information 206 or 208 in the respective excess trim region 202 or 204 can be printed periodically, intermittently, or in response to some other event (e.g. detection of a quality issue). the timing intervals for the recorded information 206 and 208 can be controlled by the controller 108 , such as based on input settings provided by a user or provided from another source. in some examples, the recorded information ( 206 or 208 ) in the excess trim region ( 202 or 204 ) of the web 102 can include non-directional encoded information. the non-directional encoded information allows the information to be read when the web 102 moves in either direction (such as left to right or right to left in fig. 2 ). in a web manufacturing process according to some examples, the material produced first in an upstream processing stage is processed in a downstream processing stage last. for example, if the upstream processing stage produces materials a, b, and c (in that sequence), then the downstream processing stage would process c first, followed by b, and followed by a. thus, it is desirable to be able to read the recorded information in either direction of web travel, from either the excess trim region 202 or 204 . the non-directional encoded information can be designed by making the encoded information symmetrical (with respect to an axis that is perpendicular to the direction of travel of the web 102 ) such that the information can be read in both web travel directions. basically, in some examples, the recorded information is recorded twice, once in a first direction of web travel, and once as a mirrored version so that the recorded information can be read in the opposite web travel direction. in other examples, instead of recording the information twice (a regular version and a mirrored version), different markings can be recorded onto the web 102 at the beginning and at the end of a given processing stage, such that such markings can be used to determine the direction of web travel so that the recorded information can be properly interpreted by a reader. fig. 3 shows an example of symmetric encoded information 206 provided in the excess trim region 202 . note that the recorded information 208 in the excess trim region 204 can have a similar format. the symmetric encoded information 206 can be read from either travel direction of the web 102 ( 316 or 318 in fig. 3 ). the symmetric encoded information 206 has a start code 302 at a first end, and a start code 304 at a second, opposite end. an end code 306 is provided between the start codes 302 and 304 . the start code 302 or 304 is used to indicate the start of recorded information immediately following the start code. the end code 306 indicates the end of the recorded information. in examples according to fig. 3 , each of the start code and end code can have a corresponding combination of bars for indicating that the respective code is a start code or an end code. in other examples, other formats of the start codes and end code can be used. between the start code 302 and end code 306 , further codes include the type of information ( 308 ), and the corresponding event data ( 310 ). the type information 308 can identify a type of the recorded information, such as whether the event data 310 includes quality issue information, or parameter information, or both. the event data 310 includes various specific information, such as process parameter measurements, and/or information pertaining to the defect (e.g. web break or tear, coating slug, equipment malfunction, process drift, etc.). between the start code 304 and end code 306 , type information 312 and event data 314 are provided, which can be a mirrored version of the type information 308 and event data 310 , respectively. the type information 312 and event data 314 contain identical content as the type information 308 and event data 310 , respectively, except in a different directional arrangement (mirrored) such that the information can be read in an opposite travel direction. the type information 308 and event data 310 are to be read when the web 102 travels in the direction indicated by an arrow 316 , while the type information 312 and event data 314 are to be read when the web 102 travels in the opposite direction, as indicated by the arrow 318 . fig. 4 illustrates an example arrangement that includes a processing stage 400 of a web manufacturing infrastructure, and an associated control portion 402 (which can be part of the controller 108 of fig. 1 , for example). although a specific arrangement of the processing stage 400 and associated control portion 402 is depicted in fig. 4 , it is noted that in alternative examples, different arrangements can be provided. the processing stage 400 has a trim information reader 404 (which can be an optical sensor or other type of sensor) that is able to read encoded information on the web 102 (such as encoded information 206 or 208 in fig. 2 ). the processing stage 400 also has a sensor array 405 , which can include one or multiple sensors for measuring various process parameters associated with a manufacturing process to be applied by the processing stage 400 . the processing stage 400 can also include a printer 403 (or other type of recording device) to print or otherwise record information onto the web. the data (collectively referred to as “sensor data”) detected by the reader 404 and sensor array 405 is provided to a sensor interface 406 that is part of the control portion 402 . the sensor data in turn is provided by the sensor interface 406 to a network interface 408 , which is communicated to a server 410 , either over a wired connection 412 or using a wireless link 414 . the server 410 , which can be implemented with a computer or a collection of computers, includes one or multiple processors 416 . sensor data from the network interface 408 is received through a network interface 415 in the server 410 the server 410 also includes a data manager 418 to receive sensor data through the network interface 415 and to manage the sensor data, such as to store the sensor data in a storage medium 422 or to communicate the sensor data to a remote entity. the server 410 also includes a decision engine 420 to determine any action to take in response to the sensor data (such as a corrective action discussed above). the decision engine 420 and data manager 418 are executable on the processor (or processors) 416 . the server 410 further includes a programmable logic controller (plc) interface 424 , which is coupled to a plc 426 that is part of the processing stage 400 . the plc 426 is coupled to various mechanisms of the processing stage 400 , to control operations of such mechanisms. for example, the plc 426 can be coupled to a material removal mechanism 428 , which can perform web material removal to remove a portion of the web 102 that has a quality issue. the processing stage 400 also includes a manufacturing process mechanism 430 , which can be controlled by the plc 426 to apply a respective manufacturing process (e.g. material deposition, coating, plating, printing, laminating, curing, etc.) of the processing stage 400 . in some examples, the plc 426 can instruct the material removal mechanism 428 and manufacturing process mechanism 430 according to commands provided from the server 410 under control of the decision engine 420 . in some examples, the processing stage 400 can be a processing stage that is downstream of an upstream processing stage. the upstream processing stage recorded information (e.g. 206 or 208 in fig. 2 ) onto the web 102 , which is detected by the trim information reader 404 of the downstream processing stage 400 and communicated to the server 410 for processing. this allows the downstream processing stage 400 to read the recorded information on the web 102 , and to take any appropriate action in the downstream manufacturing process as performed by the downstream processing stage 400 . for example, the action that can be taken can be a corrective action to remove a web portion having the quality issue, which can be performed by the material removal mechanism 428 . in alternative examples, instead of including a material removal mechanism (such as 428 ) in each processing stage, a material removal mechanism can instead by provided in a different stage, which can be referred to as a conversion stage. the conversion stage can be provided after a number of processing stages of the web manufacturing infrastructure, and the material removal mechanism in the conversion stage can perform the web material removal to address a quality issue. in other examples, other corrective actions can be taken by the downstream processing stage 400 , as determined by the decision engine 420 . for example, the decision engine 420 can decide to adjust a parameter (or multiple parameters) associated with the manufacturing process mechanism 430 , such as a temperature setting, a pressure setting, a humidity setting, and so forth. in further examples, other corrective actions can also be specified by the decision engine 420 . for example, the downstream processing stage 400 can be controlled to not apply its corresponding manufacturing process onto the web portion having the quality issue. skipping the manufacturing process with respect to the web portion having the quality issue can result in cost savings, since resources of a downstream processing stage (or multiple downstream processing stages) are not wasted in processing a web portion that would likely have to be discarded anyway. fig. 5 illustrates an example arrangement that includes multiple processing stages and corresponding control portions. the processing stages depicted in fig. 5 include an upstream processing stage 500 and the downstream processing stage 400 of fig. 4 . the upstream processing stage 500 is associated with a control portion 502 , while the downstream processing stage 400 is associated with the control portion 402 . although not shown, there can be multiple downstream processing stages. in some examples, the processing stages 500 and 400 are used for manufacturing photo paper (onto which photographic images can be printed). the upstream processing stage 500 includes input material 504 (such as pulp), which is fed to the upstream processing stage 500 (e.g. a paper making machine). the upstream processing stage 500 includes a sensor array 508 , which can be used to measure various parameters associated with the manufacturing process applied by the upstream processing stage 500 . the measured information from the sensor array 508 is provided to the control portion 502 , which can determine if a quality issue is present. the control portion 502 is able to communicate the sensor information from the sensor array 508 to a network 510 , which allows the sensor information to be stored on a network storage module 511 , for example. in addition, the control portion 502 can control a printer 512 in the upstream processing stage 500 to print encoded information onto a web 514 processed by the upstream processing stage 500 . as shown in fig. 5 , the web 514 output from the upstream processing stage 500 is provided to a conversion stage 513 , which can cull any web portion having a quality issue (as detected by the control portion 502 ). culled web material ( 516 ) is redirected to a different destination, while the remainder of the web 514 is provided as a roll of trim encoded raw base 518 . “trim encoding” refers to recording information relating to a manufacturing process of a processing stage onto an excess trim region of a web. the trim encoded raw base 518 is used as the input to the downstream processing stage 400 , which has the manufacturing process mechanism 430 to apply a corresponding manufacturing process. note that the trim encoded raw base 518 is fed to the downstream processing stage 400 in an automated manner. the downstream processing stage 400 has the trim information reader 404 (to read the trim encoded information on a web 520 ). the trim information reader 404 outputs the trim encoded information to the control portion 402 . the downstream processing stage 400 also has the sensor array 405 to measure parameter data, which can be communicated to the control portion 402 . the control portion 402 can determine, based on the trim encoded information and parameter data, whether a quality issue is present and a corresponding corrective action should be taken. the control portion 402 can also provide parameter data measured by the sensor array 405 to the network 510 . in addition, the control portion 402 can cause the printer 403 to print trim encoded information onto the web 520 . the web 520 from the output of the downstream processing stage 400 is provided to a conversion stage 525 , which can cull a portion of the web 520 having a quality issue. any culled web material ( 526 ) is redirected to a different destination, while the remainder of the web 520 is output as a roll of trim encoded processed base 528 , which can be fed to the next processing stage. further processing can be performed in further downstream stages according to some implementations, until the final output of the web manufacturing process is produced. fig. 6 is a general flow diagram of a web manufacturing process according to some implementations. the process includes recording (at 602 ), onto an excess trim region of a web that is a subject of the web manufacturing process, information relating to a given processing stage of the web manufacturing process. the process of fig. 6 next determines (at 604 ), based on reading the recorded information, a corrective action to take with respect to an issue indicated by the recorded information. the corrective action can be taken by the given processing stage, or by a downstream processing stage. the determination at 604 can be performed by the controller 108 of fig. 1 , or by a control portion depicted in fig. 4 or 5 . in the foregoing description, numerous details are set forth to provide an understanding of the subject disclosed herein. however, implementations may be practiced without some or all of these details. other implementations may include modifications and variations from the details discussed above. it is intended that the appended claims cover such modifications and variations.
|
099-114-938-388-745
|
JP
|
[
"HK",
"EP",
"CN",
"JP",
"DE",
"KR",
"ES",
"US",
"TW"
] |
A44B18/00
| 1994-08-26T00:00:00 |
1994
|
[
"A44"
] |
molded surface fastener
|
a molded surface fastener comprises a substrate sheet (1) and a multiplicity of engaging elements (2) molded in rows on one surface of the substrate sheet (1). each of the engaging elements (2) has a stem (21) standing from the one surface of the substrate sheet (1), and a pair of hooks (22, 22) extending in opposite directions from a distal end of the stem (21). and a multiplicity of parting guide members (4) stand from the one surface of the substrate sheet (1), each of which is situated centrally between adjacent engaging elements (2, 2) for parting loops (3) of of a companion surface fastener toward the engaging elements (2, 2).
|
a molded surface fastener comprising: (a) a substrate sheet (1); (b) a multiplicity of engaging elements (2) molded in rows on one surface of said substrate sheet (1), each of said engaging elements (2) having a stem (21) standing from said one surface of said substrate sheet (1), and hooks (22, 22) extending from a distal end of said stem (21); and (c) a multiplicity of parting guide members (4) standing from said one surface of said substrate sheet (1), each of said parting guide members (4) being situated centrally between adjacent said engaging elements (2, 2) for parting loops (3) of a companion surface fastener toward said engaging elements (2, 2). a molded surface fastener according to claim 1, wherein each of said engaging element (2) has a pair of said hooks (22, 22) extending in opposite directions and being formed in a front-rear symmetry in a plane perpendicular to the general plane of said substrate sheet (1) and including the center line of said stem (21). a molded surface fastener according to claim 1, wherein each of said engaging elements (2) has a pair of said hooks (22, 22) extending in opposite directions and being formed in a pair of parallel planes perpendicular to the general plane of said substrate sheet (1) on opposite sides of the central line (l) of said stem (21). a molded surface fastener according to claim 1, wherein each of said parting guide members (4) has front and rear or right and left guide surfaces (4a, 4a) gently curving from its upper end to diverge to its lower end. a molded surface fastener according to claim 1, wherein each of said parting guide members (4) has on its top one or more hooks (42) extending in a direction of row of said engaging elements (2). a molded surface fastener according to claim 1, wherein said parting guide members (4) are disposed between adjacent rows of said engaging elements (2). a molded surface fastener according to claim 1, wherein each of said parting guide members (4) is disposed between a pair of said engaging elements (2, 2) in the same row.
|
background of the invention 1. field of the invention: this invention relates to a molded synthetic resin surface fastener in which a substrate sheet and a multiplicity of engaging elements projecting from one surface of the substrate sheet are formed integrally with each other, and more particularly to a molded surface fastener which has adequate engaging strength and rate suitable for use in a joint of industrial materials, such as ceiling materials and wall materials which are subject to peeling forces and which have adequate durability without giving damage to engaging elements of the companion surface fastener during peeling. 2. description of the related art: molded surface fasteners of the described type have greater engaging strength compared to the ordinary knitted or woven surface fasteners and are therefore widely used in joining interior ornamental materials, such as wall materials and ceiling materials. generally, the individual engaging element of the molded surface fastener has a stem standing from one surface of a substrate sheet, and a hook curving in one direction from the distal end of the stem and terminating in an end directed to the surface of the substrate sheet. in the case that the individual engaging element of the molded surface fastener is a hooked member having the above-mentioned simple hook structure, in order to increase the degree of strength of engagement with a looped member, which is the companion engaging element, it has been customary to mold the engaging elements of rigid synthetic resin or to increase the thickness of the looped member. however, the rigid engaging element will give an undesirable touch, and it tends to be out of engagement of the companion looped member. in the case of the thick looped member, the surface fastener not only would become rigid but also would have less engaging elements per unit area on the substrate sheet, thus making it difficult to secure a predetermined degree of engaging strength. consequently, soft synthetic resin materials, such as polyester, polyamide and polyurethane, usually suitable for molded surface fasteners are used, and at the same time, various forms of engaging elements are put into practice in order to secure the relative strength of hooked and looped members and in order to increase the engaging strength. a typical form of engaging element, as disclosed in, for example, japanese patent laid-open publications nos. sho 47-31740 and hei 4-224703, has front and rear engaging portions symmetrically projecting from the distal end of a generally trapezoidal hook. an alternative form, as disclosed in, for example, japanese utility model laid-open publication no. hei 4-128611, has the distal end of a stem being branched and one of the branched end is made to have a hook shape. according to these known forms, the number of engaging elements per unit area on the substrate sheet increases to increase the rate of engagement with companion engaging elements so that the engaging strength of the entire surface fastener is increased. in the molded surface fastener to be used in the industrial materials, a predetermined space must be provided between each adjacent pair of engaging elements due to the mold technology. consequently the density of engaging elements on the substrate sheet surface is necessarily limited to a considerably lower degree compared to the density of looped members of the companion surface fastener. even if an attempt is made to increase the rate of engagement by providing each engaging element with hooks facing in opposite directions as disclosed in the above-mentioned publications, the rate of engagement has a limit as the number of looped members actually engaged with the engaging elements of the molded surface fastener is several ten percent of the total number of looped members. in an attempt to increase the rate of engagement of hooks with looped members entering between front and rear engaging elements adjacent to each other in the same rows, the engaging element disclosed in, for example, in european pat. no. 0464753a1 has a rear rising surface in a position on the substrate sheet surface at which position a perpendicular line passing through the end of the hook of the rear next engaging element meets the substrate sheet surface. according to this arrangement, if the looped member is raised along the rear surface of the front next engaging element, there is no guarantee that the looped member may come into engagement with the hook of the rear next engaging element. further, with this type conventional molded surface fastener, most of the looped members entered between every adjacent pair of rows of hooks remain unengaged with the hooks. summary of the invention it is therefore an object of this invention to provide a molded surface fastener which has engaging elements each in a rational form to improve the rate of engagement with loops and to secure a much higher increased degree of peeling strength and in which a substrate sheet can be prevented from being torn between the engaging elements. according to this invention, the above object is accomplished by a molded surface fastener comprising a substrate sheet and a multiplicity of engaging elements molded in rows on one surface of the substrate sheet. each of the engaging elements has a stem standing from the one surface of the substrate sheet, and hooks extending from a distal end of the stem. a multiplicity of parting guide members stand from the one surface of the substrate sheet, each of the parting guide members being situated centrally between adjacent engaging elements for parting loops of a companion surface fastener toward the engaging elements. preferably, each of the engaging element has a pair of the hooks extending in opposite directions and being formed in a front-rear symmetry in a plane perpendicular to the general plane of the substrate sheet and including the center line of the stem. alternatively, the pair of hooks is formed in a pair of parallel planes perpendicular to the general plane of the substrate sheet on opposite sides of the central line of the stem. further, each of the parting guide members has front and rear or right and left guide surfaces gently curving from its upper end to its lower end to diverge. in an alternative form, each of the parting guide members has on its top one or more hooks extending in a direction of row of the engaging elements. the one or more hooks extend in a forward or rearward direction or both directions. further preferably, the parting guide members are disposed between adjacent rows of the engaging elements. alternatively, each of the parting guide members is disposed between a pair of the engaging elements in the same row. in operation, since each of the loops entering at random between the front and rear engaging elements are parted by the parting guide member so as to come close to the front or rear engaging element, it is possible to secure a reliable engagement of the loops with the engaging elements so that the rate of engagement is increased to obtain a desired engaging force. further, contrary to the conventional surface fasteners which are easy to be torn between rows of the engaging elements, it is possible to effectively prevent the substrate sheet from being torn since the parting guide members are integrally formed on the substrate sheet between rows of the engaging elements or between the front and rear engaging elements. in case the parting guide member has a hook, the loop entering in front of the hook of the parting guide member is caught by the hook. and as the parting guide member has on opposite sides slopes, the loops entering opposite sides of the hook of the parting guide member are parted diagonally toward the adjacent engaging elements. in case that the engaging element is in a form of two adjacent conventional hook elements being joined integrally with each other and having hooks facing in the opposite directions, the thickness of the stem of the engaging element of this invention is substantially double the thickness of the conventional hooked members. when a peeling force is exerted on the engaging element with both the front and rear hooks in engagement with the loops, the stem is scarcely subject to bend due to the peeling force while the individual hooks are angularly moved about their bases in a horizontal plane independently without interfering with each other and, at the same time, the upper portion of the hook resiliently deforms in the rising direction. therefore the loops can be easily removed off the hooks without giving any damage to each other. brief description of the drawings fig. 1 is a fragmentary perspective view of a molded surface fastener according to a typical embodiment of this invention; fig. 2 is a fragmentary front view of the molded surface fastener of fig. 1, showing the action of loops of a companion surface fastener when the latter is joined with the molded surface fastener; fig. 3 is a schematic top view of the molded surface fastener of fig. 1, showing another example of arrangement of parting guide members; fig. 4 is a view similar to fig. 3, showing still another example of arrangement of parting guide members; fig. 5 is a fragmentary side view showing a modified form of the parting guide members; fig. 6 is a fragmentary perspective view of a molded surface fastener according to another typical embodiment of the invention; fig. 7 is a fragmentary front view of the molded surface fastener of fig. 6, showing the action of loops of a companion surface fastener when the latter is joined with the molded surface fastener; and fig. 8 is a cross-sectional view taken along line x-x of fig. 7, schematically showing the action of the engaging element when the molded surface fastener is peeled off a companion surface fastener. detailed description of the preferred embodiments typical embodiments of this invention will now be described in detail with reference to the accompanying drawings. fig. 1 is a fragmentary perspective view of a molded surface fastener according to a first embodiment of the invention. according to the first embodiment, a multiplicity of engaging elements 2 are integrally molded on a top surface of a substrate sheet 1. each of the engaging elements 2 is composed of a stem 21 standing from the top surface of the substrate 1, and front and rear hooks 22, 22 branched in opposite directions from the upper end of the stem 21 and each extending diagonally upwardly with a predetermined curvature and terminating in a downwardly directed end. the stem 21 has a body 21a having a rectangular cross section, and a base end 21b diverging toward the top surface of the substrate sheet 1 with smooth front and rear curved surfaces symmetrical with respect to the vertical center line of the stem body 21a. on each of the opposite sides of the base end 21b of the stem 21, a reinforcing rib 23 having a mount-shape in vertical cross section is formed integrally of the stem 21 and has front and rear smooth curved surfaces extending from its top toward the top surface of the substrate sheet 1. the opposite reinforcing ribs 23, 23 serve to prevent the stem 21, which has a relatively small width, from falling or bending sideways. a multiplicity of the engaging elements 2 of the above described form is arranged in matrix in a predetermined pitch in the front-rear direction (row) and at a predetermined distance in the right-left direction (column). in the illustrated example, a loop parting guide member 4, which is the most characteristic feature of this invention, is formed integrally on the top surface of the substrate sheet 1 at a central position among four adjacent engaging elements 2. the arrangement of the parting guide members 4 should by no means be limited to that of fig. 1; for example, they may be arranged in a manner that one is disposed centrally between each pair of the adjacent front and rear reinforcing ribs 23, 23 as shown in fig. 3, or they may be arranged in a manner that one is disposed centrally between each pair of the adjacent front and rear engaging elements 2, 2 as shown in fig. 4. as long as it has a form such as to part loops 3 coming from the above toward the hooks 22 of the front and rear arid right and left engaging elements 2, the parting guide member 4 may be in any of various forms. generally it is preferable that the parting guide member 4 stands from the top surface of the substrate sheet 1 and has front and rear side slopes each facing the respective hook 22. the directions of the front and rear side slopes are essentially such that the loops 3 are parted to come close to the respective hooks 22 of the front and rear or right and left adjacent engaging elements 2. in the example of fig. 1, the parting guide member 4 has a mount shape in vertical cross section with opposite side surfaces being flat. preferably the slopes 4a define such a parting surface as to part the loops 3, which enter centrally between the right and left adjacent engaging element rows a, b, toward the space between the front and rear engaging elements 2, 2 of the respective row. in the arrangement of the parting guide members 4 of figs. 3 and 4, the slopes 4a are determined to face the front and rear engaging elements 2, 2, respectively, to bring the loops 3, which enter centrally between the front and rear engaging elements 2, 2 in the same row, close to one of the hooks 22, 22 of the front and rear engaging elements 2. the height of the parting guide member 4 may be determined arbitrarily; however, if it exceeds the height of the stem body 21a of the engaging element 2, not only the loops are difficult to come into engagement with the hooks 22, but also the resulting surface fastener tends to loose flexibility. and if the height of the parting guide member 4 is less than that of the base end 21b, the parting guide member 4 does not perform the original parting function. it is accordingly preferable that the parting guide member 4 has a height between them. according to the molded surface fastener of the first embodiment, since the loops 3 entering at random between a multiplicity of the engaging elements 2 are parted toward the adjacent engaging elements 2 by the parting guide member 4 as shown in fig. 2, the loops 3 entering between the engaging element rows a, b are parted toward any of the right and left engaging element rows a, b to increase the rate of catching the loops 3 by the engaging elements 2, thus increasing the rate of engagement remarkably to obtain a predetermined engaging force. further, contrary to the conventional surface fasteners which are easy to be torn between rows of the engaging elements, it is possible to prevent the molded surface fastener from being torn during the ejecting of the molded surface fastener from the mold or during the sewing of the molded surface fastener or in use since the parting guide members 4 are integrally formed on the substrate sheet 1 at positions between the engaging element rows and between the front and rear engaging elements 2. fig. 5 shows a modified parting guide member 4 which serves not only to part loops 3 toward a number of adjacent engaging elements 2 but also to catch the loops 3 by itself. specifically, the modified parting guide member 4 has a stem 41 standing from the top surface of the substrate sheet 1, and a hook 42 extending in one direction from the upper end of the auxiliary stem 41. the auxiliary stem 41 has a generally frustoconical contour diverging toward and tapering away from the top surface of the substrate sheet 1. therefore, the loop 3 coming to the front side of the hook 42 is caught by the hook 42 while the loops 3 coming to the right and left sides of the hook 42 are parted diagonally to the right and left between the adjacent engaging elements 22. the contour of the stem 41 and the direction of the hook 42 should not be limited to the illustrated example and may be determined arbitrarily. fig. 6 shows a molded surface fastener according to another typical embodiment of the invention, in which the form of each engaging element 2 is different from that of the foregoing embodiment. in this embodiment, a multiplicity of engaging elements 2 integrally molded on and projecting from the top surface of a substrate sheet 1 is formed with pairs of engaging members as disclosed in, for example, u.s. pat. no. 4,984,339, and in each of which the pair of engaging members are arranged next to each other with their hooks directed in opposite directions, closely resembling a form in which the engaging members are integrally joined together at their side surfaces. in the second embodiment, the engaging element 2 is composed of a pair of members 2-1, 2-2. each member 2-1, 2-2 comprises a stem portion 21-1, 21-2 each having a rear surface 21c rising along a gentle curve from the upper surface of the substrate sheet 1 and a front surface 21d rising initially in a predetermined curvature and then perpendicularly from the upper surface of the substrate sheet 1 and composing a stem 21, and a hook 22 extending from the stem 21 and terminating in a downwardly directed end. the two engaging members 2-1, 2-2 are integrally joined partly at their respective hooks 22, 22 and at their respective stem portions 21-1, 21-2, as indicated by diagonal dotted lines in fig. 7, with the hooks 22, 22 extending from the respective stem portions 21-1, 21-2 in opposite directions. in the illustrated example, each stem 21 has on its lower outside surfaces reinforcing ribs 23. a multiplicity of such engaging elements 2 is formed on the upper surface of the substrate sheet 1 with the front and rear hooks 22, 22 of the individual engaging elements 2 arranged in straight rows. fig. 7 shows the normal manner in which companion loops 3 are in engagement with the engaging elements 2 formed on the substrate sheet 1. fig. 8 is a cross-sectional view taken along line x-x of fig. 7, showing the action of the engaging element 2, when an upward peeling force is exerted on the surface fastener, in the case that two loops 3, 3 are in engagement with the front and rear hooks 22, 22, respectively. in this case, the front and rear hooks 22, 22 tend to engage the loops 3 not right above the respective hooks, but the front and/or rear hooks 22, 22 tend to engage the loops 3 off the positions right above the respective hooks. in the conventional engaging element disclosed in the above-mentioned publications, assuming that its engaging force is equal to that of the engaging element of this invention, the stem of the conventional engaging element has a thickness about a half of the stem 21 of this invention and therefore tends to receive the great influence of the peeling force. for example, if two loops act on the engaging element in a common direction, the stem tends to bend together with the hooks so that the loops can hardly be disengaged from the hooks. according to the engaging element structure of this invention, partly since the stem 21 has a great thickness and partly since the front and rear hooks 22, 22 are integrally joined at their bases 22a, 22a, when the two loops 3, 3 are in engagement with the front and rear hooks 22, 22 respectively, the stem 21 and the base 22a of the hook 22 do not tend to bend due to an upward peeling force. in the meantime, the front and rear hooks 22, 22 deform so as to angularly move about their bases 22a in a horizontal plane independently without interfering with each other, and the upper portions 22b, 22b of the respective hooks 22, 22 deform in the rising direction. as a result, the loops 3, 3 tend to be disengaged from the hooks 22, 22 without any damage. as the foregoing function demonstrates not only when a single loop 3 is in engagement with only one of the front and rear hooks 22 of the engaging element 2 but also when the loop 3 is in hanging engagement with the engaging element 2, the loops 3, 3 can be disengaged from the hooks 22, 22 easily without giving any damage to one another. also in the second embodiment of fig. 6, a multiplicity of parting guide members 4 each having the same contour as that of fig. 1 stand from the top surface of the substrate sheet 1. because of the parting guide members 4, it is possible to increase the rate of engagement of the engaging elements 2 with the loops 3 and to minimize damage that might be caused to the engaging elements 2 and the loops 3 during peeling, thus securing a desired engaging force. as is apparent from the foregoing description, various modifications may be suggested. for example, in the embodiment of fig. 6, it is possible to further increase the rate of engagement of the engaging elements with the loops by making the front and rear hooks 22, 22 different in height from one another. according to the molded surface fastener of this invention, since the parting guide members 4 for loops 3 of a companion surface fastener stand from the top surface of the substrate sheet 1 at predetermined positions between a multiplicity of engaging elements 2 each having a set of front and rear hooks 22, 22, it is possible to part loops 3, which come from various directions, toward any of adjacent engaging elements 2 reliably so that the rate of catching the loops 3 by the engaging elements 2 increases. as a result, the rate of engagement is increased so that the surface fastener can demonstrate a desired engaging force. because of the parting guide members 4, it is possible to avoid any break or tear between engaging element rows and between front and rear engaging elements 2, which portions can be most easily broken or torn. in this invention, in the case that each engaging element is composed of the pair of engaging elements having the pair of hooks 22 extending in opposite directions from the upper end of the respective stem portions 21-1, 21-2 with a part where they are in contact with each other being joined integrally, the individual hook 22 deforms upwardly moving in a horizontal plane about the center line of the stem 21, with no undue force on the hooks 22 and loops 3 and hence no damage thereto, and is disengaged from the loops 3 smoothly during peeling. the molded surface fastener of this invention is therefore particularly useful when used in joining industrial materials, such as wall and ceiling materials, because damage can hardly be caused to the engaging elements at the time of disengagement.
|
099-502-133-075-615
|
DE
|
[
"ES",
"AT",
"GR",
"DK",
"PL",
"EP",
"US",
"DE",
"PT",
"JP",
"CA",
"WO"
] |
C04B20/10,C04B24/08,C04B28/14,C04B38/02
| 1995-12-20T00:00:00 |
1995
|
[
"C04"
] |
composition for producing light plaster, production of the foaming agent used therefor and its use
|
a composition for producing light plaster contains as main constitutive elements particles of plaster in anhydride or hemihydrate form and at least one foaming agent. the composition is characterized in that the foaming agent generates gas after a delay of 1 minute to 24 hours and constitutes 0.1 to 50% by weight of the total dry mixture. also disclosed is the use of said composition to produce in-situ cellular plastic and low density plaster moldings.
|
1. a composition for the production of light gypsum, which comprises: particulate, setting gypsum selected from the group consisting of anhydride gypsum, hemihydrate gypsum and mixtures thereof and at least one blowing agent, coated with a water permeable coating of a film forming polymer selected from the group consisting of synthetic polymers, synthetically modified naturally occurring polymers and mixtures thereof, wherein the blowing agent generates carbon dioxide gas with a delay of from about 1 minute to about 60 minutes. 2. the composition as claimed in claim 1, wherein said composition comprises about 0.1 to about 50% by weight, based on the dry mixture as a whole, of the at least one blowing agent for the delayed generation of gas. 3. the composition as claimed in claim 1, wherein said composition comprises about 1 to about 20% by weight, based on the dry mixture as a whole, of the at least one blowing agent for the delayed generation of gas. 4. the composition as claimed in claim 1, wherein the blowing agent for the delayed generation of gas comprises at least two components of which at least one is provided with the water-permeable coating. 5. the composition as claimed in claim 1, wherein the water-permeable coating further comprises an inorganic substance. 6. the composition as claimed in claim 1, wherein the synthetically modified, naturally occurring polymer is a synthetically modified polysaccharide. 7. a composition as claimed in claim 6, wherein the synthetically modified polysaccharide is selected from the group consisting of cellulose ethers, cellulose esters, starch esters, starch ethers and mixtures thereof. 8. the composition as claimed in claim 7, wherein the cellulose ether is selected from the group consisting of methyl cellulose, hydroxymethyl cellulose, carboxymethyl-hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxyethylmethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, ethyl cellulose, carboxymethyl cellulose and mixtures thereof. 9. the composition as claimed in claim 7, wherein the cellulose ester is selected from the group consisting of cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, cellulose propionate and mixtures thereof. 10. the composition as claimed in claim 7, wherein the starch ester is selected from the group consisting of starch nitrate, starch phosphate, starch xanthogenate, starch acetate, starch sulfate, starch citrate and mixtures thereof. 11. the composition as claimed in claim 7, wherein the starch ether is selected from the group consisting of starch carboxymethyl ether, hydroxyethyl starch, hydroxypropyl starch, cationic starch and a mixture of these starch ethers. 12. the composition as claimed in claim 1, wherein the synthetic polymer is selected from the group consisting of polyvinyl compounds, polyacrylic compounds, polyurethane, polyelectrolytes and mixtures thereof. 13. the composition as claimed in claim 12, wherein the polyvinyl compound is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate/crotonic acid copolymers, polyvinyl butyral and mixtures thereof. 14. the composition as claimed in claim 12, wherein the polyacrylic compound is selected from the group consisting of poly(meth)acrylate copolymers, polyacrylamides and mixtures thereof. 15. the composition as claimed in claim 1, wherein the blowing agent comprises an acidic organic or inorganic solid component and the particulate gypsum is a gypsum which comprises at least about 1 mg of carbonate per g of gypsum. 16. the composition as claimed in claim 1, wherein the blowing agent comprises a solid acid selected from the group consisting of solid organic acids, solid phenols, inorganic solid acids, inorganic solid acidic salts and mixtures thereof. 17. the composition as claimed in claim 1, wherein the blowing agent comprises a gas-generating solid component selected from the group consisting of metal powders, azo compounds, carbonates, hydrogen carbonates, sesquicarbonates, peroxides, perborates, percarbonates, azides, hydrides and mixtures thereof. 18. the composition as claimed in claim 1, wherein the blowing agent comprises two components, wherein an acidic solid component has a water-permeable coating. 19. the composition as claimed in claim 1, wherein the blowing agent comprises an organic acidic component. 20. the composition as claimed in claim 19, wherein the organic acid component comprises hydroxycarboxylic acids. 21. the composition as claimed in claim 20, wherein the hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, malic acid, ascorbic acid, glucose acid, dimethylol propionic acid and mixtures thereof. 22. the composition as claimed in claim 1, wherein, based on the dry mixture as a whole, said mixture further comprises about 0.5 to about 20% by weight of at least one water-soluble, water-dispersible or water-dispersed polymer. 23. the composition as claimed in claim 22, wherein the polymer is an, oleochemical polymer. 24. the composition as claimed in claim 22, wherein the water-soluble, water-dispersible or water-dispersed polymer is selected from the group consisting of vinyl acetate polymer, vinyl acetate copolymer, acrylate polymer, acrylate copolymer, natural rubber, polychloroprene, polyurethane, polyamide and mixtures thereof. 25. a composition as claimed in claim 1, wherein the particulate, setting gypsum is present in quantities of about 20 to about 99.9% by weight, based on the mixture as a whole. 26. a composition as claimed in claim 1, wherein the particulate, setting gypsum is present in quantities of more than about 50% by weight, based on the mixture as a whole. 27. the composition as claimed in claim 1, wherein said composition further comprises additives seleceted from the group consisting of: 0 to about 45% of carbonate-free fillers; 0to about 2% of a surface-active agent; 0 to about 5% of a wetting agent; 0 to about 5% of an accelerator; 0 to about 5% of a retarder; 0 to about 5% of a hydrophobicizing agent; 0 to about 5% of a plasticizer; and mixtures thereof, based in each case on the mixture as a whole. 28. the composition as claimed in claim 27, wherein the hydrophobicizing agent is a polysiloxane, a wax or an oleochemical additive, the oleochemical additive being selected from the gruop consisting of: at least about c.sub.8 fatty compounds containing at least one carboxyl group and having a molecular weight of about 143 to about 20,000 and/or a salt thereof; at least about c.sub.8 fatty compounds containing at least one hydroxyl group and having a molecular weight of about 130 to about 20,000; fatty compounds containing at least one ester group and having a molecular weight of about 158 to about 20,000, the acid component and/or the alcohol component containing at least about 8 carbon atoms; fatty compounds containing at least one ether group and having a molecular weight of about 144 to about 20,000, at least one of the two ether groups containing at least about 8 carbon atoms; fatty compounds containing at least one amino group or one quaternary ammonium salt and having a molecular weight of about 129 to about 20,000, at least one of the three or four groups arranged around the nitrogen atom containing at least about 8 carbon atoms; fatty compounds containing at least one amide group and having a molecular weight of about 157 to about 20,000, the acid component of the amide containing at least about 8 carbon atoms; at least about c.sub.8 fatty compounds containing at least one epoxide group and having a molecular weight of about 128 to about 20,000; at least about c.sub.8 fatty compounds containing at least one anhydride group and having a molecular weight of about 210 to about 20,000; at least about c.sub.8 organophosphorus fatty compounds having a molecular weight of about 193 to about 20,000; at least about c.sub.8 organoboron fatty compounds having a molecular weight of about 174 to about 20,000; at least about c.sub.8 organosulfur fatty compounds having a molecular weight of about 164 to about 20,000; at least about c.sub.8 fatty compounds containing at least one urethane group and having a molecular weight of about 213 to about 20,000; and mixtures thereof. 29. a process for the production of the delayed gas-generating blowing agent claimed in claim 1, which comprises the steps of: contacting an acidic component or a gas-generating component or both components separately from one another with a water-containing dispersion or solution, which comprises at least one water-swellable, water-redispersible or water-soluble substance selected from the group consisting of synthetically modified, naturally occurring polymers, synthetic polymers and mixtures thereof, for a time sufficient for a film-forming coating to form; and removing any excess solvent. 30. a process for the production of the delayed gas-generating blowing agent claimed in claim 1, comprising the steps of: contacting an acidic and/or gas-generating component with a dispersion or solution containing a non-aqueous solvent, which comprises at least one water-swellable, water-redispersible or water-soluble substance selected from the group consisting of synthetically modified, naturally occurring, synthetic polymers and mixtures thereof, for a time sufficient for producing a film-forming coating; and removing any excess solvent. 31. a pack comprising the composition claimed in claim 1, in which the particulate, setting gypsum, a blowing agent are present together in a pack, the volume of the pack being selected so that a water-containing liquid can be added at least in a quantity sufficient for setting. 32. a method for the production of in-situ foam, comprising the step of foaming the the composition claimed in claim 1 in-situ to obtain a foam. 33. the method of claim 32, wherein said foam is an assembly foam. 34. the method of claim 32, wherein said foam is an insulating foam. 35. the method of claim 32, further comprising the step of filling voids with said composition, whereby said voids are filled by in-situ foaming of the composition to form a foam filled void. 36. a method for molding, comprising the step of foaming the the composiiton claimed in claim 2 in-situ in contact with a mold. 37. the product of combining the composition of claim 1 with water, wherein a light weight gypsum is obtained having a density of about 0.05 to about 1.5 g/cm.sup.3. 38. the light weight gypsum of claim 37, wherein the light weight gypsum is in the form of a rigid-foam gypsum molding. 39. the light weight gypsum of claim 37, wherein the light weight gypsum is in the form of an insulating plaster.
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background of the invention compositions for the production of light gypsum, which contain as key components particulate setting gypsum, more particularly in the form of anhydride and/or hemihydrate, and at least one blowing agent consisting of an acid in the form of a mineral acid or an organic acid and, as an additional component, a gas-forming salt, are already known. in the context of the present invention, gypsum in anhydride form is understood to be pure calcium sulfate with no water of hydration. thus, ca 119:78617, an abstract of jp-a-05105544, relates to a low-density gypsum product in which anhydrite, sulfates and calcium carbonate are contacted with one another, resulting in the formation of carbon dioxide gas bubbles. ca 91:61734, an abstract of su 77-2522229, relates to a low-density gypsum product in which gypsum hemihydrate is reacted with a sodium carbonate melt, sodium sulfate and water. ca 89:48101, an abstract of jp-a-76-92941, relates to a low-density gypsum product in sheet form which is obtained by reacting gypsum hemihydrate together with calcium carbonate in the presence of dilute sulfuric acid and water. ca 85:24916, an abstract of jp-a-74-107006, relates to a low-density gypsum product, in which a gypsum hemihydrate is reacted together with a powder-form alkali metal or alkaline earth metal carbonate in the presence of an aqueous solution additionally containing methyl cellulose. the foamed material thus produced has a density of 0.5 g/cm.sup.3. ca 84:168779 relates to a gypsum suspension containing calcined gypsum, calcium carbonate and a 40% hexafluorosilicic acid and, for the rest, water. a light gypsum with a density of 0.55 is obtained in this way. ca 84:154766, an abstract of jp-a-74-77409, relates to a low-density gypsum product, in which a calcined gypsum is contacted with sodium stearate, calcium carbonate, dilute hydrofluoric acid and, for the rest, water and then reacted to form foamed mouldings. the light gypsum mouldings obtained in this way have a density of 0.61. ca 84:154755, an abstract of jp-a-74-66659, relates to a low-density gypsum product, in which a mixture of 95% by weight calcium sulfate hemihydrate and 5% by weight calcium carbonate is reacted with a 3% sulfuric acid, fibrous material. the mouldings obtained have a specific gravity of less than 0.1. ca 84:126033, an abstract of jp-a-74-64062, relates to a low-density gypsum product, in which calcined gypsum is reacted together with calcium stearate, calcium carbonate and a 40% aqueous hexafluorosilicic acid solution and water to obtain a molded product having a specific gravity of 0.47. ca 82:47224, an abstract of jp-a-71-119764, relates to a low-density gypsum product, in which a calcined gypsum is reacted together with water, calcium carbonate, calcium fluorosilicate and barium stearate. a calcined gypsum product with a density of 0.57 g/cm.sup.3 is obtained in this way. ca 80:73793, an abstract of jp-a-72-5988, relates to a low-density building material, in which a carbonate or bicarbonate is reacted with a phosphoric acid partial ester at room temperature or above room temperature. gypsum inter alia may be added to this mixture which, if heated to 50.degree. c., leads to a foamed gypsum product with a density of 0.4 g/cm.sup.3. ca 122:272364, an abstract of german patent 43 33 115, relates to cement, concrete or a similar building material which is obtained by reacting a curable calcium sulfate together with an alkali metal bicarbonate, boric acid, calcium hydroxide and a foaming agent, a plasticizer and a retarding agent. the low-density gypsum products obtained in this way have a density of 1.3 g/cm.sup.3. ca 120:84826, an abstract of ep-a-562651, relates to a gypsum product with an apparent density of 0.5 to 1.5 g/cm.sup.3 which is obtainable by reacting calcium sulfate, magnesium hexafluorosilicate, aluminium stearate, calcium carbonate and/or magnesium carbonate, methyl cellulose, sodium citrate and water. research disclosure, vol.135, july 1975, page 37, disclosure no. 13540, relates to the production of low-density gypsum, in which gypsum hemihydrate is first suspended together with manganese dioxide and water and hydrogen peroxide is added to the resulting suspension for foaming. in addition, pva emulsions may be added to this product to improve its properties. ca 101:11552, an abstract of jp-a-82-124909, relates to a low-density gypsum product in which a gypsum hemihydrate is reacted with barium stearate, calcium carbonate, calcium oxide, an aqueous polyvinyl alcohol solution and water. gypsum elements with a density of 0.76 are obtained in this way. ca 101:11551, an abstract of jp-a-82-124910, relates to a low-density gypsum product, in which .beta.-gypsum hemihydrate, calcium stearate, calcium carbonate, calcium oxide, polyvinyl alcohol and ammonium sulfate are reacted with hexafluorosilicic acid. the product thus obtained has a density of 0.78. ca 101:11550, an abstract of jp-a-82-124908, relates to a gypsum product with a density above 0.76 obtained by reacting gypsum hemihydrate, hydrophobic stearates, carbonates or bicarbonates and basic oxides in the presence of acidic fluorides and water and synthetic resins. ca 101:11549, an abstract of jp-a-82-124907, relates to a low-density gypsum product, i.e. a gypsum product with a density of about 0.78, obtained by reacting gypsum hemihydrate, hydrophobic stearates, carbonates or bicarbonates, basic oxides, emulsions of synthetic resins, water and acid fluorides, such as aqueous hexafluorosilicic acid. ca 100:214666, an abstract of jp-82-112342, relates to a gypsum product with a density of about 0.78 obtainable by reacting gypsum hemihydrate, stearates, carbonates or bicarbonates, basic oxides, acidic fluorides, for example hexafluorosilicic acid, in the presence of polyvinyl alcohol. ca 89:151558, an abstract of jp-a-76-128274, relates to a gypsum product with a density of 0.35 g/cm.sup.3, in which a calcined gypsum, a fibrous material, a metal oxide and a stabilizer are contacted with water, a percarbonate is added and the mixture as a whole is then subjected to a heat treatment. ca 87:89532, an abstract of jp-a-75-93352, relates to a low-density gypsum product in which an .alpha.-gypsum is stirred together with water and ammonium hydrogen carbonate is then added. ca 80:86931, an abstract of jp-a-69-84902, relates to a gypsum product with a density of about 0.56 g/cm.sup.3 obtainable by reacting a calcined gypsum suspension to which a concentrated aqueous formaldehyde solution, water and ammonium hydrogen carbonate are added. ca 82:102462, an abstract of jp-a-72-347, relates to a low-density gypsum product obtainable by reacting synthetic gypsum and sodium hydrogen carbonate to which a 1% polyvinyl alcohol solution was added before heating for 1 hour to 80.degree. c. ca 81:175233, an abstract of jp-a-72-107634, relates to gypsum products with densities of 0.15 to 0.65 g/cm.sup.3 obtainable by reacting a gypsum suspension together with a fatty acid salt, a foam stabilizer based on a fatty acid salt, calcium carbonate and aluminium sulfate. ca 115:238433 and ca 112:164011 an abstract of an article in clc chem. labor. biotech. (1990), 41 (2), pages 79-80, relates to an artificial building material, in which surfactants, barium carbonate and water are mixed and foamed and clay or inter alia gypsum is mixed with the resulting foam. jp-a-901296780 relates to a low-density gypsum product or gypsum foam obtained by reacting a gypsum suspension with a sulfonate of a c.sub.10-16 fatty acid alkyl ester as foaming agent. de-c-41 34 550 relates to a process for the production of in situ foam by reacting suspended gypsum with polyisocyanate prepolymers, in which 30 to 70% by weight of gypsum dihydrate and 30 to 30% of water, based on the slurries, are used as the suspended gypsum and 40 to 60% by weight of the gypsum dihydrate/water slurries and 60 to 40% by weight of standard diphenyl methane-4,4'-diisocyanate or diphenylmethane-4,2'-diisocyanate prepolymers with an nco content of 2 to 20% by weight or 2,4-toluene diisocyanate or 2,6-toluene diisocyanate prepolymers with an nco content of 2 to 20% by weight or a mixture of these compounds are introduced into the gap and left to cure at normal temperature and pressure. the in situ foam is produced in particular by means of a multicomponent unit, such as a spray can or spray gun. in the case of two-component systems, the aqueous component consists of a thixotropic hydrargillite/rea gypsum (rea gypsum=gypsum from flue glas desulfurizing plants) mixture with a solids content of at least 66% by weight using water-soluble, chemically modified celluloses as the thixotropicizing agent. the foam thus obtained can be machined after curing and is flame-retarded. wo 93/08142 is based on the same priority. ca 92:63584p, an abstract of jp-a 79/119528, relates to a low-density gypsum product, in which a gypsum hemihydrate is foamed with a urethane prepolymer and water, optionally in the presence of fillers, and allowed to cure. a flame-retardant gypsum product with a specific gravity of 0.52 is obtained in this way. in view of the steadily intensifying environmental debate, there is a high demand for more environmentally compatible insulating materials and low-density gypsum parts and gypsum mouldings. modern one-component and two-component polyurethane foams, which are used in containers, such as cans, or with mixing units, inter alia for heat insulation, harm the environment with some of their ingredients, for example the frigen.rtm. used as blowing agent, i.e. fluorochlorocarbons, partly halogenated fluorochlorocarbons, fluorocarbons (cfcs, hcfcs, fcs), and continue to harm the environment through halogen-containing flameproofing agents. all the above-mentioned compositions for the production of low-density gypsum have disadvantages insofar as, in the case of polyurethane-free systems, foaming by gas generation takes place immediately after addition of the gas-generating component, i.e. the pot life or induction time (=time before the increase in volume) of such systems is of the order of 1 to 10 seconds which makes systems of the type in question difficult to handle in practice for direct "in situ mixing". however, even with systems containing polyisocyanates, which normally have pot lives or induction times of 5 to 60 seconds in the case of pure pu foams, this period of time is generally not sufficient to enable such a known composition to be introduced before foaming into complicated spaces where it is used as a in-situ foam (cf. franck, kunststoff-kompendium, 1st edition, wurzburg 1984, page 211). even the rise time (=time from the beginning of mixing to the end of expansion) of pure pur foams is only 55 to 270 seconds and, accordingly, in complicated and large spaces, can never lead to a light gypsum which is uniformly foamed--a crucial requirement, for example, for good insulating properties. detailed description of the invention the problem addressed by the present invention was to provide an improved composition for the production of light gypsum which contains setting, particulate gypsum in the form of anhydride and/or hemihydrate and at least one blowing agent as key constituents and which, under in-use conditions, i.e. in the presence of water, has a pot life or induction time which can be adjusted according to a time to be individually adapted according to the particular application envisaged and which, in most cases, is longer than the pot lives of known compositions for the production of light gypsum. according to the invention, the solution to this problem is characterized in that a special blowing agent with a long induction time is used in a special concentration. accordingly, the present invention relates to a composition for the production of light gypsum which contains setting, particulate gypsum in the form of anhydride and/or hemihydrate and at least one blowing agent as key constituents, characterized in that the blowing agent generates gas with delay 1 minute to 24 hours after mixing with water. the blowing agent preferably generates gas in 1.5 to 60 minutes and, more preferably, in 3 minutes to 30 minutes. in one preferred embodiment, the composition for producing light gypsum contains 0.1 to 50% by weight and preferably 1 to 20% by weight of at least one blowing agent for the delayed generation of gas. a blowing agent in the context of the invention is a substance with which a blowing gas can be generated after addition of water to the particulate, setting gypsum. the blowing agent added causes the mixture of setting gypsum and water to expand. setting, particulate gypsum in the context of the present invention is understood to include bead gypsum, stick gypsum of randomly formed gypsum which may be present both in powder form and in the form of microbeads with diameters of typically from 1 .mu.m to 1 cm and preferably from 2 .mu.m to 1 mm. the blowing agent for the delayed generation of gas preferably consists of at least two components of which at least one is provided with a water-permeable, preferably film-forming coating. in the blowing agent of two added components, both components may of course also be coated. alternatively, the composition may also be formulated in such a way that the blowing agent for the delayed generation of gas consists of one component which is provided with a water-permeable, preferably film-forming coating. the above-mentioned water-permeable, preferably film-forming coating contains at least one water-swellable, water-dispersible or water-soluble, naturally occurring substance, at least one synthetically modified, naturally occurring, enzymatically decomposable substance or at least one synthetic substance. the above-mentioned substance may be both an inorganic substance and an organic substance. examples of inorganic substances include soda or potash waterglass, polyphosphates, magnesium sulfate and calcium sulfate and other substances with only a small solubility product. where the water-permeable, preferably film-forming coating used in accordance with the invention is a naturally occurring polymer, it contains polysaccharides, lignin, natural rubber, proteins and/or natural resins, for example colophony-based natural resins. where polysaccharide-based polymers are used as the coating material in the compositions according to the invention, they contain film-forming materials obtained from terrestrial plants, from marine plants or from microorganisms. thickeners based on polysaccharides from terrestrial plants are understood above all to be starch and starch products, i.e. for example corn starch, wheat starch and rice starch and also potato starch and tapioca starch. starch products in the context of the invention are understood to be physically modified starch products which, in contrast to native starch, neither have to be boiled before use to obtain the thickening effect nor form opaque and unstable solutions which turn into a jelly or throw a deposit on standing. starches of the type in question produced by physical modification and/or enzymatic degradation are obtained in the form of pregelatinized starches, above all by pregelatinization and subsequent drying, so-called roller drying or spray drying. other polysaccharides obtained from terrestrial plants are the galactomannans, for example carob bean flour and guar gum. other polysaccharides obtained from terrestrial plants are the so-called pectins or pectinous substances which include orange pectin, grapefruit pectin, lemon pectin and apple pectin according to the starting material. other clear differences will be apparent according to whether the product used has a high degree of esterification or a low degree of esterification. instead of pectin itself, the principal constituent of pectin, namely polygalacturonic acid, may also be used. another polysaccharide obtained from terrestrial plants is an exudate gum, for example gum arabic or acacia gum and tragacanth. other polysaccharides obtained from terrestrial plants are cellulose derivatives such as, for example, o-carboxymethyl cellulose (cmc) and o-methyl cellulose. other polysaccharides obtained from terrestrial plants are derived from quince seed mucilage and linseed mucilage, cherry gum, salepmannan, larch gum, lichenin from irish moss, tamarind seed flour, conjaku flour and tara gum. the polysaccharides obtained from marine plants, which may be used for a coating forming a layer removable by water, are understood above all to be alginates, i.e. polysaccharides obtained from the cell walls of various brown algae. other polysaccharides obtained from marine plants are agars which are obtained from the cell walls of red algae of the species gelidium and gracilaria and which represent mixtures of the gelling agarose and the non-gelling agropectin. other polysaccharides obtained from marine plants are the carrageenans obtained by extraction of certain red algae. finally, other polysaccharides obtained from marine plants are various other algal polysaccharides of which the most well known is danish agar. another group of polysaccharides which may be used as the film-forming coating material are thickeners obtained from microorganisms, for example the dextran formed by leuconostoc mesenteroides and the xanthan formed by xanthomonas campestris. normally, protein-based thickeners are essentially gelatins which are available in various qualities. depending on the production process used, gelatin is divided above all into type a, which is obtained by the acidic digestion of collagen, and type b which is produced by a corresponding alkaline digestion process. synthetically modified, naturally occurring polymers are understood in particular to be modified polysaccharides and, above all, the corresponding cellulose ethers, cellulose esters, starch esters or starch ethers or a mixture thereof. examples of cellulose ethers are methyl cellulose, hydroxymethyl cellulose, hydroxymethylhydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxyethylmethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, ethyl cellulose, carboxymethyl cellulose or a mixture of the above-mentioned cellulose ethers. examples of cellulose esters are cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, cellulose propionate or a mixture of these cellulose esters. examples of starch esters are starch nitrate, starch phosphate, starch xanthogenate, starch acetate, starch sulfate, starch citrate or a mixture of these starch esters. examples of starch ethers are starch carboxymethyl ether, hydroxyethyl starch, hydroxypropyl starch, cationic starches and mixtures of the above-mentioned starch ethers. enzymatically decomposable substances in the context of the present invention are understood in particular to be organic substances which are degraded by microorganisms. examples of such organic substances include the above-mentioned polysaccharides and modified polysaccharides. synthetic polymers which may be used as a film-forming coating material removable by water include polymers selected from polyvinyl compounds, preferably polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate/crotonic acid copolymers, polymaleic anhydride and copolymers thereof, polyvinyl butyral; from polyacrylic compounds, preferably poly(meth)-acrylic acid ester copolymers; poly-2-ethyl oxazoline and polyacrylamides. in addition, polyethylene oxides with molecular weights of 100,000 to 5,000,000 may also be used as the synthetic, permeable film-forming coating materials. finally, the synthetic polymers removable by water also include polyelectrolytes, such as anionic polyelectrolytes, for example poly(acrylic acid) and salts thereof, poly(methacrylic acid) and salts thereof, poly(vinylsulfonic acid) and salts thereof, poly(styrene sulfonic acid) and salts thereof, 2-methacryloyloxyethane sulfonate (sem), 3-methacryloyloxy-2-hydroxypropane sulfonic acid (shpm), 2-acrylamido-2-methyl propane sulfonic acid (amps), sodium-3-acrylamido-3-methyl butanoate, sodium-3-methacrylamido-3-methyl butanoate, poly(vinyl phosphonic acid) salts, poly(maleic) acid, poly(4-vinylbenzoic acid) salts, poly(3-vinyloxypropane-1-sulfonic acid) salts, poly(4-vinylphenol) salts and poly(n-vinyl succinic acid imide) acid. polyelectrolytes of the type in question are also understood to include cationic polyelectrolytes, for example cations based on polyacrylamide, diallyl dimethyl ammonium chloride, diallyl diethyl ammonium chloride, diethyl aminoethyl methacrylate, dimethyl aminoethyl methacrylate, methacryloyloxyethyl trimethyl ammonium sulfate, methacryloyloxyethyl dimethyl ammonium chloride and 3-(methacrylamido)-propyl trimethyl ammonium chloride. an overview of these water-soluble polymers suitable for use in accordance with the invention can be found in encyclopedia of polymer science and engineering, vol. 17 (1989), pages 730 to 784. polyurethane dispersions (cationic, anionic and nonionic) may also be used. another group of water-permeable polymers are, for example, polyethylene glycols with molecular weights of more than 600 g/mole. in their case, the blowing agent(s) may be coated by grinding of the component(s) together with the polyethylene glycol, the polymer being applied to the surface of the blowing agent. other water-permeable, preferably film-forming polymers are polypropylene glycol, poly(1,2-)dimethoxyethylene, poly(methyl vinyl ether), poly(4(5)vinyl imidazole), poly(vinyl-4-chlorobenzoate). also suitable are the ionenes, i.e. strong polybases with tertiary nitrogen in the main chain which are described, for example, in the book by e. a. bekturov and z. kh. bakauova entitled "synthetic water-soluble polymers in solution" huthig, basel, 1986, pages 79 to 83. other water-soluble polymers which may be used in accordance with the invention to produce a film-forming coating can be found in this book. it is of course also possible to use monomer mixtures for the polymerization and to employ mixtures of various polymers. the water-permeable, preferably film-forming polymer coating mentioned above is normally applied to at least one of the two components of the blowing agent by a coating process. suitable coating processes are generally known to the expert and may be carried out, for example, in typical coating machines such as, for example, coating pans, tumblers, fluidized beds or bead coaters. a review of coating techniques as used in food technology was published, for example, in an article in the company journal of haarmann und reimer entitled "contakt", no. 57, pages 4-8 and no. 58, pages 3-7. it is apparent from this literature reference that the solutions employed for coating are typically used in quantities of about 10 to 40%. where synthetic polymers are used, 5 to 80% by weight solutions are normally employed. in one preferred embodiment of the present invention, a blowing agent which generates carbon dioxide gas, oxygen gas, hydrogen gas, dinitrogen oxide gas, a noble gas or nitrogen gas with delay is used in the composition for producing light gypsum. if the blowing agent mentioned above is required to generate a noble gas, noble gases, for example argon in inclusion compounds, are used for this purpose. one example is hydroquinone which forms cage lattices in which not only noble gases, but also oxygen is accommodated. inclusion compounds such as these can be constructed in such a way that gas is released from them with delay. in one preferred alternative embodiment of the present invention, the composition for producing light gypsum contains an acidic organic or inorganic solid component provided with a water-permeable, preferably film-forming coating as the blowing agent and the particulate gypsum is a gypsum which contains at least 1 mg of carbonate per gram of gypsum. carbonate-containing gypsums of the type in question either occur in nature, as for example natural anhydrite in the form of the rocks trias and colpa, which have a total percentage content of calcium carbonate and magnesium carbonate of 2.5%, or flue gas gypsum with a calcium carbonate content of 1% by weight, or may be made with a carbonate content by addition of carbonate. an overview of gypsum as a natural raw material and as a residual material of industrial processes was published in "chemie in unserer zeit", vol. 17, 1985, no. 4, pages 137 to 143. the carbonate content can vary from 0 to at most 5%, depending on how the rocks are crushed. in another preferred embodiment, the composition according to the invention consists of an blowing agent with at least two components of which at least one component contains an acidic organic solid component selected from organic acids or phenols or an inorganic solid component selected from acids or acidic salts of this compound optionally provided with a water-permeable preferably film-forming coating. in another preferred embodiment, the composition according to the invention contains a component of the blowing agent which contains a gas-generating solid component selected from metal powders such as, for example, magnesium powder, aluminium powder, azo compounds, carbonates, hydrogen carbonates, sesquicarbonates, peroxides, perborates, percarbonates, azides or hydrides which is optionally provided with a water-soluble, film-forming coating. if the blowing agent in the composition according to the invention contains two components, the solid acidic component preferably has a water-soluble coating. the acidic component of the blowing agent preferably contains an organic acid which is preferably selected from hydroxycarboxylic acids, such as citric acid, tartaric acid or malic acid, ascorbic acid or glucose acid, dimethylol propionic acid, etc. or mixtures thereof. the gas-generating blowing agents mentioned above are preferably solid compounds which generate carbon dioxide gas or an oxygen gas selected from carbonates, hydrogen carbonates, sesquicarbonates, peroxides, perborates and percarbonates of mono- to tetravalent cations, more particularly alkali metals and alkaline earth metals, more especially sodium, potassium, magnesium, calcium or barium. if a blowing agent which generates gas with delay is not the only important aspect of the composition according to the invention, i.e. if a light gypsum of high strength and high homogeneity is also to be obtained, the composition must also contain--based on the dry mixture as a whole--from 0.5 to 50% by weight of at least one water-soluble, water-dispersible or water-dispersed polymer. the polymer in question may be, for example, a redispersion powder or a polymer dispersion which is added during mixing with water or instead of water. any dispersions which form a stable mixture with gypsum over the corresponding processing time (for example acrylate, vinyl acetate, urethane, amide dispersions, copolymers and mixtures) are suitable for this purpose. the polymer in question may also be an oleochemical polymer, for example a reaction product of a soybean oil epoxide with ethylenediamine having an average molecular weight of about 30,000 g/mole. the polymer may also be a water-soluble, preferably film-forming organic polymer of the type defined above. the redispersion powder is preferably a vinyl acetate or a vinyl acetate copolymer, for example an ethylene/vinyl acetate. the redispersion powder may also be a water-soluble, water-dispersible or water-dispersed polymer based on acrylate or an acrylate copolymer, for example styrene/acrylate or styrene/butadiene/acrylate. natural rubber, polychloroprene, polyurethane and polyamide is also suitable for this purpose. according to the invention, a mixture of the polymers mentioned above may also be used as a cohesion agent. in the composition according to the invention, the principal component is a gypsum in the form of the anhydride or hemihydrate in all the chemical modifications occurring (.alpha.- and .beta.-hemihydrate, anhydrite i, ii, iii) based on natural gypsum and synthetic gypsum. in principle, these hydraulically setting versions based on caso.sub.4 may be present both in pure form and in the form of mixtures. a .beta.-gypsum of the type obtained by the rotary calciner process or by the kettle process is normally used as the natural gypsum. a corresponding multiphase gypsum may be obtained by the travelling grate process while an .alpha.-gypsum may be obtained by the autoclave process. in the case of the gypsums used in the form of synthetic gypsums, the .beta.-gypsum is obtained by the knauf rotary calciner process, the knauf kettle process and by the kettle process without recrystallization. a corresponding multiphase gypsum may be obtained as synthetic gypsum by the knauf aggregate process while an .alpha.-gypsum may be obtained by the giulini autoclave process. today, however, a large proportion of gypsum comes from the desulfurization of flue gases where it is produced in the bischoff process, in the saarberg-holter process and in the bergbau-forschung (mining research) process, around 2 million tonnes of so-called residue gypsum having been produced for example in 1990. the .alpha.-hemihydrate from rea gypsum above all has acquired particular significance. this low-carbonate gypsum is used, for example, when the acidic blowing agent component or both components required for the blowing gas (added carbonate and acidic component) are present in coated form. in the compositions according to the invention, gypsum of the provenances mentioned above is present as the main product in quantities of 20 to 99.9% by weight and preferably 50 to 98% by weight, based on the inorganic binder component of the dry mixture. other constituents of the gypsum-containing compositions according to the invention are, for example, typical fillers, auxiliaries and additives which vary according to the application envisaged. the fillers are, above all, mineral and/or inorganic fillers such as, for example, clays, sand, gravel, cement, slag, glass, silica gels, sulfates (for example calcium sulfate dihydrate), oxides (for example magnesium oxide, calcium oxide), glass and mineral fibers, manmade fibers, hollow microbeads, organic light fillers (for example polystyrene foam), granules (fined) from recycling plants, paper powder, starch powder, wood chips and sawdust, cellulose fibers, etc. preservatives, rustproofing agents, dyes and flame retardants, for example vermiculite, aluminium or magnesium hydroxide or organic flame retardants, may also be used as additives. other constituents of the gypsum composition according to the invention are substances with a wetting effect which reduce the water demand and are normally known as wetting agents. examples are alkylaryl sulfonates, salts of lignin sulfonic acid or melamine resins. an overview of wetting agents can be found, for example, in an article in "zement, kalk, gips", vol. 21, pages 415 to 419 (1968). these wetting agents are normally added to the composition according to the invention in quantities of 0 to 10% and, through the relatively low water content, often reduce the late drying time of the set gypsum formulations. the water demand can also be increased by addition of flocculating agents, for example polyethylene oxides of the type described, for example, in gb-a-1,049,184. these auxiliaries may be added in quantities of 0 to 10% by weight, based on the dry mixture. the stabilization of a water/gypsum slurry to prevent sedimentation or separation is achieved by adding chemicals with a thickening effect, for example cellulose and starch ethers. these thickeners have hardly any effect on the water demand. they are added to the dry mixture according to the invention in quantities of 0 to 5% by weight, based on the dry mixture. as already mentioned, polymer dispersions may also be added to the gypsum during mixing in order in particular to improve elasticity and adhesion. the compositions according to the invention may also contain auxiliaries which act as accelerators. these accelerators may be selected in particular from various inorganic acids and salts thereof, more particularly sulfuric acid and salts thereof. a special position in this regard is occupied by calcium sulfate dihydrate which, in fine distribution, has a pronounced accelerating effect and, accordingly, has to be completely removed in the calcination of crude gypsum. the accelerating effect of these substances is mostly attributable to an increase in the solubility and dissolving rate of the calcined gypsum and to an increase in the nucleation rate. other auxiliaries in the gypsum-containing composition according to the invention are known retarders which slow down the stiffening and hardening process. they include, above all, organic acids and salts thereof and organic colloids which are also formed, for example, as degradation products in the hydrolysis of high molecular weight naturally occurring substances, for example proteins, and also salts of phosphoric acid or boric acid. dextrins and hisbiscus roots are also suitable. there are various retarding mechanisms. relatively high molecular weight colloids prolong the induction period because they are nucleus poisons. other retarders slow down the dissolving rate of the hemihydrate and the growth of the dihydrate crystals. retarding anhydride ii is generally of no practical interest because it already changes into dihydrate sufficiently slowly and is generally accelerated. based on the dry mixture, this particular component may make up from 0 to 5% by weight of the gypsum compositions according to the invention. as known to the expert, the quantity of water used required upon the type of gypsum starting material used, i.e. to obtain a free-flowing slurry of the same consistency, a rotary calciner .beta.-gypsum needs more water than a kettle gypsum which in turn needs more water than a multiphase gypsum which, for its part, needs more water than an autoclave gypsum. in addition, the quantity of water has a critical bearing both on the density and on the strength of the gypsum product formed. without requiring any special measures, .alpha.-gypsums which can be molded with quite small amounts of water give gypsum products of high density and high strength which, on account of their unwanted brittleness, are avoided for many applications in the building industry. .beta.-gypsums and multiphase gypsums need more water than .alpha.-gypsums for a free-flowing consistency. accordingly, they give gypsum products combining average strength and relatively high elasticity with relatively low densities which are widely used in the building industry. the present invention also relates to a composition of the above-mentioned type which, besides particulate gypsum in the form of anhydride and/or hemihydrate and gas-generating agent, also contains 0 to 45% of fillers (and fibers, light fillers, etc.), 0 to 2% of a wetting agent, 0 to 5% of a wetting agent, 0 to 5% of an accelerator, 0 to 5% of a retarder, 0 to 5% of a hydrophobicizing agent, 0 to 5% of a plasticizer, based in each case on the mixture as a whole. in one preferred embodiment, the hydrophobicizing agent present in the composition according to the invention is a polysiloxane, a wax (in pure form, dispersed or adsorbed onto a support material) or an oleochemical additive (which may act both as a hydrophobicizing agent and as a polymer strengthener), the oleochemical additive being selected from at least one at least c.sub.8 fatty compound containing at least one carboxyl group and having a molecular weight of 143 to 20,000 and/or a salt thereof, at least one at least c.sub.8 fatty compound containing at least one hydroxyl group and having a molecular weight of 130 to 20,000, at least one fatty compound containing at least one ester group and having a molecular weight of 158 to 20,000, the acid component and/or the alcohol component containing at least 8 carbon atoms, at least one fatty compound containing at least one ether group and having a molecular weight of 144 to 20,000, at least one of the two ether groups containing at least 8 carbon atoms, at least one fatty compound containing at least one amino group or one quaternary ammonium salt and having a molecular weight of 129 to 20,000, at least one of the three or four groups arranged around the nitrogen atom containing at least 8 carbon atoms, at least one fatty compound containing at least one amide group and having a molecular weight of 157 to 20,000, the acid component of the amide containing at least 8 carbon atoms, at least one at least c.sub.8 fatty compound containing at least one epoxide group and having a molecular weight of 128 to 20,000, at least one at least c.sub.8 fatty compound containing at least one anhydride group and having a molecular weight of 210 to 20,000, at least one at least c.sub.8 organophosphorus fatty compound having a molecular weight of 193 to 20,000, at least one at least c.sub.8 organoboron fatty compound having a molecular weight of 174 to 20,000, at least one at least c.sub.8 organosulfur fatty compound having a molecular weight of 164 to 20,000 and at least one at least c.sub.8 fatty compound containing at least one urethane group and having a molecular weight of 213 to 20,000. the present invention also relates to a process for the production of the retarded gas-generating blowing agent mentioned above which is characterized in that either an acidic component or a gas-generating component or both components separately from one another is/are contacted with a water-containing dispersion or solution, which contains at least one water-permeable, naturally occurring substance, at least one synthetically modified naturally occurring substance, at least one enzymatically degradable or synthetic substance or at least one polymer of the type described above, for a time sufficient for the film-forming coating to form and any excess solvent is removed. the film-forming coating is normally produced by a coating process known to the expert, for example by fluidized bed coating, by tumbler coating, by pan coating or by coating in a bead coater. alternatively, the retarded gas-generating blowing agent which may be used in the compositions according to the invention may also be produced by contacting the acidic component and/or the gas-generating component with a dispersion or solution containing a non-aqueous solvent, which contains or consists of at least one water-permeable, naturally occurring substance, at least one synthetically modified naturally occurring substance or synthetic substance or at least one polymer of the type mentioned above, for a time sufficient for the preferably film-forming coating to form and removing any excess solvent. non-aqueous solvents in the context of the present invention are understood to be organic solvents which are inert both to the acidic component and to the gas-generating component so that no premature gas generation can occur. examples of such organic solvents are substantially water-free hydrophilic solvents for the polymers, particularly synthetic polymers, mentioned above. in another alternative embodiment, the components may also be coated by using as the water-permeable, preferably film-forming coating a substance of wax-like consistency which, in the event of contacting, for example by grinding, applies both to the acidic component and to the gas-generating component a coating which is permeable to water with delay and, accordingly, is capable of generating gas with delay. in another preferred embodiment, the problem addressed by the present invention was to use the above-mentioned composition in a pack in which the particulate, setting gypsum, the blowing agent(s) and the auxiliaries and additives are present together, the volume of the pack being selected so that a water-containing liquid can be added at least in a quantity sufficient for setting. another problem addressed by the present invention was to enable the compositions according to the invention to be used for the production of in-situ foam or gap-filling foam. foams of this type are foams which are produced at the point of use, i.e. in situ. in-situ foams are preferably used as assembly foams, for filling voids and as insulating foams both indoors and outdoors. foams of the type in question may also be used with particular advantage for applications where the applied but as yet non-foamed mixture has to be prevented from flowing under the effect of gravity, for example between door frames or window frames and masonry. another potential application is the filling of empty spaces, for example in mines for consolidating loose rock, for the heat insulation and sound insulation of domestic appliances, containers, roofs and molds of complex geometry, in the petroleum industry and for the rapid and relatively simple construction of emergency accommodation. the compositions according to the invention are also suitable for the production of assembly adhesives and modeling compounds. another problem addressed by the present invention was to enable the compositions according to the invention to be used for the production of low-density gypsum products, i.e. gypsum products with a density of 0.05 to 1.5 g/cm.sup.3 and preferably 0.1 to 1.0 g/cm.sup.3. such products are, on the one hand, the so-called prefabricated rigid-foam gypsum moldings which are widely used in the building industry in the form of sandwich type gypsum plasterboards, gypsum wallboards, heat insulation boards, gypsum partition blocks and gypsum ceiling boards. a relevant overview can be found in ullmann's encyklopadie der technischen chemie, vol. 12, page 307 (1976). the gypsum-containing compositions according to the invention may also be used in the form of gypsum plaster, more particularly insulating plaster. the invention is illustrated by the following examples in which the blowing agent is shown by way of example as a system generating carbon dioxide gas with delay. examples production example 1 (two-component blowing agent, one component coated) a1. coated blowing agent component: 50 g of dimethylol propionic acid are mixed while stirring with a methyl cellulose solution of 10 g in 200 ml of water and the water is removed in vacuo in a rotary evaporator. a free-flowing powder is obtained after cooling. b1. uncoated blowing agent component: calcium carbonate, technical, for example calcilith 16b, a product of alpha-calcit application example 1 (two-component blowing agent, carbonate-free gypsum hemihydrate and water) a composition for the production of light gypsum was produced by mixing 3 g of a1, 11.5 g of b1 and 50 g of gypsum (calcium sulfate hemihydrate) of the alfor type (manufacturer: borgardts-sachsenstein, density 2.63, bulk density 900 g/l). this composition was named g1. 64.5 g of g1 were introduced into 30 ml of water with vigorous stirring and poured into a casting mold over a period of up to 1 minute. the generation of gas and foaming to a volume of around 300% began after about 2 minutes and was over after about 5 minutes; the curing process itself was over after about 60 minutes. the dried gypsum foam had a density of 0.5 g/ml. application example 2 (two-component blowing agent, carbonate-free gypsum hemihydrate, water-dispersible polymer and water) application example 1 was varied by adding 5 g of a dimensionally stabilizing polymer in the form of polyvinyl acetate redispersion powder (elotex.rtm. hm-110, a product of elotex ag, switzerland) to 100 g of composition g1. this mixture was named g2. 69.5 g of g2 were introduced into 33 ml of water with vigorous stirring and poured into a casting mold over a period of up to 1 minute. the generation of gas and foaming to a volume of around 260% began after about 2 minutes and was over after about 5 minutes; the curing process itself was over after about 50 minutes. the added polymer considerably improved the strength of the foamed gypsum product in relation to application example 1. the density of the air-dry gypsum molding was 0.56 g/ml. production example 2 (one-component blowing agent, coated) a coated dimethylol propionic acid was produced in the same way as in production example 1, except that the methyl cellulose was replaced by the same quantity of polyvinyl alcohol as the water-soluble polymer. application example 3 (one-component blowing agent, coated; carbonate-containing gypsum hemihydrate; water) a composition for the production of light gypsum was produced by mixing 3 g of a1 and 60 g of gypsum (calcium sulfate hemihydrate, carbonate-containing) of the alfor type (manufacturer: borgardts, carbonate content 3%, density 2.63, bulk density ca. 900 g/l). this composition was named g3. 63 g of g3 were introduced into 30 ml of water with vigorous stirring and poured into a casting mold over a period of up to 1 minute. the generation of gas and foaming to a volume of about 150% began after about 2 minutes and was over after about 4 minutes; the curing process itself was over after about 60 minutes. the dry gypsum molding had a density of about 1.1 g/ml. production example 3 (two-component blowing agent, both components coated at the same time) ab2. 30 g of dimethylol propionic acid and 100 g of calcium carbonate were ground together with 10 g of peg 6000 for 1 hour in a 1000 ml ball mill. a free-flowing powder was obtained. application example 4 (two-component blowing agent with delayed gas generation, gypsum hemihydrate, water) a composition for the production of light gypsum was produced by mixing 13 g of a ab2 and 50 g of gypsum (calcium sulfate hemihydrate) of the alfor type according to application example 1. this composition was named g4. 63 g of g4 were introduced with vigorous stirring into 30 ml of water at 20.degree. c. and poured into a casting mold over a period of up to 1 minute. the generation of gas and foaming to a volume of around 270% began after about 1.5 minutes and was over after about 3 minutes; the curing process itself was over after about 60 minutes. the air-dry molding had a density of 0.55 g/ml.
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101-691-961-735-725
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EP
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[
"EP"
] |
E21B33/12,E21B33/127,E21B43/10
| 2021-11-10T00:00:00 |
2021
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[
"E21"
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downhole expandable tubular
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the present invention relates to a downhole expandable tubular for expansion in a well downhole from a first outer diameter to a second outer diameter to abut against an inner face of a well tubular metal structure or borehole, the downhole expandable tubular having an outer face, a longitudinal extension and a tubular length along the longitudinal extension. the invention also relates to an annular barrier for expansion in an annulus between a well tubular metal structure and an inner face of a borehole or another well tubular metal structure for providing zone isolation between a first zone and a second zone of the borehole. moreover, the invention relates to a downhole system comprising a well tubular metal structure having an inner face, an outer face, a downhole expandable tubular being connected to the inner face, and a downhole closure unit arranged on the outer face for permanently sealing off a control line controlling a well component of the well tubular metal structure prior to plug and abandonment of a well having a top. finally, the invention relates to a method of permanently closing fluid communication in the downhole closure unit for permanently sealing off a control line prior to plug and abandonment of a well.
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a downhole expandable tubular (1) for expansion in a well (2) downhole from a first outer diameter (d 1 ) to a second outer diameter (d 2 ) to abut against an inner face (4) of a well tubular metal structure (3) or borehole (5), the downhole expandable tubular having an outer face (6), a longitudinal extension (l) and a tubular length (l t ) along the longitudinal extension, comprising: - at least one first circumferential edge (7) and at least one second circumferential edge (8) spaced apart in the longitudinal extension and provided on the outer face, forming a circumferential groove (9), and - a sealing unit (10) arranged in the circumferential groove, wherein the sealing unit has a unit length (l u ) along the longitudinal extension being less than 20% of the tubular length, and the sealing unit comprises a post-transition metal material. a downhole expandable tubular according to claim 1, wherein the post-transition metal material comprises bismuth or a bismuth alloy. a downhole expandable tubular according to claim 1 or 2, wherein the sealing unit comprises more than one element, and at least one of the elements comprises the post-transition metal material. a downhole expandable tubular according to any of the preceding claims, wherein the sealing unit further comprises an annular sealing element (11) and a retaining element (12), and at least the retaining element comprises a post-transition metal material such as bismuth or a bismuth alloy. a downhole expandable tubular according to claim 3 or 4, wherein the element comprising a post-transition metal material such as bismuth or a bismuth alloy is one monolithic whole. a downhole expandable tubular according to claim 4, wherein the retaining element has a first end and a second end, and the first end overlaps the second end when seen along the longitudinal extension or along a circumference of the downhole expandable tubular. a downhole expandable tubular according to claim 5 or 6, wherein the retaining element is a split ring-shaped retaining element having more than one winding, so that when the expandable tubular is expanded from the first outer diameter (d 1 ) to the second outer diameter (d 2 ), the split ring-shaped retaining element partly unwinds. a downhole expandable tubular according to claim 7, wherein the split ring-shaped retaining element unwinds by less than one winding when the expandable tubular is expanded from the first outer diameter (d 1 ) to the second outer diameter (d 2 ). a downhole expandable tubular according to any of the preceding claims, wherein the material expands upon solidification. a downhole expandable tubular according to any of the preceding claims, wherein the material liquifies at above 130 degrees centigrade. an annular barrier (50) for expansion in an annulus (103) between a well tubular metal structure (3a) and an inner face (4) of a borehole (5) or another well tubular metal structure (3) for providing zone isolation between a first zone (101) and a second zone (102) of the borehole, comprising: - a tubular metal part (20) for mounting as part of the well tubular metal structure (3a), - a downhole expandable tubular (1) according to any of the preceding claims surrounding the tubular metal part (20) and having an outer face facing towards the inner face of the borehole or the well tubular metal structure, each end (31, 32) of the downhole expandable tubular being connected with the tubular metal part, - a annular space (21) between the downhole expandable tubular and the tubular metal part, and - an expansion opening (23) in the tubular metal part through which fluid may enter into the annular space in order to expand the downhole expandable tubular. an annular barrier (50) according to claim 10, further comprising a downhole closure unit (61) in the annular space for permanently sealing off a control line controlling a well component (52) of a well tubular metal structure (3) prior to plug and abandonment of a well (2) having a top (51), comprising: - a first element (105) comprising a first opening (106), a second opening (107) and fluid communication (108) between the first opening and the second opening, the first opening being arranged closer to the top than the second opening, the first opening having a first connection (109) to a first part (110) of a tubular line (104), and the second opening having a second connection (111) to a second part (112) of the tubular line, wherein the first element has a first state in which the fluid communication is open and a second state in which the fluid communication is closed. a downhole system comprising a well tubular metal structure (3) having an inner face (4), an outer face (64), a downhole expandable tubular (1) according to any of the preceding claims 1-10 being connected to the inner face, and a downhole closure unit (1) arranged on the outer face for permanently sealing off a control line controlling a well component of the well tubular metal structure (3) prior to plug and abandonment of a well (2) having a top (51), the downhole expandable tubular comprising: - a first element (105) comprising a first opening (106), a second opening (107) and fluid communication (108) between the first opening and the second opening, the first opening being arranged closer to the top than the second opening, the first opening having a first connection (109) to a first part (110) of a tubular line (104), and the second opening having a second connection (111) to a second part (112) of the tubular line, wherein the first element has a first state in which the fluid communication is open and a second state in which the fluid communication is closed. a downhole system comprising a well tubular metal structure (3) having an inner face (4), an outer face (64) and an annular barrier according to claim 12. a method of permanently closing fluid communication in the downhole closure unit for permanently sealing off a control line prior to plug and abandonment of a well, comprising: - inserting a well tubular metal structure (3) having a completion component and an annular barrier according to claim 13 comprising the downhole closure unit and a control line in a tubular line (104) for operating the completion component, - heating the first element of the downhole closure unit in the annular space of the annular barrier so that the material of the first element at least partly changes condition to a more liquified or mouldable condition, and - expanding the material of the first element during solidification of the material of the first element and thus closing the fluid communication between the first opening and the second opening.
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the present invention relates to a downhole expandable tubular for expansion in a well downhole from a first outer diameter to a second outer diameter to abut against an inner face of a well tubular metal structure or borehole, the downhole expandable tubular having an outer face, a longitudinal extension and a tubular length along the longitudinal extension. the invention also relates to an annular barrier for expansion in an annulus between a well tubular metal structure and an inner face of a borehole or another well tubular metal structure for providing zone isolation between a first zone and a second zone of the borehole. moreover, the invention relates to a downhole system comprising a well tubular metal structure having an inner face, an outer face, a downhole expandable tubular being connected to the inner face, and a downhole closure unit arranged on the outer face for permanently sealing off a control line controlling a well component of the well tubular metal structure prior to plug and abandonment of a well having a top. finally, the invention relates to a method of permanently closing fluid communication in the downhole closure unit for permanently sealing off a control line prior to plug and abandonment of a well. when using elastomer seals in components downhole, the seals cannot be used for safe plug and abandonment. such elastomer seals are used in a variety of completion components, such as patches, liner hangers and annular barriers, e.g. packers, etc., and over a long period of time such elastomer seals may become leaky. these components are often set in place by expanding a vital metal part, and when expanding such metal parts of the components it is very difficult to pull them out of the well in order to plug and abandon the well in a safe manner. it is an object of the present invention to wholly or partly overcome the above disadvantages and drawbacks of the prior art. more specifically, it is an object to provide an improved sealing unit which can be used in a safe plug and abandonment operation. the above objects, together with numerous other objects, advantages and features, which will become evident from the below description, are accomplished by a solution in accordance with the present invention by a downhole expandable tubular for expansion in a well downhole from a first outer diameter to a second outer diameter to abut against an inner face of a well tubular metal structure or borehole, the downhole expandable tubular having an outer face, a longitudinal extension and a tubular length along the longitudinal extension, comprising: at least one first circumferential edge and at least one second circumferential edge spaced apart in the longitudinal extension and provided on the outer face, forming a circumferential groove, and a sealing unit arranged in the circumferential groove, wherein the sealing unit has a unit length along the longitudinal extension being less than 20% of the tubular length, and the sealing unit comprises a post-transition metal material. also, the unit length along the longitudinal extension may be less than 10% of the tubular length, and preferably less than 5% of the tubular length. furthermore, the post-transition metal material may comprise bismuth or a bismuth alloy. in addition, the sealing unit may comprise more than one element, and at least one of the elements may comprise the post-transition metal material. moreover, the sealing unit may further comprise an annular sealing element and a retaining element, and at least the retaining element may comprise a post-transition metal material such as bismuth or a bismuth alloy. further, the element comprising a post-transition metal material such as bismuth or a bismuth alloy may be one monolithic whole. additionally, the retaining element may have a first end and a second end, and the first end may overlap the second end when seen along the longitudinal extension or along a circumference of the downhole expandable tubular. also, the circumferential groove may be formed between two projections. furthermore, the annular sealing unit may comprise an annular sealing element and a back-up sealing element abutting and supporting the annular sealing element. in addition, the annular sealing unit may further comprise a second back-up sealing element arranged so that the annular sealing element is between the two back-up sealing elements when seen along the axial extension. moreover, the annular sealing unit may also comprise an anchoring element arranged in a second circumferential groove, the anchoring element comprising a first anchoring part at least partly overlapping a second anchoring part in a radial direction perpendicular to the axial extension so that an inner face of the first anchoring part at least partly abuts an outer face of the second anchoring part. further, the retaining element may be a split ring-shaped retaining element having more than one winding so that when the expandable tubular is expanded from the first outer diameter to the second outer diameter, the split ring-shaped retaining element partly unwinds. additionally, the split ring-shaped retaining element may unwind by less than one winding when the expandable tubular is expanded from the first outer diameter to the second outer diameter. also, the split ring-shaped retaining element may have more than one winding in the second outer diameter of the downhole expandable tubular. furthermore, the split ring-shaped retaining element may have a width in the longitudinal extension, the width being substantially the same in the first outer diameter and the second outer diameter of the downhole expandable tubular. in addition, the split ring-shaped retaining element may have a plurality of windings. moreover, the downhole expandable tubular may have a first thickness between the first and second circumferential edges and a second thickness in adjacent areas, the first thickness being smaller than the second thickness. further, the downhole expandable tubular may have a first thickness between the first and second circumferential edges, and the sealing unit may have an extension radial to the longitudinal extension of the downhole expandable tubular being less than twice the first thickness, and preferably equal to or smaller than the first thickness. additionally, the material may expand upon solidification. furthermore, the material may liquify at above 130 degrees centigrade. in addition, the retaining element may be arranged in an abutting manner to the sealing element. moreover, the retaining element and the sealing element may substantially fill a gap created between the first and second circumferential edges. further, the split ring-shaped retaining element may at least partly be made of a spring material. additionally, the split ring-shaped retaining element may be arranged on a first side of the sealing element, and a second split ring-shaped retaining element may be arranged on another side of the sealing element opposite the first side. also, the split ring-shaped retaining element may retain the sealing element in a position along the longitudinal extension of the downhole expandable tubular while expanding the split ring-shaped retaining element and the sealing element. furthermore, the ring-shaped retaining element may be a split ring. in addition, the first and second circumferential edges may be extending in a radial extension in relation to the downhole expandable tubular, said radial extension being perpendicular to the longitudinal extension of the downhole expandable tubular. moreover, the back-up sealing element may be arranged between the split ring-shaped retaining element and the sealing element. further, the split ring-shaped retaining element and the back-up sealing element may be arranged in an abutting manner to the sealing element so that at least one of the split ring-shaped retaining element and the back-up sealing element abuts the sealing element. additionally, the back-up sealing element may be made of polytetrafluoroethylene (ptfe) or polymer. also, the sealing element may be made of elastomer, rubber, polytetrafluoroethylene (ptfe) or another polymer. furthermore, the downhole expandable tubular may be a patch to be expanded within a casing or well tubular metal structure in a well, a liner hanger to be at least partly expanded within a casing or well tubular metal structure in a well, or a casing to be at least partly expanded within another casing. in addition, the invention relates to an annular barrier for expansion in an annulus between a well tubular metal structure and an inner face of a borehole or another well tubular metal structure for providing zone isolation between a first zone and a second zone of the borehole, comprising: a tubular metal part for mounting as part of the well tubular metal structure, a downhole expandable tubular surrounding the tubular metal part and having an outer face facing towards the inner face of the borehole or the well tubular metal structure, each end of the downhole expandable tubular being connected with the tubular metal part, a annular space between the downhole expandable tubular and the tubular metal part, and an expansion opening in the tubular metal part through which fluid may enter into the annular space in order to expand the downhole expandable tubular. moreover, the annular barrier may further comprise the downhole closure unit in the annular space for permanently sealing off a control line controlling a well component of a well tubular metal structure prior to plug and abandonment of a well having a top, comprising: a first element comprising a first opening, a second opening and fluid communication between the first opening and the second opening, the first opening being arranged closer to the top than the second opening, the first opening having a first connection to a first part of a tubular line, and the second opening having a second connection to a second part of the tubular line, wherein the first element has a first state in which the fluid communication is open and a second state in which the fluid communication is closed. by having a downhole closure unit arranged in the expandable space of the annular barrier fluidly connecting the first part and the second part of the tubular line, a very simple way of fluidly disconnecting the tubular line passing therethrough is provided, and the annular barrier can therefore form part of plug and abandonment of the well as no leaks can occur across the annular barrier when the first element has changed from the first state to the second state. further, the invention relates to a downhole system comprising a well tubular metal structure having an inner face, an outer face, a downhole expandable tubular being connected to the inner face, and a downhole closure unit arranged on the outer face for permanently sealing off a control line controlling a well component of the well tubular metal structure prior to plug and abandonment of a well having a top, the downhole expandable tubular comprising: a first element comprising a first opening, a second opening and fluid communication between the first opening and the second opening, the first opening being arranged closer to the top than the second opening, the first opening having a first connection to a first part of a tubular line, and the second opening having a second connection to a second part of the tubular line, wherein the first element has a first state in which the fluid communication is open and a second state in which the fluid communication is closed. additionally, the downhole system may comprise a well tubular metal structure having an inner face, an outer face and an annular barrier. by having a downhole closure unit fluidly connecting the first part and the second part of the tubular line, a very simple way of fluidly disconnecting the tubular line passing therethrough is provided, and the well can therefore easily proceed to the subsequent steps of plug and abandonment of the well as no leaks can occur across the control line when the first element has changed from the first state to the second state. the fluid communication can be closed in a simple manner, and the first part of the tubular line/control line can be pulled out of the well before plugging and abandoning the well by cement. also, in the second state a distance between the first part and the second part of the tubular line may be created. furthermore, the fluid communication may be provided by a through-bore in the first element of the downhole closure unit from the first opening to the second opening. in addition, the tubular line may not penetrate the first element of the downhole closure unit. moreover, the fluid communication may be a fluid channel. further, the first element of the downhole closure unit may be tubeless, meaning that the tubular line does not extend through the first element. additionally, the through-bore may be tubeless, meaning that the tubular line does not extend through the through-bore of the first element. also, the well tubular metal structure may have an axial extension, and the first element may have a length along the axial extension being at least 2 cm. moreover, the well tubular metal structure may have an axial extension, and the first element may have a length along the axial extension being at least 2 cm, and preferably at least 5 cm. further, the length of the first element may be at least 5 metres, preferably at least 10 metres, and more preferably more than 10 metres. additionally, the first element of the downhole closure unit may comprise a post-transition metal. also, the first element of the downhole closure unit may comprise a material expanding upon solidification. furthermore, the first element of the downhole closure unit may comprise a material liquifying at above 130 degrees centigrade. additionally, the first element of the downhole closure unit may comprise a flange at the second opening. also, the first element of the downhole closure unit may comprise a flange at the second opening forming a skirt upon solidification. furthermore, the first element of the downhole closure unit may be made of/comprise a post-transition metal such as bismuth. in addition, the first element of the downhole closure unit may be made of a low-melt-point alloy and/or a eutectic alloy. moreover, the first element of the downhole closure unit may be made of/comprise a low-melt-point alloy such as a bismuth tin (bi/sn) alloy and may be a eutectic alloy. the alloy may be a 58/42 bismuth tin (bi/sn) alloy, which melts/freezes at 138 degrees centigrade. an alloy will be denser than the fluid filling the well, typically water or brine, and will therefore displace the ambient well fluid in the fluid communication, facilitating the creation of a secure and fluid-tight bond and closure of the fluid communication when activated. the relatively high density of the alloy will also result in a flowable or mouldable alloy behaving in a relatively predictable manner. alloys may be selected for high mobility such that the mouldable or flowable alloy may flow into and occupy the through-bore. the solidified alloys may thus be effective in sealing the fluid communication and may also securely engage the cement when cement is arranged around the first element to provide the plug for plug and abandonment. alloys may be selected to be compatible with the other elements of the downhole closure unit and the bore wall material, and to be compatible with the conditions in the bore, e.g. relatively high ambient bore temperatures or the presence of corrosive materials, such as hydrogen sulphide and carbon dioxide, which might degrade or otherwise adversely affect other materials. alternatively, or in addition, the first element may comprise a thermoplastic or some other material or blend of materials. in its hardened state, the material of the first element may comprise an amorphous solid. further, the first element of the downhole closure unit may comprise at least a first material and a second material, the first material being a post-transition metal, such as bismuth or a bismuth alloy, and the second material being a non-post-transition metal having a higher melting point than the first material. additionally, the first element of the downhole closure unit may comprise at least a first material and a second material, the first material comprising a eutectic alloy, such as a bismuth alloy, and the second material being a non-post-transition metal having a higher melting point than the first material. also, the second material may be formed as a mesh near a second element end comprising the second opening. furthermore, the second material may be formed as a mesh in the lower part to form a skirt around which the bismuth solidifies. in addition, the downhole closure unit may further comprise a heating element. moreover, the downhole closure unit may further comprise a power source such as a battery. further, the downhole closure unit may fluidly connect a first part of a tubular line and a second part of the tubular line. additionally, the downhole closure unit may be arranged in the annular space. also, each end of the expandable metal sleeve may be connected to the tubular metal part by means of first and second connection parts. furthermore, the first part of the tubular line may penetrate a first connection part connecting one end of the expandable metal sleeve and the tubular metal part, and/or the second part of the tubular line may penetrate a second connection part connecting one end of the expandable metal sleeve and the tubular metal part. additionally, the downhole closure unit, the first part and the second part of the tubular line may fluidly connect the first zone and the second zone. also, the downhole annular barrier may comprise a valve unit for controlling the flow of fluid from within the tubular metal part into the annular space for expanding the expandable metal sleeve. the valve unit may also comprise a pressure-equalising function in which the annular space is pressure-equalised with the higher of the pressure in the first zone and the second zone. furthermore, the fluid communication in the first element may comprise a fuel part of a thermite material. in addition, the wall of the through-bore may be at least partly made of thermite. moreover, the battery may power an igniter for making a spark to ignite the thermite material for heating the first element. further, the tubular line may comprise a hydraulic fluid or an electric conductor. additionally, the invention also relates to a method of permanently closing fluid communication in the downhole closure unit for permanently sealing off a control line prior to plug and abandonment of a well, comprising: inserting a well tubular metal structure having a completion component and an annular barrier comprising the downhole closure unit and a control line in a tubular line for operating the completion component, heating the first element of the downhole closure unit in the annular space of the annular barrier so that the material of the first element at least partly changes condition to a more liquified or mouldable condition, and expanding the material of the first element during solidification of the material of the first element and thus closing the fluid communication between the first opening and the second opening. also, heating may be performed by activating a heating element in the first element or in a wireline tool arranged in abutment to the first element. furthermore, heating may be performed by pumping an activation fluid down the tubular line. in addition, the activation fluid may be a chemical creating an exothermal process in the first element. moreover, the activation fluid may comprise aluminium metal oxide, e.g. particles of aluminium metal oxide. further, the method may also comprise separating a first part of the well tubular metal structure from a second part of the well tubular metal structure at a position opposite the first element before heating of the first element. additionally, the method may further comprise pulling the first part of the well tubular metal structure out of the well, setting a plug in the second part of the well tubular metal structure and arranging cement on top of the plug and the downhole closure unit. also, after heating the first element the method may further comprise separating the first part of the tubular line from the second part of the tubular line as the first element changes state. furthermore, the separation may be performed by means of a wireline tool having a cutting tool and an anchoring section. in addition, the wireline tool may comprise a stroking tool. moreover, the wireline tool may have a driving unit, such as a self-propelling unit for propelling the wireline tool forward in the well. finally, the method may further comprise pulling the first part of the well tubular metal structure out of the well and inserting a second first part of the well tubular metal structure instead of the pulled first part of the well tubular metal structure. the invention and its many advantages will be described in more detail below with reference to the accompanying schematic drawings, which for the purpose of illustration show some non-limiting embodiments and in which: fig. 1 shows a cross-sectional view of part of a downhole expandable tubular in an unexpanded condition to the left and in an expanded condition to the right, fig. 2a shows a retaining element as a split ring-shaped retaining element in an unexpanded condition, fig. 2b shows the retaining element of fig. 2a in an expanded condition being partly unwound, fig. 2c shows another retaining element in an unexpanded condition, fig. 3 shows a cross-sectional view of a downhole expandable tubular as a straddle being expanded and straddling over a perforated zone, fig. 4 shows a cross-sectional view of a downhole expandable tubular as a liner hanger being expanded in a top part of the liner hanger, fig. 5 shows a cross-sectional view of an annular barrier comprising a downhole expandable tubular as an expandable metal sleeve expanded to seal against an inner face of a borehole, fig. 6 shows a cross-sectional view of another annular barrier comprising a downhole expandable tubular in an unexpanded condition in a borehole, fig. 7 shows a cross-sectional view of yet another annular barrier comprising a downhole expandable tubular in an unexpanded condition in another well tubular metal structure, fig. 8 shows a cross-sectional view of yet another annular barrier having anchoring elements, fig. 9a shows a cross-sectional view of another annular barrier having a downhole closure unit, fig. 9b shows a cross-sectional view of the annular barrier of fig. 9a in which the first element of the downhole closure unit has relocated to close a second part of a tubular line penetrating the annular space of the annular barrier, fig. 10 shows a partly cross-sectional view of a well having a well tubular metal structure and a downhole closure unit connecting a first part of a control line and a second part of a control line, fig. 11 shows a partly cross-sectional view of a well having another downhole closure unit connecting three control lines, fig. 12 shows a partly cross-sectional view of a well having yet another downhole closure unit, and fig. 13 shows a downhole system having several annular barriers. all the figures are highly schematic and not necessarily to scale, and they show only those parts which are necessary in order to elucidate the invention, other parts being omitted or merely suggested. fig. 1 shows a downhole expandable tubular 1 for expansion in a well 2 downhole from a first outer diameter d 1 to a second outer diameter d 2 to abut against an inner face 4 of a well tubular metal structure 3 or borehole 5. the downhole expandable tubular 1 has an outer face 6, a longitudinal extension l and a tubular length l t along the longitudinal extension l. the downhole expandable tubular 1 comprises at least one first circumferential edge 7 and at least one second circumferential edge 8 spaced apart in the longitudinal extension l and provided on the outer face 6, forming a circumferential groove 9. the downhole expandable tubular 1 further comprises a sealing unit 10 arranged in the circumferential groove 9, where the sealing unit 10 has a unit length l u along the longitudinal extension l being less than 20% of the tubular length l t , and the sealing unit 10 comprises a post-transition metal material. as can be seen in figs. 3-9b , the unit length l u along the longitudinal extension l may be less than 10% of the tubular length l t , and preferably less than 5% of the tubular length l t . the post-transition metal material comprises bismuth or a bismuth alloy. the sealing unit 10 comprises more than one element, at least one of the elements comprising the post-transition metal material. the sealing unit 10 comprises several elements in the form of an annular sealing element 11 and a retaining element 12, and at least the retaining element 12 comprises a post-transition metal material such as bismuth or a bismuth alloy. the element comprising a post-transition metal material such as bismuth or a bismuth alloy is one monolithic whole, as shown in figs. 2a and 2b . the material of at least part of the sealing unit 10 expands upon solidification so that the material in a first state is arranged in the circumferential groove 9 and in another condition becomes mouldable or is liquified, moves downwards in the well 2 away from a top 51 and solidifies at a location further down in a second state. in its liquified or mouldable condition, the material decreases in volume as compared to its solid condition and is then able to enter further into cavities and fill out such cavities even more, and upon solidification the material expands, forming a proper seal at the new location. thus, as a result of heating the material first liquifies or becomes mouldable and then flows into and accumulates in cavities 19 between the downhole expandable tubular 1 and the surrounding wall on which the downhole expandable tubular 1 abuts. upon solidification, the material expands and provides an excellent seal. in one embodiment, the material liquifies at above 130 degrees centigrade. the material is made of a low-melt-point alloy such as a bismuth tin (bi/sn) alloy and may be a eutectic alloy. the alloy may be a 58/42 bismuth tin (bi/sn) alloy, which melts/solidifies at 138 degrees centigrade. an alloy will be denser than the fluid filling the well, typically water or brine, and will therefore displace the ambient well fluid in the fluid communication, facilitating the creation of a secure and fluid-tight bond and closure of the fluid communication when activated. the relatively high density of the alloy will also result in a flowable or mouldable alloy behaving in a relatively predictable manner. alloys may be selected for high mobility such that the mouldable or flowable alloy may flow into and occupy the through-bore. the solidified alloys may thus be effective in sealing the fluid communication and may also securely engage the cement when cement is arranged around the first element to provide the plug for plug and abandonment. alloys may be selected to be compatible with the other elements of the downhole closure unit and the bore wall material, and to be compatible with the conditions in the bore, e.g. relatively high ambient bore temperatures or the presence of corrosive materials, such as hydrogen sulphide and carbon dioxide, which might degrade or otherwise adversely affect other materials. alternatively, or in addition, the material may comprise a thermoplastic or some other material or blend of materials. in its hardened state, the material may comprise an amorphous solid. the retaining element has a first end 33 and a second end 34, and the first end 33 overlaps the second end 34 when seen along the longitudinal extension l, as shown in figs. 2a and 2b , or along a circumference of the downhole expandable tubular 1, as shown in fig. 2c . in fig. 2a , the retaining element 12 is a split ring-shaped retaining element 12 having more than one winding, so that when the expandable tubular 1 is expanded from the first outer diameter d 1 to the second outer diameter d 2 , the split ring-shaped retaining element 12 partly unwinds as shown in fig. 2b . the split ring-shaped retaining element 12 unwinds by less than one winding when the expandable tubular 1 is expanded from the first outer diameter d 1 to the second outer diameter d 2 , and the split ring-shaped retaining element 12 is thus able to fully support the sealing element 11 even in its expanded condition. the split ring-shaped retaining element 12 has more than one winding in the second outer diameter d 2 and the expanded condition of the downhole expandable tubular 1. as shown in fig. 1 , the split ring-shaped retaining element 12 has a width w in the longitudinal extension l, the width w being substantially the same in the first outer diameter d 1 and the second outer diameter d 2 of the downhole expandable tubular 1. furthermore, the split ring-shaped retaining element 12 has a plurality of windings 7', 7", 7"', as shown in figs. 2a and 2b . thus, the ring-shaped retaining element 12 is a split ring. in figs. 1 and 4 , the retaining element 12 is arranged in an abutting manner to the sealing element 11 to hold the sealing element 11 in place during the insertion of the downhole expandable tubular 1 and during the expansion of the downhole expandable tubular 1. the retaining element 12 and the sealing element 11 substantially fill a gap created between the first and second circumferential edges 7, 8. the split ring-shaped retaining element 12 retains the sealing element 11 in a position along the longitudinal extension l of the downhole expandable tubular 1 while expanding the split ring-shaped retaining element 12 and the sealing element 11. the first and second circumferential edges 7, 8 are extending in a radial extension in relation to the downhole expandable tubular 1, where the radial extension is perpendicular to the longitudinal extension l of the downhole expandable tubular 1. upon heating, the material of the retaining elements 12 changes state from a first state as shown in figs. 3 , 4 , 5 , 9a to a second state as shown in fig. 9b in which the material fills a cavity 19 for providing an even tighter seal than before heating. the retaining element 12 thus leaves the circumferential groove 9 and moves down to fill and seal the cavity 19 as shown in fig. 9b as indicated by the reference number 12b. the downhole expandable tubular 1 forms part of a straddle as shown in fig. 3 for straddling over perforations 13 and sealing off these perforations 13 when the downhole expandable tubular 1 is expanded so that the sealing units 10 are pressed against the inner face 4 of the well tubular metal structure 3 on either side of the perforated zone having the perforations 13. the annular sealing unit 10 comprises an annular sealing element 11 and a back-up sealing element 24 abutting and supporting the annular sealing element 11 and the retaining element 12. the downhole expandable tubular 1 has several projections 44, and the circumferential groove 9 is formed between two projections 44. a second back-up sealing element 24, 24b is arranged so that the annular sealing element 11 is between the two back-up sealing elements 24 when seen along the axial extension, and the retaining elements 12 press onto the back-up sealing elements 24, which again press on the sealing element 11. the back-up sealing element 24 is arranged between the split ring-shaped retaining element 12 and the sealing element 11. the split ring-shaped retaining element 12 is thus arranged on a first side of the sealing element 11, and a second split ring-shaped retaining element 12 is arranged on another side of the sealing element 11 opposite the first side. as shown in figs. 3 , 4 , 5 , 9a and 9b , an annular cavity 19 is thus formed between two adjacent sealing units 10. during the liquifying of the material of bismuth or bismuth alloy of part of the sealing unit 10, the material enters into the nearest cavity 19 further down the well, and upon solidification the material expands to provide a very efficient seal, e.g. before the well is plugged and abandoned. in fig. 4 , the downhole expandable tubular 1 forms part of a liner hanger expanded within a casing or well tubular metal structure 3 in a well, or a casing to be at least partly expanded within another casing. fig. 5 shows a downhole annular barrier 50 to be expanded in an annulus 103 between a well tubular metal structure 3a and a wall of the borehole 5 or another well tubular metal structure 3 (as shown in fig. 7 ) in a well in order to provide zone isolation between a first zone 101 and a second zone 102 of the borehole 5. the annular barrier 50 comprises a tubular metal part 20 mounted as part of the well tubular metal structure 3a, the tubular metal part 20 having an outer face 64 and an inside 25. the downhole annular barrier 50 further comprises the downhole expandable tubular 1 surrounding the tubular metal part 20 and having an inner sleeve face 27 facing the tubular metal part 20 and an outer sleeve face 28 facing the wall of the borehole 5. each end 31, 32 of the downhole expandable tubular 1 is connected with the tubular metal part 20, defining an annular space 21 between the inner sleeve face 27 of the downhole expandable tubular 1 and the tubular metal part 20. in order to expand the downhole annular barrier 50, fluid is let into an opening 23 from within the well tubular metal structure 3a. as shown in fig. 5 , each end 31, 32 of the downhole expandable tubular 1 is connected to the tubular metal part 20 by means of first and second connection parts 41, 42. in fig. 6 , each end 31, 32 of the downhole expandable tubular 1 is connected directly to the tubular metal part 20, e.g. by means of welding, and a combination of one end 31 connected to the tubular metal part 20 by a connection part 41 and the other end 32 directly connected to the tubular metal part is shown in fig. 7 . the sealing units 10 are arranged in grooves of the downhole expandable tubular 1, and the retaining elements 12 are at least partly made of a post-transition metal material such as bismuth or a bismuth alloy. in fig. 5 , the downhole expandable tubular 1 has a first thickness t 1 between the first and second circumferential edges 7, 8 and a second thickness t 2 in adjacent areas, the first thickness t 1 being smaller than the second thickness t 2 . the sealing unit 10 has an extension radial to the longitudinal extension l of the downhole expandable tubular 1 being less than twice the size of the first thickness t 1 , and preferably equal to or smaller than the first thickness t 1 . fig. 6 shows another annular barrier 50 in cross-section along the axial extension, where the annular sealing element 11 has a first width w1, a second width w2 and a third width w3, the second width w2 being larger than the first width w1 and the third width w3 and being arranged between the first width w1 and the third width w3. the back-up sealing element 24 has a first contact area a1, and the annular sealing element 11 has a second contact area a2, where the first contact area a1 has a shape that mates with the second contact area a2, as shown in fig. 6 . by having the back-up sealing element 24 with a mating shape as that of the annular sealing element 11 having the second width w2 that is larger than the first width w1 and the third width w3, the back-up sealing element 24 is able to restrict the annular sealing element 11 from opening a potential crack therein. in fig. 8 , the sealing element 11 has another cross-section with a groove facing towards the well tubular metal structure 3. the sealing units 10 are arranged in the circumferential grooves 9, and between these grooves 9 are second circumferential grooves 9b, in each of which a circumferential groove 9b and an anchoring element 14 are arranged. the anchoring element 14 comprises a first anchoring part 15, 15b at least partly overlapping a second anchoring part 16, 16b in a radial direction perpendicular to the axial extension so that an inner face 17, 17b of the first anchoring part 15, 15b at least partly abuts an outer face 18, 18b of the second anchoring part 16, 16b. in order to provide increased anchoring during axial loading of the annular barrier 50, the inner face 17 of the first anchoring part 15 and the outer face 18 of the second anchoring part 16 are inclined in relation to the axial and longitudinal extension. thus, when the temperature changes, and at least part of an expandable metal sleeve 26/the downhole expandable tubular 1 moves in one direction along the axial direction, the first anchoring part 15 moves in an opposite direction along the inclined outer face 18 of the second anchoring part 16, and the first anchoring part 15 is then forced radially outwards, anchoring the expandable metal sleeve 26 even further to the other well tubular metal structure 3 or the wall of the borehole 5. the split ring-shaped retaining element 12 is at least partly made of bismuth or a bismuth alloy and a spring material. the back-up sealing element 24 is preferably made of polytetrafluoroethylene (ptfe) or polymer. the sealing element 11 is preferably made of elastomer, rubber, polytetrafluoroethylene (ptfe) or another polymer. fig. 13 shows a downhole system 100 comprising the well tubular metal structure 3 having the inner face 4, the outer face 64, two downhole annular barriers 50, each having the downhole expandable tubular 1, and a downhole closure unit 61 as shown in figs. 10-12 arranged on the outer face 64 for permanently sealing off a control line 104 controlling a well component of the well tubular metal structure 3 prior to plug and abandonment of the well 2 having the top 51, the downhole closure unit 61 having a first state in which fluid communication 108 is open to operate a completion component 52 and a second state in which the fluid communication 108 is closed (not shown). the downhole system 100 further comprises a screen 60 for letting production fluid into the well tubular metal structure 3. figs. 9a and 9b show a downhole annular barrier 50 to be expanded in the annulus 103 between the well tubular metal structure 3 and the wall of the borehole 5 or another well tubular metal structure (not shown) in a well in order to provide zone isolation between the first zone 101 and the second zone 102 of the borehole 5. the downhole annular barrier 50 comprises a tubular metal part 20 mounted as part of the well tubular metal structure 3, the tubular metal part 20 having the outer face 64 and the inside 25. the downhole annular barrier 50 further comprises the expandable metal sleeve 26 in the form of the downhole expandable tubular 1 surrounding the tubular metal part 20 and having the inner sleeve face 27 facing the tubular metal part 20 and the outer sleeve face 28 facing the wall of the borehole 5. each end 31, 32 of the expandable metal sleeve 26 is connected with the tubular metal part 20, defining the annular space 21 between the inner sleeve face 27 of the expandable metal sleeve 26 and the tubular metal part 20. the downhole annular barrier 50 further comprises the downhole closure unit 61 arranged on the outer face 24 in the annular space 21. the downhole closure unit 61 fluidly connects a first part of a tubular/control line 104 and the second part of the tubular line 104. the first part of the tubular line 104 penetrates the first connection part 41 connecting one end of the expandable metal sleeve 26 and the tubular metal part 20, and the second part of the tubular line 104 penetrates the second connection part 42 connecting one end of the expandable metal sleeve 26 and the tubular metal part 20. the downhole closure unit 61, the first part and the second part of the tubular line 104 fluidly connect the first zone 101 and the second zone 102. the downhole closure unit 61 is shown in more detail in figs. 10-12 . the downhole closure unit 61 is used for permanently sealing off the control line 104 controlling a well component (not shown) of the well tubular metal structure 3 prior to plug and abandonment of the well 2 having the top 51. the downhole closure unit 61 comprises a first element 105 comprising a first opening 106, a second opening 107 and fluid communication 108 between the first opening 106 and the second opening 107. the first opening 106 is arranged closer to the top 51 than the second opening 107 and at a distance from the second opening 107. the first opening 106 has a first connection 109 and is connected to a first part 110 of the tubular line 104, and the second opening 107 has a second connection 111 and is connected to a second part 112 of the tubular line 104. the first element 105 has a first state in which the fluid communication 108 is open and a second state in which the fluid communication 108 is closed. the first element 105 is shown in its first state where the first part 110 of the tubular line 104 is fluidly connected with the second part 112 of the tubular line 104 through a fluid channel 114 in the first element 105 of the downhole closure unit 61. the first part of the control line 104 is thus not directly connected to the second part 112 of the tubular line 104, but connected via the tubular line 104 so that the tubular line 104 does not penetrate the first element 105. the control line 104 is thus formed by the first part 110 of the tubular line 104, the fluid channel 114 in the first element 105 and the second part 112 of the tubular line 104. the fluid communication 108 is provided by a through-bore 114 forming the fluid channel 114 in the first element 105 from the first opening 106 to the second opening 107. thus, the first element 105 is tubeless, meaning that the tubular line 104 does not extend through the first element 105, nor through the through-bore 114 of the first element 105. by having a downhole closure unit 61 fluidly connecting the first part 110 of the tubular line 104 with the second part 112 of the tubular line 104, the fluid communication 108 can be closed in a simple manner, and the first part 110 of the tubular line 104 can be pulled out of the well 2 before plugging and abandoning of the well by cement. the downhole closure unit 61 thus provides a very safe way of abandoning a well having a control line for controlling a downhole component. the fluid communication 108 can be closed in two ways: either by closing the fluid channel 114 providing the fluid communication 108 in the first element 105 of the downhole closure unit 61, or by separating the first part 110 of the tubular line 104 from the second part 112 of the tubular line 104 and sealing off the end of the second part 112 of the tubular line 104. when the fluid channel 114 is closed, the cement surrounds, abuts and seals against the first element 105, and when separation is provided cement surrounds, abuts and seals an outer face 64 of the well tubular metal structure 3 directly as the first element 105 has been displaced downwards, creating access to the outer face 64 of the well tubular metal structure 3 all around the circumference of the well tubular metal structure 3. in either way, the cement does not surround the tubular line/control line 104, and the risk of the well leaking along the tubular line/control line 104 is not present. the first element 105 changes state when the first element 105 is heated above a pre-set temperature at which the first element 105 becomes mouldable or is liquified so that the first element 105 disconnects from the first part 110 of the tubular line 104 and accumulates around and above the second part 112 of the tubular line 104 so as to seal off the second part 112 of the tubular line 104 from the first part 110 of the tubular line 104. as can be seen in fig. 10 , the well tubular metal structure 3 has an axial extension, and the first element 105 has a length l e along the axial extension being at least 2 cm, and preferably at least 5 cm. the first element 105 comprises a post-transition metal material, such as bismuth, so that the first element 105 comprises a material expanding upon solidification. the first element 105 may be made of a low-melt-point alloy, such as a material liquifying at above 130 degrees centigrade, and/or a eutectic alloy. the first element 105 may comprise a low-melt-point alloy such as a bismuth tin (bi/sn) alloy and may be a eutectic alloy. the alloy may be a 58/42 bismuth tin (bi/sn) alloy, which melts/freezes at 138 degrees centigrade. in fig. 9a , the material of the first element 105 is in its first state, providing fluid communication 108 between the first part 110 and the second part 112 of the tubular line 104. in fig. 9b , the first element 105 has liquified and subsequently solidified around the second part 112 of the tubular line 104, thereby sealing off an opening 39 in an upper end 40 of the second part 112 of the tubular line 104. thus, the first element 105 deforms in the lower part of the annular space 21, sealing off the second part 112 of the tubular line 104 in the annular space 21. thus, by having the downhole closure unit 61 arranged in the annular space 21 of the annular barrier 50 a very simple way of fluidly disconnecting the tubular line 104 passing therethrough is provided, and the annular barrier 50 can therefore form part of plug and abandonment of the well as no leaks can occur across the annular barrier 50 when the first element 105 has changed from the first state to the second state. the downhole annular barrier 50 further comprises a valve unit 43 for controlling the flow of fluid from within the tubular metal part 20 into the annular space 21 for expanding the expandable metal sleeve 26, as shown in figs. 9a and 9b . the valve unit 43 further comprises a pressure-equalising function in which the annular space 21 is pressure-equalised with the higher of the pressure in the first zone 101 and the second zone 102. in order to mould or liquify at least part of the first element 105, the fluid communication 108 in the first element 105 may comprise at least a fuel part of a thermite material. the wall of the through-bore 114 creating the fluid communication 108 between the first part 110 and the second part 112 of the tubular line 104 is at least partly made of thermite or covered by thermite, being a pyrotechnic composition of metal powder and metal oxide. instead of a heating element 116, the heating may be performed by pumping an activation fluid down the tubular line 104. the activation fluid is a chemical creating an exothermal process in the first element 105, or the activation fluid comprises aluminium metal oxide, e.g. particles of aluminium metal oxide. oxidizers may include bismuth(iii) oxide, boron(iii) oxide, silicon(iv) oxide, chromium(iii) oxide, manganese(iv) oxide, iron(iii) oxide, iron(ii,iii) oxide, copper(ii) oxide or lead(ii,iv) oxide. the fuel part in the first element 105 may include aluminium, magnesium, titanium, zinc, silicon or boron. the downhole closure unit 61 may also comprise a battery powering an igniter for making a spark to ignite the thermite material for heating the first element 105. by having a downhole closure unit 61 fluidly connecting the first part 110 and the second part 112 of the tubular line 104, a very simple way of fluidly disconnecting the tubular line 104 passing therethrough is provided, and the well can therefore easily proceed to the subsequent steps of plug and abandonment of the well as no leaks can occur along the control line 104 when the first element 105 has changed from the first state to the second state. the fluid communication 108 can be closed in a simple manner, and the first part 110 of the tubular line/control line 104 can be pulled out of the well before plugging and abandoning of the well by cement. as shown in fig. 9b , a distance 47 is created between the first part 110 and the second part 112 of the tubular line 104 in the second state. in fig. 11 , the downhole closure unit 61 comprises a flange 115 at the second opening 107. when the first element 105 is heated and thus enters into a mouldable or liquified condition, the flange 115 forms a skirt upon solidification so that the first element 105 solidifies around the flange 115 and thus above the second part 112 of the tubular line 104. by having the flange 115, the solidification is controlled to occur at the position around the flange 115 and the second part 112 of the tubular line 104 to seal off the end of the second part 112 closest to the first part 110. the first part 110 of the tubular line 104 remains open after the first element 105 has changed from the first state to the second state in which the fluid communication 108 is closed. as shown in fig. 12 , the downhole closure unit 61 comprises a mesh 119 in the lower part of the first element 105 to form a skirt around which the material of the first element 105, such as bismuth or a low-melt-point alloy, solidifies. the downhole closure unit 61 may comprise one fluid communication 108 as shown in fig. 10 for providing one fluid communication 108 of the control line 104. in fig. 11 , the downhole closure unit 61 comprises three fluid communications 108 in the form of three fluid channels 114, and thus fluid is connecting the first part 110 and the second part 112 of three tubular lines 104, 104a, 104b, 104c. the tubular lines 104, 104a, 104b, 104c may be used for hydraulic communication or electric communication and thus carry hydraulic fluid or an electric conductor/line. accordingly, the downhole closure unit 61 may comprise a plurality of fluid communications 108 fluidly connecting the first and second parts 110, 112 of a plurality of the tubular lines 104, 104a, 104b, 104c. in order to heat the first element 105, the downhole closure unit 61 may comprise the heating element 116 and a power source 117, such as a battery, as shown in fig. 12 . the heating element 116 is arranged in two through-bores 114 in the first element 105 on either side of the fluid channel 114 connecting the first part 110 and the second part 112 of the tubular line 104. by heating locally, the material of the first element 105 first becomes mouldable or liquified and then expands during solidification, closing the fluid communication 108 between the first part 110 and the second part 112 of the tubular line 104. thus, the first element 105 merely changes form locally to fill the fluid channel 114 and thus close the fluid communication 108. the remaining part of the first element 105 remains unchanged even though the first element 105 changes state from the first state to the second state. the mouldable or liquified part of the material of the first element 105 solidifies around the mesh 119 and fills up at least the lower part of the fluid channel 114 nearest the second part 112 of the tubular line 104. the heating element 116 may thus be arranged in the upper part of the downhole closure unit 61 nearest the first part 110 of the tubular line 104, and the mouldable or liquified part of the first element 105 solidifies when flowing down into the lower part of the fluid channel 114. the downhole closure unit 61 may be heated from within the well tubular metal structure 3 by a wireline tool having the heating element 116. the downhole closure unit 61 completely surrounds the well tubular metal structure 3 in fig. 11 and only partly surrounds it in fig. 10 . the downhole closure unit 61 may be clamped onto the well tubular metal structure 3 or welded thereto. the downhole closure unit 61 may also only be fastened to the first part 110 and the second part 112 of the tubular line 104, and thus not to the well tubular metal structure 3. the fluid communication 108 in the downhole closure unit 61 is permanently closed for permanently sealing off the control line 104 prior to plug and abandonment of the well, comprising inserting the well tubular metal structure 3 having a completion component and the annular barrier comprising the downhole closure unit 61 and the control line 104 in the tubular line 104 for operating the completion component, heating the first element 105 of the downhole closure unit 61 in the annular space 21 of the annular barrier 50 so that the material of the first element 105 at least partly changes condition to a more liquified or mouldable condition, and then expanding the material of the first element 105 during solidification of the material of the first element 105 and thus closing the fluid communication 108 between the first opening 106 and the second opening 107. the heating may be performed by activating the heating element 116 in the first element 105 or in the wireline tool arranged in abutment to the first element 105, or by pumping an activation fluid down the tubular line 104. the activation fluid is a chemical creating an exothermal process in the first element 105 and may comprise aluminium metal oxide, e.g. particles of aluminium metal oxide. after heating the first element 105, the method may further comprise separating the first part 110 of the tubular line 104 from the second part 112 of the tubular line 104 as the first element 105 changes condition. the separation of the first part of the well tubular metal structure 3 from the second part of the well tubular metal structure 3 occurs at a position opposite the first element 105 before heating of the first element 105. the method further comprises pulling the first part of the well tubular metal structure 3 out of the well, setting a plug in the second part of the well tubular metal structure 3 and arranging cement on top of the plug and the downhole closure unit 61. the separation is performed by means of the wireline tool having a cutting tool and an anchoring section. the wireline tool may comprise a stroking tool and/or a driving unit, such as a self-propelling unit for propelling the wireline tool forward in the well. instead of plugging and abandoning the well, the first part of the well tubular metal structure 3 may be pulled out of the well, and a second first part of the well tubular metal structure 3 may be inserted instead of the pulled first part of the well tubular metal structure 3. a stroking tool is a tool providing an axial force. the stroking tool comprises an electric motor for driving a pump. the pump pumps fluid into a piston housing to move a piston acting therein. the piston is arranged on the stroker shaft. the pump may pump fluid out of the piston housing on one side and simultaneously suck fluid in on the other side of the piston. by "fluid" or "well fluid" is meant any kind of fluid that may be present in oil or gas wells downhole, such as natural gas, oil, oil mud, crude oil, water, etc. by "gas" is meant any kind of gas composition present in a well, completion or open hole, and by "oil" is meant any kind of oil composition, such as crude oil, an oil-containing fluid, etc. gas, oil and water fluids may thus all comprise other elements or substances than gas, oil and/or water, respectively. by "annular barrier" is meant an annular barrier comprising a tubular metal part mounted as part of the well tubular metal structure and an expandable metal sleeve surrounding and connected to the tubular metal part defining an annular barrier space. by "casing" or "well tubular metal structure" is meant any kind of pipe, tubing, tubular, liner, string, etc., used downhole in relation to oil or natural gas production. in the event that the tool is not submergible all the way into the casing, a driving unit, such as a self-propelling unit or a downhole tractor can be used to push the tool all the way into position in the well. the downhole tractor may have projectable arms having wheels, wherein the wheels contact the inner surface of the casing for propelling the tractor and the tool forward in the casing. a downhole tractor is any kind of driving tool capable of pushing or pulling tools in a well downhole, such as a well tractor ® . although the invention has been described above in connection with preferred embodiments of the invention, it will be evident to a person skilled in the art that several modifications are conceivable without departing from the invention as defined by the following claims.
|
105-417-712-926-348
|
FR
|
[
"FR",
"CN",
"EP",
"JP",
"WO",
"KR",
"US"
] |
A61K8/91,A61K8/85,A61K8/92,A61Q1/04,A61Q5/00,A61Q1/00,A61K8/31,A61Q19/00,C08G63/06,C08G63/91
| 2020-06-24T00:00:00 |
2020
|
[
"A61",
"C08"
] |
cosmetic composition comprising grafted polyhydroxyalkanoate copolymer in fat medium
|
the present invention relates to a cosmetic composition comprising: a) one or more polyhydroxyalkanoate (pha) copolymers containing and preferably consisting of at least two different repeating polymer units selected from the group consisting of the following units (a) and (b), and also their optical or geometric isomers, their organic or inorganic acid or alkali salts, and their solvates such as hydrates:-[-o-ch (r1)-ch2-c (o)-]-unit (a)-[-o-ch (r2)-ch2-c (o)-]-unit (b), in these polymer units (a) and (b):-r1 represents a hydrocarbyl chain selected from i) a linear or branched (c5-c28) alkyl group, ii) a linear or branched (c6-c28) alkenyl group, iii) a linear or branched (c6-c28) alkynyl group; preferably, the hydrocarbyl group is linear; the hydrocarbyl chain is optionally substituted and/or intercalated by an atom or group, as described in the specification; -r2 represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbyl group comprising from 3 to 30 carbon atoms; b) a fatty medium comprising one or more fatty substances, the fatty substances preferably being a liquid at 25 deg c and atmospheric pressure; it is understood that (a) is different from (b).
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claims [claim 1] composition, notably a cosmetic composition, comprising: a) one or more polyhydroxyalkanoate (pha) copolymers which contain, and preferably consist of, at least two different repeating polymer units chosen from the units (a) and (b) below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch 2 -c(o)-]- unit (a) -[-o-ch(r 2 )-ch 2 -c(o)-]- unit (b) in which polymer units (a) and (b): - r1 represents a hydrocarbon-based chain chosen from i) linear or branched (c 5 - c28)alkyl, ii) linear or branched (c6-c28)alkenyl, iii) linear or branched (c6-c28)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being: ^ ^ substituted with one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(c1-c4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide –c(o)-n(ra)2 or c(s)-n(ra)2, f) cyano, g) iso(thio)cyanate, h) (hetero)aryl such as phenyl, naphtyl or furyl, and i) (hetero)cycloalkyl such as anhydride, or epoxide, j) cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from uva and/or uvb screening agents, anti-ageing active agents and fragranceses; k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) cosmetic active agent as defined previously and x representing a’) o, s, n(r a ) or si(r b )(r c ), b’) s(o) r , or (thio)carbonyl, c’) or combinations of a’) with b’) such as (thio)ester, (thio)amide, (thio)urea; r being equal to 1 or 2, r a representing a hydrogen atom, or a (c 1 - c4)alkyl group or an aryl(c1-c4)alkyl group such as benzyl, preferably ra represents a hydrogen atom; r b and r c , which may be identical or different, represent a (c 1 -c 4 )alkyl or (c 1 -c 4 )alkoxy group, particularly only one substituent ; preferably chosen from b) halogen, and j) such as epoxide; and/or ^ ^ interrupted with one or more heteroatoms a’) such as o, s, n(r a ) and si(r b )(r c ), b’) s(o) r or (thio)carbonyl, c’) or combinations of a’) with b’) such as (thio)ester, (thio)amide, (thio)urea, with r and ra being as defined previously, preferably ra represents a hydrogen atom, rb and rc being as defined previously; - r2 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 3 to 30 carbon atoms; in particular chosen from linear or branched (c 1 -c 28 )alkyl and linear or branched (c 2 -c 28 )alkenyl, in particular a linear hydrocarbon-based group, more particularly (c 3 -c 20 )alkyl or (c 3 - c 20 )alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical r 1 from which two carbon atoms are subtracted; and b) a fatty medium comprising one or more fatty substances; which are preferably liquid at 25°c and at atmospheric pressure; it being understood that (a) is different from (b). [claim 2] composition according to claim 1, in which the pha copolymer(s) a) contain the repeating unit of formula (i), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: in which formula (i): ^ ^ r1 and r2 are as defined in claim 1; ^ ^ m and n are integers greater than or equal to 1; preferably, the sum n + m is inclusively between 450 and 1400; preferably m < n. [claim 3] composition according to claim 1, in which the pha copolymer(s) a) contain three different repeating polymer units (a), (b) and (c), and preferably consist of three different polymer units (a), (b) and (c), below, and also the optical or geometrical isomers thereof and the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch 2 -c(o)-]- unit (a) -[-o-ch(r 2 )-ch2-c(o)-]- unit (b) -[-o-ch(r 3 )-ch2-c(o)-]- unit (c) in which polymer units (a), (b) and (c): - r1 and r2 are as defined in claim 1; - r3 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 1 to 30 carbon atoms; - optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 in claim 1; in particular represents a hydrocarbon-based group chosen from linear or branched, substituted and/or interrupted (c 1 -c 28 )alkyl and linear or branched (c 2 - c 28 )alkenyl, in particular a linear hydrocarbon-based group, more particularly (c 4 - c 20 )alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 1 , or else corresponding to the number of carbon atoms of the radical r 1 from which at least three carbon atoms are subtracted, preferably corresponding to the number of carbon atoms of the radical r 1 from which four carbon atoms are subtracted; and it being understood that: - (a) is different from (b) and (c), (b) is different from (a) and (c), and (c) is different from (a) and (b); and preferably, the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c) notably if r 2 represents an alkyl group and/or r 3 represents an alkyl group; preferably r 3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted; preferably, the pha copolymer(s) a) contain the repeating unit of formula (ii), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: in which formula (ii): ^ ^ r1, r2 and r3 are as defined previously; ^ ^ m, n and p are integers greater than or equal to 1; preferably, the sum n + m + p is inclusively between 450 and 1400 ^ ^ preferably, m < n + p, preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r2 from which two carbon atoms are subtracted. [claim 4] composition according to any one of the preceding claims, in which the pha copolymer(s) a) contain four different repeating polymer units (a), (b), (c) and (d), and preferably consist of four different polymer units (a), (b), (c) and (d), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch2-c(o)-]- unit (a) -[-o-ch(r 2 )-ch2-c(o)-]- unit (b) -[-o-ch(r 3 )-ch2-c(o)-]- unit (c) -[-o-ch(r 4 )-ch2-c(o)-]- unit (d) in which polymer units (a), (b), (c) and (d): - r1, r2 and r3 are as defined in claims 1 to 3; - r4 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon- based group comprising from 3 to 30 carbon atoms, optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (c 4 -c 28 )alkyl substituted with one or more atoms or groups a) to l) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; and it being understood that: - (a) is different from (b), (c) and (d), (b) is different from (a), (c) and (d), (c) is different from (a), (b) and (d), and (d) is different from (a), (b) and (c); - preferably the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c), notably if r2 represents an alkyl group and/or r3 represents an alkyl group; and r4 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group; preferably r 3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted, and r4 represents an optionally substituted and/or interrupted alkyl, optionally substituted and/or interrupted alkenyl or optionally substituted and/or interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon attoms are subtracted; preferably, the pha copolymer(s) comprise the repeating unit of formula (iii), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: in which formula (iii): ^ ^ r1, r2, r3 and r4 are as defined previously; ^ ^ m, n, p and v are integers greater than or equal to 1; preferably, the sum n + m + p + v is inclusively between 450 and 1400; ^ ^ preferably, n > m + v; more preferentially n + p > m + v – preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted, and r4 represents an optionally substituted and/or optionally interrupted alkyl, optionally substituted and/or optionally interrupted alkeny or substituted and/or optionally interrupted alkynyl group, with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted. [claim 5] composition according to any one of the preceding claims, in which the pha copolymer(s) a) contain five different repeating polymer units (a), (b), (c), (d) and (e), and preferably consist of five different polymer units (a), (b), (c), (d) and (e), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch2-c(o)-]- unit (a) -[-o-ch(r 2 )-ch2-c(o)-]- unit (b) -[-o-ch(r 3 )-ch2-c(o)-]- unit (c) -[-o-ch(r 4 )-ch2-c(o)-]- unit (d) -[-o-ch(r 5 )-ch2-c(o)-]- unit (e) in which polymer units (a), (b), (c), (d) and (e): - r1, r2, r3 and r4 are as defined in claims 1 to 4; - r5 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon- based group comprising from 3 to 30 carbon atoms, optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (c 4 -c 28 )alkyl substituted with one or more atoms or groups a) to l) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 4 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical r 4 from which at least two carbon atoms are subtracted, preferably from which two carbon atoms are subtracted; it being understood that: - (a) is different from (b), (c), (d) and (e); (b) is different from (a), (c), (d) and (e); (c) is different from (a), (b), (d) and (e); (d) is different from (a), (b), (c) and (e); and (e) is different from (a), (b), (c) and (d); and - preferably, the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c), notably if r2 represents an alkyl group and/or r3 represents an alkyl group; and r4 and r5 represent an optionally substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group; preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r2 from which two carbon atoms are subtracted and r4 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r1 from which two carbon atoms are subtracted, and r5 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which four carbon atoms are subtracted. preferably, the pha copolymer(s) comprise the repeating unit of formula (iv), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: in which formula (iv): ^ ^ r1, r2, r3, r4 and r5 are as defined previously; ^ ^ m, n, p, v and z are integers greater than or equal to 1; preferably, the sum n + m + p + v + z is inclusively between 450 and 1400; and ^ ^ preferably, when r1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, r2 and r3 represent an alkyl group, and the groups r4 and r5 represent an optionally substituted and/or optionally interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, then n > m + v + z; more preferentially n + p > m + v + z; preferably r 3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted and r4 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted, and r5 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which four carbon atoms are subtracted. [claim 6] composition according to any one of the preceding claims, in which r1 represents a linear or branched, preferably linear, (c 5 -c 28 )alkyl hydrocarbon-based chain; more particularly, r1 is an alkyl group substituted with one or more atoms or groups a) to k), said alkyl group comprising from 5 to 12, preferably between 6 and 10 carbon atoms, more preferentially between 7 and 9 carbon atoms such as n-octyl; preferably, r1 represents a hydrocarbon-based chain, substituted with one or more (preferably one) groups chosen from b) hydroxyl, c) thiol, d) (di)(c 1 - c 4 )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as anhydride, or epoxide, j) a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as optical brighteners, uv-screening agents, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) a cosmetic active agent as defined previously and x representing a’) o, s, n(r a ), b’) carbonyl, c’) or combinations thereof of a’) with b’) such as ester, amide or urea; ra represents a hydrogen atom or a (c1-c4)alkyl or aryl(c 1 -c 4 )alkyl group such as benzyl, preferably r a represents a hydrogen atom; even more preferentially, the pha copolymer(s) are such that r1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is substituted with one or more (preferably one) groups chosen from b) hydroxyl, d) (di)(c 1 -c 4 )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, and x representing a’) o, s or n(ra), preferably s; ra representing a hydrogen atom or a (c 1 -c 4 )alkyl group, preferably r a represents a hydrogen atom; better still, said hydrocarbon-based chain r 1 is substituted at the end of the chain on the opposite side from the carbon atom which bears said radical r 1 . [claim 7] composition according to any one of the preceding claims, in which r 1 represents a hydrocarbon-based chain, notably alkyl, in particular c 7 -c 20 , more particularly c 8 -c 18 and even more particularly c 9 -c 16 alkyl, which is interrupted with one or more (preferably one) atoms or groups chosen from o, s, n(r a ), carbonyl, or combinations thereof such as ester, amide or urea, with r a being as defined in the preceding claims; preferably, r a represents a hydrogen atom; preferably an alkyl group which is interrupted with one or more atoms chosen from o and s, more preferentially with an o or s, notably s, atom; preferably, said interrupted hydrocarbon-based chain, notably alkyl, is linear. [claim 8] composition according to any one of the preceding claims, in which r 1 has the following formula –(ch 2 ) r -x-(alk) u -g with x being as defined previously in any one of claims 1 or 6, in particular representing o, s or n(r a ), preferably s, alk represents a linear or branched, preferably linear, (c 1 -c 10 )alkylene and more particularly (c 1 -c 8 )alkylene chain, r represents an integer inclusively between 6 and 11, preferably between 7 and 10 such as 8; u is equal to 0 or 1; and g represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(c 1 -c 4 )(alkyl)amino, (hetero)aryl in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or a sugar, in particular a monosaccharide optionally protected with one or more groups such as acyl, preferably sug represents with r e representing a group r f -c(o)-, with r f representing a (c 1 -c 4 )alkyl group such as methyl; preferably, when u is equal to 0, g represents a cycloalkyl group such as cyclohexyl, or a sugar as defined previously; according to another advantageous variant, when u is equal to 1, g represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(c 1 -c 4 )(alkyl)amino or (hetero)aryl, in particular aryl such as phenyl. [claim 9] composition according to any one of the preceding claims, in which the pha copolymer(s) a) are such that r2 is chosen from linear or branched (c1-c28)alkyl, and linear or branched (c 2 -c 28 )alkenyl, in particular a linear hydrocarbon-based group, particularly (c 3 -c 20 )alkyl or (c 3 -c 20 )alkenyl. [claim 10] composition according to any one of the preceding claims, in which the pha copolymer(s) a) are such that the radical r2 is a linear or branched, preferably linear, (c 1 -c 8 )alkyl, particularly (c 2 -c 6 )alkyl, preferably (c 4 -c 6 )alkyl group such as n-pentyl or n-hexyl. [claim 11] composition according to any one of the preceding claims, in which the pha copolymer(s) a) are such that: - the unit (a) is present in a molar percentage ranging from 0.1% to 99%, preferably a molar percentage ranging from 0.5% to 50%, more preferentially a molar percentage ranging from 1% to 40%, even more preferentially a molar percentage ranging from 2% to 30%, better still a molar percentage ranging from 5% to 20%, even better still a molar percentage ranging from 10% to 30% of units (a); and - the unit (b) is present in a molar percentage ranging from 1% to 40%, preferentially a molar percentage from 2% to 10%, more preferentially a molar percentage from 5% to 35% of units (b); and/or - the unit (c) is present in a molar percentage ranging from 0.5% to 20%, preferentially a molar percentage from 1% to 7%, more preferentially from 0.5% to 7% of units (c). [claim 12] composition according to any one of the preceding claims, in which the pha copolymer(s) a) are such that they comprise the following repeating units, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: m and n are as defined previously, hal represents a halogen atom such as bromine and t represents an integer between 1 and 10, preferably between 3 and 8 such as 6. ar: represents a (hetero)aryl group such as phenyl; ar’: represents a (c1-c4)alkyl(hetero)aryl group such as t-butylphenyl, preferably 4-t- butylphenyl; cycl: represents a cyclohexyl group; fur: represents a furyl group, preferably 2-furyl; sug: represents a sugar group, in particular a monosaccharide optionally protected with one or more groups such as acyl; preferably, sug represents: preferentially, the pha copolymer(s) have the following formula, and also the optical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: m, n, hal, t, ar, ar’, cycl, fur and sug are as defined previously for compounds (1) to (14). m, n, hal, t, ar, ar’, cycl, fur and sug are as defined previously for compounds (1) to (14). [claim 13] composition according to any one of the preceding claims, in which the fatty medium comprises one or more substances chosen from: ■ branched c 8 -c 16 alkanes such as c 8 -c 16 isoalkanes of petroleum origin (also known as isoparaffins) such as isododecane, isodecane or isohexadecane, ■ linear c 8 -c 16 alkanes, such as n-dodecane (c 12 ) and n-tetradecane (c 14 ), and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (c11) and n-tridecane (c13), and mixtures thereof; ■ ester oils particularly chosen from oils of plant origin, such as triglycerides consisting of fatty acid esters of glycerol in which the fatty acids may have varied chain lengths from c 4 to c 24 , these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides. the oils of plant origin may be chosen from wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, groundnut oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, coconut oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil and argan oil; shea butter; or alternatively caprylic/capric acid triglycerides; ■ monoester oils of formula r 9 -c(o)-or 10 in which r 9 represents a linear or branched hydrocarbon-based chain including from 5 to 19 carbon atoms and r 10 represents a linear or branched, notably branched, hydrocarbon-based chain containing from 4 to 20 carbon atoms, on condition that r 9 + r 10 ^ 9 carbon atoms and preferably less than 29 carbon atoms, for instance palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; cetearyl octanoate (purcellin oil), isopropyl myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate or octyl octanoate; ■ esters of lactic acid and of c10-c20 alcohol, such as isostearyl lactate, 2-octyldodecyl lactate, myristyl lactate, c 12 -c 13 alkyl lactate, cetyl lactate or lauryl lactate; ■ diesters of malic acid and of c10-c20 alcohol, such as diisostearyl malate, di(c12- c 13 )alkyl malate, dibutyloctyl malate, diethylhexyl malate or dioctyldodecyl malate; ■ esters of pentaerythritol and of c8-c22 carboxylic acid (in particular tetraesters or diesters), such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate, pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate/tetracaprate, pentaerythrityl tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tetraisostearate, pentaerythrityl tetralaurate, pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or pentaerythrityl distearate; ■ diesters of formula r 11 -o-c(=o)-r 12 -c(=o)-o-r 13 , with r 11 and r 13 , which may be identical or different, representing a linear or branched, saturated or unsaturated (preferably saturated) c 4 to c 12 and preferentially c 5 to c 10 alkyl chain, optionally containing at least one saturated or unsaturated, preferably saturated, ring, and r 12 representing a saturated or unsaturated c 1 to c 4 , preferably c 2 to c 4 , alkylene chain, for instance an alkylene chain derived from succinate (in this case r 12 is a saturated c 2 alkylene chain), maleate (in this case r 12 is an unsaturated c 2 alkylene chain), glutarate (in this case r 12 is a saturated c 3 alkylene chain) or adipate (in this case r 12 is a saturated c 4 alkylene chain); in particular, r 11 and r 13 are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl and isononyl; mention may be made preferentially of dicaprylyl maleate or bis(2- ethylhexyl) succinate; ■ diesters of formula r 14 -c(=o)-o-r 15 -o-c(=o)-r 16 , with r 14 and r 16 , which may be identical or different, representing a linear or branched, saturated or unsaturated (preferably saturated) c 4 to c 12 and preferentially c 5 to c 10 alkyl chain and r 15 representing a saturated or unsaturated c 1 to c 4 and preferably c 2 to c 4 alkylene chain, notably 1,3-propanediol dicaprylate (r 14 as c 7 and r 16 as c 3 ), or dipropylene glycol dicaprylate; ■ the carbonate oils may be chosen from the carbonates of the following formula r 17 -o-c(o)-o-r 18 , with r 17 and r 18 , which may be identical or different, representing a linear or branched c 4 to c 12 and preferentially c 6 to c 10 alkyl chain; the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), bis(2- ethylhexyl) carbonate, dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate; ■ and mixtures thereof. [claim 14] composition according to any one of the preceding claims, in which the fatty medium comprises one or more fatty substances in a content ranging from 2% to 99.9% by weight, relative to the total weight of the composition, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight, preferably ranging from 20% to 80% by weight relative to the total weight of the composition. [claim 15] composition according to any one of the preceding claims, in which the fatty medium comprises one or more solvents, preferably polar and/or protic solvents, other than water, more preferentially c 2 -c 6 alkanols, such as those chosen from ethanol, propanol, butanol, pentanol and hexanol, preferably ethanol; more particularly, the solvent(s) are present in the composition in a weight percentage of between 0 and 10% relative to the total weight of the solvent mixture, preferentially between 0.5% and 8%, more particularly between 1% and 5%, such as 2% by weight relative to the total weight of the composition. [claim 16] composition according to any one of the preceding claims, which also comprises one or more colouring agents chosen from pigments, direct dyes and mixtures thereof, preferably pigments; more preferentially, the pigment(s) of the invention are chosen from carbon black, iron oxides, notably black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as blue 1 lake, azo pigments, notably red azo pigments, such as d&c red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red b, even more preferentially red iron oxides. [claim 17] process for treating keratin materials, preferably α) keratin fibres, notably human keratin fibres such as the hair, or β) human skin, in particular the lips, by applying the composition as defined in any one of the preceding claims. [claim 18] copolymer pha as defined in any one of the preceding claims 8 to 12, preferably copolymer pha in which r 1 has the following formula –(ch 2 ) r -x-(alk) u - g with alk representing a linear or branched, preferably linear, (c 1 -c 8 )alkylene and preferably copolymer pha is different from compounds (7) and/or (7’), prefereably different from compounds (7). [claim 19] process for preparing copolymer pha as defined in the preceeding claim, starting from pha copolymer selected from a) to g) : a) a pha copolymer bearing an unsaturated hydrocarbon-based chain, according to scheme 1 below: in which scheme 1: - r2, m and n are as defined 1 à 5, 9, 10 et 12 ; - y represents a group chosen from hal (halide) such as chlorine or bromine, hydroxyl, thiol, (di)(c1-c4)(alkyl)amino, r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl; δ) a cosmetic active agent as defined previously; ε) (c1-c20)alkyl, (c2-c20)alkenyl, (c2- c 20 )alkynyl; and x representing a’) o, s, n(r a ) or si(r b )(r c ) or e) linear or branched (c 1 -c 20 )alkyl, with r a , r b and r c as defined previously; - q’ represents an integer inclusively between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8 such as 6, better still between 3 and 8, preferably between 4 and 6, such as 5; a) copolymer pha with unsaturations may also be chemically modified : via addition reactions, such as radical additions, michael additions, electrophilic additions, diels-alder, halogenation, hydration or hydrogenation reaction, and preferably hydrothiolation reaction with particles, chemical compounds or polymers. in particular, the hydrothiolation reactions may be performed in the presence of a thermal initiator, a redox initiator or a photochemical initiator and of an organic compound bearing a sulfhydryl group, notably chosen from: - linear, branched, cyclic or aromatic alkanethiols including 1 to 14 carbon atoms; - organosiloxane bearing a thiol function; - thiol-based silicone oils ; - thiol-based oligomers or polymers bearing a reactive function, such as an amine, an alcohol, an acid, a halogen, a thiol, an epoxide, a nitrile, an isocyanate, a heteroatom ; and - thiols which may be obtained from disulfide reduction, such as phenyl disulfide or furfuryl disulphide; b) copolymer pha with unsaturations may also be chemically modified via oxidation reactions, which may or may not be controlled, for example with the permanganates of a concentrated or dilute alkaline agent, or ozonolysis, oxidation in the presence of a reducing agent, making it possible to obtain novel materials bearing hydroxyl, epoxide or carboxyl groups in the terminal position of the side chains; b) a pha copolymers bearing a hydrocarbon-based chain containing an epoxide group, according to scheme 2 below: in which scheme 2, y, m, n, q’ and r 2 are as defined in scheme 1; c) a pha copolymer bearing a hydrocarbon-based chain containing a nucleofugal group, according to scheme 3 below: in which scheme 3 y, m, n, q’ and r 2 are as defined in scheme 1; m corresponds to an organic or inorganic nucleofugal group, which may be substituted with a nucleophilic group; preferably, said nucleophile is a heteroatom which is electron-donating via the +i and/or +m effect such as o, s or n; preferably, the nucleofugal group m is chosen from halogen atoms such as br, and mesylate, tosylate or triflate groups; d) a pha copolymer bearing a hydrocarbon-based chain containing a cyano group, according to scheme 4 below: in which scheme 4 y, m, n, q’ and r2 are as defined in scheme 1; in a first step i), the pha copolymer bearing a side chain containing a cyano or nitrile group reacts with an organo-alkali metal or organomagnesium compound y-mghal, y-li or y-na, followed by hydrolysis to give the pha copolymer bearing a side chain containing a group y grafted with a ketone function; the ketone function may be converted into a thio ketone by thionation, for example with s8 in the presence of amine, or with lawesson’s reagent; said thio ketone, after total reduction ii) (for example by clemmensen reduction) leads to the pha copolymer bearing a side chain containing a group y grafted with an alkylene group; alternatively, said thio ketone may undergo a controlled reduction iii) with a conventional reducing agent to give the pha copolymer bearing a side chain containing a group y grafted with a hydroxyalkylene group; the cyano group of the starting pha copolymer can react with water after hydration v) to give the amide derivative, or after hydrolysis iv) to the carboxyl derivative; the cyano group of the starting pha copolymer may also, after reduction vi), give the amine derivative or the ketone derivative; e) a pha copolymer bearing a hydrocarbon-based chain at the chain end, according to scheme 5 below: in which scheme 5 r 1 , r 2 , m, n and y are as defined previously, and r’1 represents a hydrocarbon-based chain chosen from i) linear or branched (c1-c20)alkyl, ii) linear or branched (c2-c20)alkenyl, iii) linear or branched (c2-c20)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being substituted with one or more atoms or groups chosen from: a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(c1-c4)(alkyl)amino, e) (thio)carboxyl, f) (thio)carboxamide – c(o)-n(ra)2 or –c(s)-n(ra)2, f) cyano, g) iso(thio)cyanate, h) (hetero)aryl such as phenyl or furyl, and i) (hetero)cycloalkyl such as anhydride, or epoxide, j) a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from uva and/or uvb screening agents, and anti-ageing active agents; or f) a pha copolymers with reactive atom otr group according to scheme 6: in which scheme 6 r’ 1 , r 2 , m, n and y are as defined previously, and x’ represents a reactive atom or group that is capable of reacting with an electrophilic e or nucleophilic nu atom or group to create a σ covalent bond; if x’ is an electrophilic or nucleofugal group, then it can react with a reagent r’ 1 - nu; if x’ is a nucleophilic group nu, then it can react with r’ 1 - e to create a σ covalent bond; the σ covalent bonds or bonding group that may be generated are listed in the table below, from condensation of electrophiles with nucleophiles: *the activated esters of general formula -co-lg, with lg representing a leaving group such as oxysuccinimidyl, oxybenzotiiazolyl oraryloxy, optionally substituted; **the acyl azides can rearrange to give isocyanate. g) a pha functionalized on a side chain, to perform chain-end grafting in a second stage as described in scheme 7; the reciprocal is also true, in which the chain-end grafting may be performed in a first stage, followed by performing functionalization of a functionalizable side chain in a second stage. in which scheme 7 r’ 1 , r 2 , m, n and y are as defined previously. [claim 20] cosmetic use of the copolymer pha as defined in any one of the preceding claims 8 to 12, preferably a cosmetic use of the copolymer pha in which r 1 has the following formula -(ch2) r -x-(alk) u -g with alk representing a linear or branched, preferably linear, (ci-cs)alkylene and preferably copolymer pha is different from compounds (7) and/or (7’), prefereably different from compounds (7).
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de title: cosmetic composition comprising a grafted polyhydroxyalkanoate copolymer in a fatty medium [0001] the present invention relates to a cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing grafted or functionalized hydrocarbon-based groups in a fatty medium, and also to a process for treating keratin materials using such a composition. [0002] it is known practice to use, in cosmetics, film-forming polymers which can be conveyed in organic media, such as hydrocarbon-based oils. polymers are notably used as film-forming agents in makeup products such as mascaras, eyeliners, eyeshadows or lipsticks. [0003] fr-a-2964663 describes a cosmetic composition comprising pigments coated with a c 3 -c 21 polyhydroxyalkanoate, such as poly(hydroxybutyrate-co-hydroxyvalerate). [0004] wo 2011/154508 describes a cosmetic composition comprising a 4-carboxy-2- pyrrolidinone ester derivative and a film-forming polymer which may be a polyhydroxyalkanoate, such as polyhydroxybutyrate, polyhydroxyvalerate and polyhydroxybutyrate-co-polyhydroxyvalerate. [0005] us-a-2015/274972 describes a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in aqueous dispersion and a silicone elastomer. on the other hand, wo 2018/178899 describes a cosmetic composition comprising at least one polyhydroxyalkanoate (pha) in the form of particles with an average diameter (d50) from 0.1 ^m to 100 ^m, in an amount of from 0.1 % by weight to 30 % by weight, with respect to the total weight of the composition.in order to absorb oily substances, such as sebum. however most phas are not solubilized satisfactorily in fatty substances such as volatile oil as isododecane. [0006] the majority of the polyhydroxyalkanoates are polymers derived from the polycondensation of polymeric repeating units that are for the most part identical and derived from the same carbon source or substrate. these documents do not describe the use of copolymers derived from polycondensation using an aliphatic substrate or first carbon source, and at least one second substrate different from the first, comprising one or more reactive functions, the chemical nature of which is different from that of the first carbon source. [0007] there is thus a need for a composition comprising phas with varied functionalization or which are functionalizable with lipophilic or non-lipophilic active agents, which can make them active and soluble in a fatty phase. this makes it possible to obtain a film on keratin materials which has good cosmetic properties, notably good resistance to oils and to sebum, and also to be able to modify the gloss or the mattness. [0008] the applicant has discovered that polyhydroxyalkanoate copolymers bearing particular grafted or functionalized hydrocarbon-based groups, as defined below, may be readily used in fatty media, thus making it possible to obtain homogeneous compositions. moreover, the pha according to the invention are film forming polymers. the composition shows good stability, notably after storage for one month at room temperature (25°c). the composition, notably after its application to keratin materials, makes it possible to obtain a film having good cosmetic properties, in particular good resistance to oils and to sebum, and also a matt or glossy appearance. furthermore, by grafting, it is possible to introduce into the polymer active agents, notably organic active agents, such as uv-screening agents, fluorescent or non-fluorescent chromophores, anti-ageing active agents, said active agents then being able to become more resistant once they have been grafted, notably resistant to oils, water and sebum. [0009] thus, the main subject of the present invention is a composition comprising: a) one or more polyhydroxyalkanoate (pha) copolymers which contain, and preferably consist of, at least two different repeating polymer units chosen from the units (a) and (b) below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch2-c(o)-]- unit (a) -[-o-ch(r 2 )-ch2-c(o)-]- unit (b) in which polymer units (a) and (b): - r1 represents a hydrocarbon-based chain chosen from i) linear or branched (c5- c 28 )alkyl, ii) linear or branched (c 6 -c 28 )alkenyl, iii) linear or branched (c 6 -c 28 )alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being: ^ ^ substituted with one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(c 1 -c 4 )(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide –c(o)-n(r a ) 2 or c(s)-n(r a ) 2 , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl, naphtyl or furyl, and j) (hetero)cycloalkyl such as anhydride, or epoxide, k) cosmetic active agent; l) r- x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) cosmetic active agent as defined previously and x representing a’) o, s, n(r a ) or si(r b )(r c ), b’) s(o) r , or (thio)carbonyl, c’) or combinations of a’) with b’) such as (thio)ester, (thio)amide, (thio)urea or sulfonamide; ra representing a hydrogen atom, or a (c1-c4)alkyl group or an aryl(c 1 -c 4 )alkyl group such as benzyl, preferably r a represents a hydrogen atom; rb and rc, which may be identical or different, represent a (c1-c4)alkyl or (c1- c 4 )alkoxy group, particularly only one substituent ; preferably chosen from b) halogen, and j) such as epoxide; and/or ^ ^ interrupted with one or more heteroatoms a’) such as o, s, n(r a ) and si(r b )(r c ), b’) s(o) r , (thio)carbonyl, c’) or combinations of a’) with b’) such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being equal to 1 or 2, ra being as defined previously, preferably ra represents a hydrogen atom, rb and rc being as defined previously; - r2 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 3 to 30 carbon atoms; in particular chosen from linear or branched (c 3 -c 28 )alkyl and linear or branched (c 3 -c 28 )alkenyl, in particular a linear hydrocarbon-based group, more particularly (c 4 -c 20 )alkyl or (c 4 - c 20 )alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical r 1 from which two carbon atoms are subtracted; and b) a fatty medium comprising one or more fatty substances; which are preferably liquid at 25°c and at atmospheric pressure; it being understood that (a) is different from (b). [0010] another subject of the invention is the use in cosmetics of a) one or more pha copolymers as defined previously and b) one or more fatty substances as defined previously in cosmetics. [0011] another subject of the invention is a process for treating keratin materials, preferably α) keratin fibres, notably human keratin fibres such as the hair, or β) human skin, in particular the lips, using a) one or more pha copolymers as defined previously and b) one or more fatty substances as defined previously. [0012] another subject of the invention is novel grafted pha copolymers. [0013] more particularly, a subject of the invention is a non-therapeutic cosmetic process for treating keratin materials, comprising the application to the keratin materials of a composition as defined previously. the treatment process is in particular a process for caring for or making up keratin materials. [0014] for the purposes of the present invention and unless otherwise indicated: - the term “cosmetic active agent” means the radical of an organic or organosilicon compound which can be integrated into a cosmetic composition to give an effect on keratin materials, whether this effect is immediate or provided by repeated applications. as examples of cosmetic active agents, mention may be made of coloured or uncoloured, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from uva and/or uvb screening agents, anti-ageing active agents or active agents intended for providing a benefit to the skin such as active agents having action on the barrier function, deodorant active agents other than mineral particles, antiperspirant active agents other than mineral particles, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active agents, active agents intended for limiting the sheen of the skin, active agents intended for combating the effects of pollution, antimicrobial or bactericidal active agents, antidandruff active agents, and fragrances. - the term “(hetero)aryl” means aryl or heteroaryl groups; - the term “(hetero)cycloalkyl” means cycloalkyl or heterocycloalkyl groups; - the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from: ● a c 1 -c 6 and preferably c 1 -c 4 alkyl radical; ● a halogen atom such as chlorine, fluorine or bromine; ● a hydroxyl group; ● a c 1 -c 2 alkoxy radical; a c 2 -c 4 (poly)hydroxyalkoxy radical; ● an amino radical; ● an amino radical substituted with one or two identical or different c 1 -c 6 , and preferably c 1 -c 4 alkyl radicals; ● an acylamino radical (-nr-cor’) in which the radical r is a hydrogen atom; ● a c 1 -c 4 alkyl radical and the radical r’ is a c 1 -c 4 alkyl radical; a carbamoyl radical ((r) 2 n-co-) in which the radicals r, which may be identical or different, represent a hydrogen atom or a c 1 -c 4 alkyl radical; ● an alkylsulfonylamino radical (r’so 2 -nr-) in which the radical r represents a hydrogen atom or a c 1 -c 4 alkyl radical and the radical r’ represents a c 1 -c 4 alkyl radical, or a phenyl radical; ● an aminosulfonyl radical ((r) 2 n-s(o) 2 -) in which the radicals r, which may be identical or different, represent a hydrogen atom or a c 1 -c 4 alkyl radical; ● a carboxyl radical in the acid or salified form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium); ● a cyano group (cn); ● a polyhalo(c 1 -c 4 )alkyl group, preferentially trifluoromethyl (cf 3 ); - the cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups: ● hydroxyl, ● c 1 -c 4 alkoxy, c 2 -c 4 (poly)hydroxyalkoxy, ● alkylcarbonylamino (rco-nr’-), in which the radical r’ is a hydrogen atom or a c 1 - c 4 alkyl radical and the radical r is a c 1 -c 2 alkyl radical or an amino radical substituted with one or two identical or different c 1 -c 4 alkyl groups; ● alkylcarbonyloxy (rco-o-), in which the radical r is a c 1 -c 4 alkyl radical or an amino radical substituted with one or two identical or different c 1 -c 4 alkyl groups; ● alkoxycarbonyl ((ro-co-) in which the radical r is a c 1 -c 4 alkyl radical or an amino radical substituted with one or two identical or different c 1 -c 4 alkyl groups; - a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups; - a hydrocarbon-based chain is unsaturated when it includes one or more double bonds and/or one or more triple bonds; - an “aryl” radical represents a monocyclic or fused or non-fused polycyclic hydrocarbon- based group comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferably phenyl; - a “heteroaryl” radical represents a monocyclic or fused or non-fused polycyclic, 5- to 22-membered group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthylyl; - a “cyclic” or “cycloalkyl” radical is a monocyclic or fused or non-fused polycyclic, non- aromatic cyclic hydrocarbon-based radical containing from 5 to 22 carbon atoms, which may include one or more unsaturations; the cycloalkyl is preferably a cyclohexyl group; - a “heterocyclic” or “heterocycloalkyl” radical is a monocyclic or fused or non-fused polycyclic 3- to 9-membered non-aromatic cyclic radical, including from 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms; preferably, the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidyl and morpholinyl; - an “alkyl” radical is a linear or branched, in particular c1-c6 and preferably c1-c4 saturated hydrocarbon-based radical; - an “alkenyl” radical is a linear or branched unsaturated hydrocarbon-based radical comprising one or more conjugated or non-conjugated double bonds; - an “alkynyl” radical is a linear or branched unsaturated hydrocarbon-based radical comprising one or more conjugated or non-conjugated triple bonds; - an “alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a linear or branched c 1 -c 6 and preferentially c 1 -c 4 hydrocarbon-based radical; - a “sugar” radical is a monosaccharide or polysaccharide radical, and the o-protected sugar derivatives thereof such as sugar esters of (c 1 -c 6 )alkylcarboxylic acids such as sugar esters of acetic acid, sugars containing amine group(s) and (c 1 -c 4 )alkyl derivatives, such as methyl derivatives, for instance methylglucose. sugar radicals that may be mentioned include: sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose. - the term “monosaccharides” refers to a monosaccharide sugar comprising at least 5 carbon atoms of formula c x (h 2 o) x with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is between 5 and 7 inclusive, preferably x = 6, they may be of d or l configuration, and of alpha or beta anomer, and also the salts thereof and the solvates thereof such as hydrates; - the term “polysaccharides” refers to a polysaccharide sugar which is a polymer constituted of several saccharides bonded together via o-oside bonds, said polymers being constituted of monosaccharide units as defined previously, said monosaccharide units comprising at least 5 carbon atoms, preferably 6; in particular, the monosaccharide units are linked together via a 1,4 or 1,6 bond as α (alpha) or β ^ (beta) anomer, it being possible for each oside unit to be of l or d configuration, and also the salts thereof and the solvates thereof such as the hydrates of said monosaccharides; more particularly, they are polymers formed from a certain number of saccharides (or monosaccharides) having the general formula: -[c x (h 2 o) y )] w - where x is an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is between 5 and 7 inclusive and preferably x = 6, and y is an integer which represents x - 1, and w is an integer greater than or equal to 2, particularly of between 3 and 3000 inclusive, more particularly between 5 and 2500 and preferentially between 10 and 2300; - the term “sugar bearing amine group(s)” means that the sugar radical is substituted with one or more amino groups nr 1 r 2 i.e. at least one of the hydroxyl groups of at least one saccharide unit of the sugar radical is replaced with a group nr 1 r 2 with r 1 and r 2 , which may be identical or different, representing i) a hydrogen atom, ii) a (c 1 -c 6 )alkyl group, iii) an aryl group such as phenyl, iv) an aryl(c 1 -c 4 )alkyl group such as benzyl, vii) –c(y)-(y’) f -r’ 1 with y and y’, which may be identical or different, representing an oxygen atom, a sulfur atom or n(r’ 2 ), preferably oxygen, f = 0 or 1, preferably 0; and r’ 1 and r’ 2 representing i) to vi) of r 1 and r 2 defined previously, and in particular r’ 1 denoting a (c 1 -c 6 )alkyl group such as methyl. preferably, r 1 and r 2 represent a hydrogen atom or a (c 1 -c 4 )alkylcarbonyl group such as acetyl; - the term “organic or mineral acid salt” more particularly means organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid hcl, ii) hydrobromic acid hbr, iii) sulfuric acid h 2 so 4 , iv) alkylsulfonic acids: alk-s(o) 2 oh such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: ar-s(o) 2 oh such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: alk-o-s(o)oh such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid h 3 po 4 ; ix) triflic acid cf 3 so 3 h and x) tetrafluoroboric acid hbf 4 ; xi) organic carboxylic acids r°-c(o)- oh (i’), in which formula (i’) r° represents a (hetero)aryl group such as phenyl, (hetero)aryl(c 1 -c 4 )alkyl group such as benzyl, or (c 1 -c 10 )alkyl, said alkyl group being optionally substituted preferably with one or more hydroxyl groups or amino or carboxyl radicals, r° preferably denoting a (c 1 -c 6 )alkyl group optionally substituted with 1, 2 or 3 hydroxyl or carboxyl groups; more preferentially, the monocarboxylic acids of formula (i’) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid; and the polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof; and xii) amino acids including more carboxylic acid radicals than amino groups, such as γ-carboxyglutamic acid, aspartic acid or glutamic acid, in particular γ-carboxyglutamic acid; - an “anionic counterion” is an anion or an anionic group associated with the cationic charge; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including c 1 -c 6 alkylsulfonates: alk- s(o) 2 o- such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: ar-s(o) 2 o- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: alk-o-s(o)o- such as methyl sulfate and ethyl sulfate; x) aryl sulfates: ar-o-s(o)o- such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: alk-o-s(o) 2 o- such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: ar-o-s(o) 2 o-; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate. - the “solvates” represent hydrates and also the combination with linear or branched c 1 -c 4 alcohols such as ethanol, isopropanol or n-propanol. the term “chromophore” means a radical derived from a colourless or coloured compound that is capable of absorbing in the uv and/or visible radiation range at a wavelength λabs of between 250 and 800 nm. preferably, the chromophore is coloured, i.e. it absorbs wavelengths in the visible range, i.e. preferably between 400 and 800 nm. preferably, the chromophores appear coloured to the eye, particularly between 400 and 700 nm (ullmann’s encyclopedia, 2005, wiley-vch, verlag “dyes, general survey”, § 2.1 basic principle of color); - the term “fluorescent chromophore” means a chromophore which is also capable of re- emitting in the visible range at an emission wavelength λem of between 400 and 800 nm, and higher than the absorption wavelength, preferably with a stoke’s shift, i.e. the difference between the maximum absorption wavelength and the emission wavelength is at least 10 nm. preferably, fluorescent chromophores are derived from fluorescent dyes that are capable of absorbing in the visible range λabs, i.e. at a wavelength of between 400 and 800 nm, and of re-emitting in the visible range λem between 400 and 800 nm. more preferentially, fluorescent chromophores are capable of absorbing at a λabs of between 420 and 550 nm and of re-emitting in the visible range λem between 470 and 600 nm; - the term “optical brightening chromophore” means a chromophore derived from an optical brightening compound or “optical brighteners, optical brightening agents (obas)” or “fluorescent brightening agents (fbas)” or “fluorescent whitening agents (fwas)”, i.e. agents which absorb uv radiation, i.e. at a wavelength λabs of between 250 and 350 nm, and of subsequently re-emitting this energy by fluorescence in the visible range at an emission wavelength λem of between 400 and 600 nm, i.e. wavelengths between blue-violet and blue-green with a maximum in the blue range. optical brightening chromophores are thus colourless to the eye; - the term “uv-a screening agent” means a chromophore derived from a compound which screens out (or absorbs) uv-a ultraviolet rays at a wavelength of between 320 and 400 nm. a distinction may be made between short uv-a screening agents (which absorb rays at a wavelength of between 320 and 340 nm) and long uv-a screening agents (which absorb rays at a wavelength of between 340 and 400 nm); - the term “uv-b screening agent” means a chromophore derived from a compound which screens out (or absorbs) uv-b ultraviolet rays at a wavelength of between 280 and 320 nm. furthermore, unless otherwise indicated, the limits delimiting the extent of a range of values are included in that range of values. a) the pha copolymer(s) [0015] the composition of the invention comprises as first ingredient a) one or more pha copolymers which contain, or preferably consist of, at least two different repeating polymer units chosen from the units (a) and (b) as defined previously. [0016] the term “copolymer” means that said polymer is derived from the polycondensation of repeating polymer units that are different from each other, i.e. said polymer is derived from the polycondensation of repeating polymer units (a) with (b), it being understood that the polymer units (a) are different from the polymer units (b). [0017] according to a particular embodiment of the invention, the pha copolymer(s) consist of two different repeating polymer units chosen from the units (a) and (b) as defined previously. [0018] more particularly, the pha copolymer(s) according to the invention comprise the repeating unit of formula (i), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0019] [chem.1] : in which formula (i): 1 2 ● r and r are as defined previously, ● m and n are integers greater than or equal to 1, preferably the sum n + m is inclusively between 450 and 1400, preferably m < n. [0020] according to a particular embodiment, the pha copolymer(s) of composition a) contain three different repeating polymer units (a), (b) and (c), and preferably consist of three different polymer units (a), (b) and (c) below, and also the optical or geometrical isomers thereof and the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch 2 -c(o)-]- unit (a) -[-o-ch(r 2 )-ch 2 -c(o)-]- unit (b) -[-o-ch(r 3 )-ch2-c(o)-]- unit (c) in which polymer units (a), (b) and (c): - r1 and r2 are as defined previously; - r3 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 1 to 30 carbon atoms; - optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; in particular represents a hydrocarbon-based group chosen from substituted and/or interrupted, linear or branched (c 1 -c 28 )alkyl and linear or branched (c 2 -c 28 )alkenyl, in particular a linear hydrocarbon-based group, more particularly (c 4 -c 20 )alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 1 , or else corresponding to the number of carbon atoms of the radical r 1 from which at least three carbon atoms are subtracted, preferably corresponding to the number of carbon atoms of the radical r 1 from which four carbon atoms are subtracted; and it being understood that: - (a) is different from (b) and (c), (b) is different from (a) and (c), and (c) is different from (a) and (b); and - preferably, the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c) notably if r 2 represents an alkyl group and/or r 3 represents an alkyl group; preferably, r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted. [0021] according to a particular embodiment of the invention, the pha copolymer(s) comprise the repeating unit of formula (ii), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0022] [chem.2] : in which formula (ii): ^ ^ r1, r2 and r3 are as defined previously; ^ ^ m, n and p are integers greater than or equal to 1; preferably, the sum n + m + p is inclusively between 450 and 1400; and - preferably, m < n + p, preferably r 3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted. [0023] according to a particular embodiment, the pha copolymer(s) of composition a) contain four different repeating polymer units (a), (b), (c) and (d), and preferably consist of four different polymer units (a), (b), (c) and (d), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch2-c(o)-]- unit (a) -[-o-ch(r 2 )-ch2-c(o)-]- unit (b) -[-o-ch(r 3 )-ch2-c(o)-]- unit (c) -[-o-ch(r 4 )-ch2-c(o)-]- unit (d) in which polymer units (a), (b), (c) and (d): - r1, r2 and r3 are as defined previously; - r4 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon- based group comprising from 3 to 30 carbon atoms optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (c 4 -c 28 )alkyl optionally substituted with one or more atoms or groups a) to l) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; and it being understood that: - (a) is different from (b), (c) and (d), (b) is different from (a), (c) and (d), (c) is different from (a), (b) and (d), and (d) is different from (a), (b) and (c); and - preferably the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c), notably if r2 represents an alkyl group and/or r3 represents an alkyl group; and r4 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group; preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted and r4 represents an optionally substituted and/or interrupted alkyl, optionally substituted and/or interrupted alkenyl or optionally substituted and/or interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted . [0024] according to a particular embodiment of the invention, the pha copolymer(s) comprise the repeating unit of formula (iii), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0025] [chem.3] : in which formula (iii): ^ ^ r1, r2, r3 and r4 are as defined previously; ^ ^ m, n, p and v are integers greater than or equal to 1; preferably, the sum n + m + p + v is inclusively between 450 and 1400; and - preferably, n > m + v; more preferentially n + p > m + v – preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted and r4 represents an optionally substituted and/or optionally interrupted alkenyl or substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted. [0026] according to a more particular embodiment, the pha copolymer(s) of composition a) contain five different repeating polymer units (a), (b), (c), (d) and (e), and preferably consist of five different polymer units (a), (b), (c), (d) and (e), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates: -[-o-ch(r 1 )-ch 2 -c(o)-]- unit (a) -[-o-ch(r 2 )-ch 2 -c(o)-]- unit (b) -[-o-ch(r 3 )-ch 2 -c(o)-]- unit (c) -[-o-ch(r 4 )-ch 2 -c(o)-]- unit (d) -[-o-ch(r 5 )-ch2-c(o)-]- unit (e) in which polymer units (a), (b), (c), (d) and (e): - r1, r2, r3 and r4 are as defined previously; - and - r5 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon- based group comprising from 3 to 30 carbon atoms optionally substituted with one or more atoms or groups a) to l) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (c 4 -c 28 )alkyl, optionally substituted with one or more atoms or groups a) to l) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for r 1 ; preferably, the hydrocarbon- based group has a carbon number corresponding to the number of carbon atoms of the radical r 4 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical r 4 from which at least two carbon atoms are subtracted, preferably from which two carbon atoms are subtracted; it being understood that: - (a) is different from (b), (c), (d) and (e); (b) is different from (a), (c), (d) and (e); (c) is different from (a), (b), (d) and (e); (d) is different from (a), (b), (c) and (e); and (e) is different from (a), (b), (c) and (d); and - preferably, the molar percentage of units (a) is less than the molar percentage of units (b) and less than the molar percentage of units (c), notably if r2 represents an alkyl group and/or r3 represents an alkyl group, and r4 and r5 represent an optionally substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group; preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted, and r4 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted, and r5 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which four carbon atoms are subtracted. [0027] according to a particular embodiment of the invention, the pha copolymer(s) comprise the repeating unit of formula (iv), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0028] [chem.4] : in which formula (iv): ^ ^ r1, r2, r3, r4 and r5 are as defined previously; ^ ^ m, n, p, v and z are integers greater than or equal to 1; preferably, the sum n + m + p + v + z is inclusively between 450 and 1400; and - preferably, when r1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, r2 and r3 represent an alkyl group, and the groups r4 and r5 represent an optionally substituted and/or optionally interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, then n > m + v + z; more preferentially n + p > m + v + z; preferably r3 represents an alkyl group with a carbon number corresponding to the carbon number of r 2 from which two carbon atoms are subtracted, and r4 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which two carbon atoms are subtracted, and r5 represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group with a carbon number corresponding to the carbon number of r 1 from which four carbon atoms are subtracted.. [0029] preferably, r1 represents a linear or branched, preferably linear, (c 5 -c 28 )alkyl hydrocarbon-based chain. according to one embodiment of the composition according to the invention, the pha copolymer(s) are such that the radical r1 is a substituted alkyl group comprising 5 to 14 and preferably between 6 and 12 carbon atoms, more preferentially between 7 and 10 carbon atoms such as n-pentyl, n-hexyl, n-octyl or n-nonyl. [0030] according to another embodiment, the hydrocarbon-based chain of the radical r1 of the invention is 1) either substituted, 2) or interrupted, 3) or substituted and interrupted. [0031] according to a particular embodiment of the invention, the pha copolymer(s) are such that r1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is interrupted with one or more (preferably one) atoms or groups chosen from o, s, n(ra) and carbonyl, or combinations thereof such as ester, amide or urea, with ra being as defined previously, preferably ra represents a hydrogen atom; preferably, r1 represents an alkyl group which is interrupted with one or more atoms chosen from o and s, more preferentially with an o or s, notably s, atom. in particular, when it represents an interrupted hydrocarbon-based chain, notably alkyl, r1 is c7-c20, more particularly c 8 -c 18 and even more particularly c 9 -c 16 . preferably, said interrupted hydrocarbon-based chain, notably alkyl, is linear. [0032] according to another embodiment of the invention, the pha copolymer(s) are such that r1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, substituted with one or more (preferably one) atoms or groups chosen from: a) to k) as defined previously. preferably, said hydrocarbon-based chain is substituted with only one atom or group chosen from: a) to k) as defined previously. [0033] according to a particular embodiment of the invention, the pha copolymer(s) are such that r1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is substituted with one or more (preferably one) groups chosen from b) hydroxyl, c) thiol, d) (di)(c 1 -c 4 )(alkyl)amino and preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as anhydride, or epoxide, j) a cosmetic active agent such as coloured or uncoloured, fluorescent or non-fluorescent chromophores such as optical brighteners, uv-screening agents, anti-ageing active agents, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar radical, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) an organic active agent as defined previously and x representing a’) o, s, n(r a ), b’) carbonyl, c’) or combinations thereof of a’) with b’) such as ester, amide or urea; ra represents a hydrogen atom or a (c1- c 4 )alkyl or aryl(c 1 -c 4 )alkyl group such as benzyl, preferably r a represents a hydrogen atom. [0034] even more preferentially, the pha copolymer(s) are such that r1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is substituted with one or more (preferably one) groups chosen from b) hydroxyl, d) (di)(c 1 - c 4 )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, and x representing a’) o, s or n(ra), preferably s; ra representing a hydrogen atom or a (c1-c4)alkyl group, preferably r a represents a hydrogen atom. [0035] preferably, said substituted hydrocarbon-based chain, notably alkyl, is linear. [0036] according to another particular embodiment of the invention, the hydrocarbon- based chain of the radical r1 of the invention is substituted and interrupted. [0037] according to a particular embodiment of the invention, the hydrocarbon-based chain (notably an alkyl group as defined previously) of the radical r1 of the invention is: - substituted with one or more (preferably one) groups chosen from b) hydroxyl, c) thiol, d) (di)(c 1 -c 4 )(alkyl)amino and preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as anhydride, or epoxide, j) a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as optical brighteners, uv-screening agents, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) a cosmetic active agent as defined previously and x representing a’) o, s, n(r a ), b’) carbonyl, c’) or combinations thereof of a’) with b’) such as ester, amide or urea; ra representing a hydrogen atom or a (c1-c4)alkyl or aryl(c 1 -c 4 )alkyl group such as benzyl, preferably r a represents a hydrogen atom; and - interrupted with one or more (preferably one) atoms or groups chosen from o, s, n(ra) and carbonyl, or combinations thereof such as ester, amide or urea, with ra being as defined previously, preferably r a represents a hydrogen atom; preferably an alkyl group which is interrupted with one or more atoms chosen from o and s, more preferentially with an o or s, notably s, atom. in particular, when it represents an interrupted hydrocarbon-based chain, notably alkyl, r1 is c7-c20, more particularly c 8 -c 18 and even more particularly c 9 -c 16 . [0038] according to a preferred embodiment of the invention, the hydrocarbon-based chain (notably an alkyl group as defined previously) of the radical r1 of the invention is: - substituted with one or more (preferably one) groups chosen from b) hydroxyl, d) (di)(c 1 -c 4 )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, and x representing a’) o, s or n(r a ), preferably s; r a representing a hydrogen atom or a (c 1 -c 4 )alkyl group, preferably r a represents a hydrogen atom; and - interrupted with one or more (preferably one) atoms or groups chosen from o, s, n(r a ) and carbonyl, or combinations thereof such as ester, amide or urea, with r a being as defined previously, preferably r a represents a hydrogen atom; preferably an alkyl group which is interrupted with one or more atoms chosen from o and s, more preferentially with an o or s, notably s, atom. in particular, when it represents an interrupted hydrocarbon-based chain, notably alkyl, r1 is c7-c20, more particularly c 8 -c 18 and even more particularly c 9 -c 16 . [0039] preferably, said substituted and interrupted hydrocarbon-based chain, notably alkyl, is linear. [0040] more preferentially, when said hydrocarbon-based chain r 1 is substituted, it is substituted at the end of the chain on the opposite side from the carbon atom which bears said radical r 1 . [0041] according to one embodiment of the invention, said hydrocarbon-based chain r 1 has the following formula –(ch 2 ) r -x-(alk) u -g with x being as defined previously, in particular representing o, s or n(r a ), preferably s, alk represents a linear or branched, preferably linear, (c 1 -c 10 )alkylene and more particularly (c 1 -c 8 )alkylene chain, r represents an integer inclusively between 6 and 11, preferably between 7 and 10 such as 8; u is equal to 0 or 1; and g represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(c 1 -c 4 )(alkyl)amino, (hetero)aryl in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or a sugar, in particular a monosaccharide optionally protected with one or more groups such as acyl, preferably sug represents: [0042] [chem.4] : [0043] according to another particular embodiment of the invention, the pha copolymer(s) are such that r1 represents (c3-c30)alkyl substituted with one or more halogen atoms such as fluorine, chlorine or bromine, more particularly linear (c 4 -c 20 )alkyl, even more particularly (c 5 -c 13 )alkyl, substituted with a halogen atom such as bromine. preferably, the halogen atom is substituted at the end of said alkyl group. more preferentially, r 1 represents 1-halo-5-yl such as 1-bromo-5-yl. [0044] according to another particular embodiment of the invention, the pha copolymer(s) are such that r1 represents a (c3-c30)alkyl group substituted with one or more groups chosen from a) cyano, and more particularly represents a (c 3 -c 13 )alkyl group, which is preferably linear, substituted with a cyano group, such as 1-cyano-3-propyl. [0045] according to another particular embodiment of the invention, the pha copolymer(s) are such that r1 represents vii) a (hetero)aryl(c1-c2)alkyl and more particularly aryl(c1- c 2 )alkyl group, preferably phenylethyl. [0046] according to another particular embodiment of the invention, the pha copolymer(s) are such that r1 represents a (c3-c30)alkyl group substituted with one or more groups chosen from c) (hetero)cycloalkyl. more particularly, r1 represents a (c5-c13)alkyl group, which is preferably linear, substituted with a heterocycloalkyl group such as epoxide. [0047] in particular, the pha copolymer(s) are such that r2 is chosen from linear or branched (c 1 -c 28 )alkyl, and linear or branched (c 2 -c 28 )alkenyl, in particular a linear hydrocarbon-based group, particularly (c 3 -c 20 )alkyl or (c 3 -c 20 )alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical r 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical r 1 from which two carbon atoms are subtracted. [0048] according to one embodiment of the invention, the pha copolymer(s) are such that the radical r2 is a linear or branched, preferably linear, (c1-c8)alkyl, in particular (c2- c6)alkyl, preferably (c4-c6)alkyl group such as n-pentyl or n-hexyl. [0049] according to another embodiment of the composition according to the invention, the pha copolymer(s) comprise a branched (c 2 3-c8)alkyl, particularly (c4-c6)alkyl radical r , preferably a branched (c 4 -c 5 )alkyl radical such as isobutyl. [0050] according to another embodiment of the composition according to the invention, the pha copolymer(s) of the invention comprise the units (a) bearing an alkyl radical r1 as defined previously, the units (b) as defined previously and the units (c) bearing a linear or branched (c 6 -c 20 )alkenyl, particularly (c 7 -c 14 )alkenyl and more particularly (c 8 - c 10 )alkenyl radical, which is preferably linear and comprising only one unsaturation at the chain end, in particular, –[cr 4 (r 5 )] q -c(r 6 )=c(r 7 )-r 8 with r 4 , r 5 , r 6 , r 7 and r 8 , which may be identical or different, representing a hydrogen atom or a (c 1 -c 4 )alkyl group such as methyl, preferably a hydrogen atom, and q represents an integer inclusively between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8 such as 6, such as –[ch 2 ] q -ch=ch 2 and q represents an integer inclusively between 3 and 8, preferably between 4 and 6, such as 5. [0051] according to one embodiment of the composition according to the invention, the pha copolymer(s) comprise units (a) bearing an alkyl radical r1 comprising between 8 and 16 carbon atoms substituted with one or more (preferably one) groups chosen from hydroxyl, (di)(c 1 -c 4 )(alkyl)amino, carboxyl, and r-x- as defined previously, preferably r-s- with r representing a cycloalkyl group such as cyclohexyl, heterocycloalkyl such as a sugar, more preferentially a monosaccharide such as glucose, optionally substituted aryl(c 1 -c 4 )alkyl such as (c 1 -c 4 )(alkyl)benzyl or phenylethyl, or heteroaryl(c 1 -c 4 )alkyl such as furylmethyl. [0052] according to one embodiment of the composition according to the invention, the copolymer(s) comprise units b bearing a linear or branched, preferably linear, (c 1 - c )alkyl, particularly (c -c )alkyl, preferably (c -c 2 8 2 6 4 5)alkyl radical r such as pentyl. [0053] according to another embodiment of the composition according to the invention, the pha copolymer(s) comprise units (a) containing an alkyl radical r1 as defined previously, units (b) as defined previously and units (c) containing a linear or branched (c 6 -c 20 )alkenyl, particularly (c 7 -c 14 )alkenyl radical and more particularly (c 8 -c 10 )alkenyl radical, which is preferably linear, and comprising only one unsaturation at the chain end such as –[ch 2 ] q -ch=ch 2 and p represents an integer inclusively between 3 and 8, preferably between 4 and 6, such as 5. [0054] according to a particular embodiment of the invention, in the pha copolymer(s), the unit (a) comprises a hydrocarbon-based chain r 1 which is a substituted and/or interrupted alkyl, substituted and/or interrupted alkenyl, or substituted and/or interrupted alkynyl group, as defined previously, said unit (a) is present in a molar percentage ranging from 0.1% to 50%, more preferentially a molar percentage ranging from 0.5% to 40%, even more preferentially a molar percentage ranging from 1% to 40%, better still a molar percentage ranging from 2% to 30%, or a molar percentage ranging from 5% to 20%. [0055] preferably, when r 1 of the unit (a) is a substituted and/or interrupted alkyl, substituted and/or interrupted alkenyl or substituted and/or interrupted alkynyl hydrocarbon-based chain, said unit (a) is present in a molar percentage of less than or equal to 30%, more particularly less than 20%, preferably between 8% and 13%. [0056] according to a more particular embodiment of the invention in the pha copolymer(s), the unit (a) is present in a molar percentage ranging from 0.1 mol% to 99 mol%, preferentially a molar percentage ranging from 0.5 mol% to 50 mol%, more preferentially a molar percentage ranging from 1 mol% to 40 mol%, even more preferentially a molar percentage ranging from 2 mol% to 30 mol%, better a molar percentage ranging from 5 mol% to 20 mol%; better still a molar percentage ranging from 10 mol% to 30 mol% of units (a); the unit (b) is present in a molar percentage ranging from 1 mol% to 40 mol%; preferentially a molar percentage from 2 mol% to 10 mol%, more preferentially a molar percentage ranging from 5 mol% to 35 mol% of units (b); and/or the unit (c) is present in a molar percentage ranging from 0.5 mol% to 20 mol%, preferentially a molar percentage ranging from 1 mol% to 7 mol%, more preferentially from 0.5 mol% to 7 mol% of units (c). [0057] according to a more particular embodiment of the invention in the pha copolymer(s), the unit (a) is present in a molar percentage ranging from 0.1% to 50%, more preferentially a molar percentage ranging from 0.5% to 40%, even more preferentially a molar percentage ranging from 1% to 40%, better still a molar percentage ranging from 5% to 30%, a molar percentage ranging from 8% to 20%; the unit (b) is present in a molar percentage ranging from 70% to 99.5%, preferably between 60% and 95%; and the unit (c) is present in a molar percentage ranging from 0% to 30%, preferably between 1% and 25%, more preferentially between 5% and 24%, relative to the sum total, the unit (d) is present in a molar percentage ranging from 0% to 10%, preferably between 0.1% and 5%, more preferentially between 0.5% and 2% relative to the sum total and the unit (e) 0% to 10%, preferably between 0.1% and 5%, more preferentially between 0.5 % and 2% relative to the sum total and the unit. advantageously, the pha copolymer(s) of the invention comprise from 70 mol% to 90 mol% of units (b); and from 6 mol% to 24 mol% of units (c). [0058] the values of the molar percentages of the units (a), (b) and (c) of the pha copolymer(s) are calculated relative to the total number of moles of (a) + (b) if the copolymer(s) do not comprise any additional units (c); otherwise, if the copolymer(s) of the invention contain three different units (a), (b) and (c), then the molar percentage is calculated relative to the total number of moles (a) + (b) + (c); otherwise, if the copolymer(s) of the invention contain four different units (a), (b), (c) and (d), then the molar percentage is calculated relative to the total number of moles (a) + (b) + (c) + (d); otherwise, if the copolymer(s) of the invention contain four different units (a), (b), (c), (d) and (e), then the molar percentage is calculated relative to the total number of moles (a) + (b) + (c) + (d) + (e). [0059] preferentially, the pha copolymer(s) of the invention comprise the following repeating units, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0060] [chem.5] : m and n are as defined previously, hal represents a halogen atom such as bromine and t represents an integer between 1 and 10, preferably between 3 and 8 such as 6. ar: represents a (hetero)aryl group such as phenyl; ar’: represents a (c1-c4)alkyl(hetero)aryl group such as t-butylphenyl, preferably 4-t- butylphenyl; cycl: represents a cyclohexyl group; fur: represents a furyl group, preferably 2-furyl; sug: represents a sugar group, in particular a monosaccharide optionally protected with one or more groups such as acyl; preferably, sug represents: [0061] [chem.6] : in particular, the stereochemistry of the carbon atoms bearing the radicals r 1 and r 2 is of the same (r) or (s) configuration, preferably of (r) configuration. more particularly, the stereochemistry of the carbon atoms bearing the radicals r 1 , r 2 and r 3 is of the same (r) or (s) configuration, preferably of (r) configuration. more particularly, the stereochemistry of the carbon atoms bearing the radicals r 1 , r 2 , r 3 and r 4 is of the same (r) or (s) configuration, preferably of (r) configuration. more particularly, the stereochemistry of the carbon atoms bearing the radicals r 1 , r 2 , r 3 , r 4 and r 5 is of the same (r) or (s) configuration, preferably of configuration. [0062] more preferentially, the pha copolymer(s) have the following formula, and also the optical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: [0063] [chem.7] : m, n, hal, t, ar, ar’, cycl, fur and sug are as defined previously for compounds (1) to (14). [0064] [chem 8]: [0066] the pha copolymer(s) of the invention preferably have a number-average molecular weight ranging from 50000 to 150000. according to one embodiment, pha copolymer(s) of the invention are preferably different from the compounds (7) and/or (7’), more preferably pha copolymer(s) of the invention different from compound (7). according to one embodiment preferably pha copolymer(s) bears a r 1 of formula -(ch 2 )r-x-(alk) u -g wherein r, u and x are as defined previously, alk represents a linear or branched, preferably linear, (ci-cs)alkylene. [0067] the molecular weight may notably be measured by size exclusion chromatography. a method is described below in the examples. [0068] the pha copolymer(s) are particularly present in the composition according to the invention in a content ranging from 0.1% to 30% by weight and preferably ranging from 0.1 % to 25% by weight relative to the total weight of the composition. [0069] the pha copolymer(s) preferably have a number-average molecular weight ranging from 50000 to 150000. [0070] the molecular weight may notably be measured by size exclusion chromatography. a method is described below in the examples. [0071] the copolymer may be present in the composition according to the invention in a content ranging from 0.1% to 30% by weight, and preferably from 0.1% to 25% by weight, relative to the total weight of the composition. method for preparing the pha copolymer(s): [0072] the methods for preparing the pha copolymer(s) of the invention are known to those skilled in the art. mention may notably be made of the use of “functionalizable” pha-producing microbial strains. [0073] the term “functionalizable” means that the pha copolymer(s) comprise a hydrocarbon-based chain comprising one or more atoms or groups that are capable of reacting chemically with another reagent - also referred to as “reactive atoms or reactive groups” - to give a σ covalent bond functionalized by said reagent. the reagent is, for example, a compound comprising at least one nucleophilic group and said functionalized hydrocarbon-based chain comprises at least one electrophilic or nucleofugal atom or group, the nucleophilic group(s) reacting with the electrophilic group(s) to covalently graft σ the reagent. the nucleophilic reagent may also react with one or more unsaturations of the alkenyl group(s) to also lead to grafting by covalent bonding of the functionalized hydrocarbon-based chain with said reagent. the addition reaction may also be radical-based, an addition of markovnikov or anti-markovnikov type, or nucleophilic or electrophilic substitution. the addition or condensation reactions may or may not take place via a radical route, with or without the use of catalysts or of enzymes, with heating preferably less than or equal to 100°c, under a pressure of greater than 1 atm , under an inert atmosphere or under oxygen. [0074] the term “nucleophilic” refers to any atom or group which is electron-donating by an inductive effect +i and/or a mesomeric effect +m. electron-donating groups that may be mentioned include hydroxyl, thiol and amino groups. [0075] the term “electrophilic” refers to any atom or group which is electron-withdrawing by an inductive effect -i and/or a mesomeric effect -m. electron-withdrawing species that may be mentioned include. [0076] the microorganisms which produce phas of the invention notably bearing a hydrocarbon-based c 3 -c 5 chain may be naturally produced by the bacterial kingdom, such as cyanobacteria of the order of nostocales (e.g.: nostoc muscorum, synechocystis and synechococcus) but mainly by the proteobacteria, for example in the class of: -beta-proteobacteria, of the order burkholderiales (cupriavidus negator synonym rasltonia eutropha) [0077] -alpha-proteobacteria, of the order rhodobacteriales (rhodobacter capsulatus marine and photosynthetic) [0078] -gamma-proteobacteria, of the order pseudomonales of the family moraxellaceae (acinetobacter junii). [0079] among the microorganisms of the bacterial kingdom, the genera azotobacter, hydrogenomomas or chromatium are the most representative of the pha-producing organisms. [0080] the organisms which naturally produce phas notably bearing a c3-c5 hydrocarbon- based chain are notably proteobacteria, such as gamma-proteobacteria, and more particularly of the order pseudomonales of the family pseudomonas such as pseudomonas resinovorans, pseudomonas putida, pseudomonas fluorescens, pseudomonas aeruginosa, pseudomonas citronellolis, pseudomonas mendocina, pseudomonas chlororaphis and preferably pseudomonas putida gpo1 and pseudomonas putida kt2440, preferably pseudomonas putida and pseudomonas putida and in particular pseudomonas putida gpo1 and pseudomonas putida kt2440. [0081] certain organisms may also naturally produce phas without belonging to the order of pseudomonales, such as commamonas testosteroni which belongs to the class of beta-proteobacteria of the order burkholderiales of the family of comamonadaceae. [0082] the pha-producing microorganism according to the invention may also be a recombinant strain if a 3-oxidation pha synthase metabolic pathway is present. the 3- oxidation pha synthase metabolic pathway is mainly represented by four classes of enzymes, ec: 2.3.1 b2, ec: 2.3.1 b3, ec: 2.3.1 b4 and ec: 2.3.1 b5. [0083] the recombinant strain may be from the bacteria kingdom, for example escherichia coli or from the plantae kingdom, for example chlorella pyrenoidosa: international journal of biological macromolecules, 116, 552-562 “influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (phas) by microalgae”) or from the fungi kingdom, for instance saccaromyces cerevisiae or yarrowia lipolytica: applied microbiology and biotechnology 91, 1327–1340 (2011) “engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast yarrowia lipolytica by modifying the β-oxidation multifunctional protein”). [0084] use may also be made of genetically modified microorganisms, which may make it possible, for example, to increase the production of pha, and/or to increase the oxygen consumption capacity, and/or to reduce the autolysis and/or to modify the monomer ratio. [0085] it is known that, for phas, a large portion of the total production cost is devoted to the culture medium and mainly to the substrate/carbon source. use may thus be made of genetically modified microorganisms using a smaller amount of nutrient (carbon source) for their growth, for example microorganisms that are photo-autotrophic by nature, i.e. using light and co 2 as main energy source. [0086] the copolymer may be obtained in a known manner by biosynthesis, for example with the microorganisms belonging to the genus pseudomonas, such as pseudomonas resinovorans, pseudomomonas putida, pseudomonas fluorescens, pseudomonas aeruginosa, pseudomonas citronellolis, pseudomonas mendocina, pseudomonas chlororaphis and preferably pseudomonas putida; and with a carbon source which may be a c 2 -c 20 , preferably c 6 -c 18 , carboxylic acid, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; a saccharide, such as fructose, maltose, lactose, xylose, arabinose, etc.); an n-alkane, such as hexane, octane or dodecane; an n-alcohol, such as methanol, ethanol, octanol or glycerol; methane or carbon dioxide. [0087] the biosynthesis may optionally be performed in the presence of an inhibitor of the β-oxidation pathway, such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, and preferably acrylic acid. [0088] according to one embodiment, the process for preparing the phas of the invention uses microbial cells, which produce phas via genetically modified microorganisms (gmos). the genetic modification may increase the production of pha, increase the oxygen absorption capacity, increase the resistance to the toxicity of solvents, reduce the autolysis, modify the ratio of the pha comonomers, and/or any combination thereof. in some of these embodiments, the modification of the comonomer ratio of the unit (a) increases the amount of predominant monomer versus (b) of the pha of the invention, which is obtained. in another embodiment, the pha-producing microbial cells reproduce naturally. [0089] an example of genetically modified pha-producing microbial strains is pseudomonas entomophila lac23 (adv. healthcare mater. 2017, 1601017 (doi: 10.1002/adhm.201601017.) [0090] by way of example, a genetically modified microbial strain producing pha that is functionalizable or comprising a reactive group that may be mentioned is pseudomonas entomophila lac23 (biomacromolecules. 2014 jun 9;15(6):2310-9. doi: 10.1021/bm500669s). [0091] it is also possible to use wild-type strains which produce 100% pho (according to the publication dx.doi.org/10.1021/bm2001999 | biomacromolecules 2011, 12, 2126– 2136). [0092] it is also possible to use genetically modified microorganisms which produce phenylvaleric-co-3-hydroxydodecanoic copolymers hdd (sci. china life sci., shen r., et al., 57 no.1, (2014) with a strain: pseudomonas entomophila lac23. [0093] nutrients, such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium and iron, may also be used for the biosynthesis. [0094] the known appropriate temperature, ph and dissolved oxygen (od) conditions may be used for the culturing of the microorganisms. [0095] the microorganisms may be cultured according to any known method of culturing, such as in a bioreactor in continuous or batch mode, in fed or unfed mode. [0096] the biosynthesis of the polymers used according to the invention is notably described in the article “biosynthesis and properties of medium-chain-length polyhydroxyalkanoates with enriched content of the dominant monomer”, xun juan et al., biomacromolecules 2012, 13, 2926−2932, and in patent application wo 2011/069244. the microbial strains producing pha which is functionalizable or comprising a reactive group, as defined previously, are, for example, of the genus pseudomonas such as p. cichorii yn2, p. citronellolis, p. jessenii, and more generally with species of pseudomonas putida such as pseudomonas putida gpo1 (synonym of pseudomonas oleovorans), p. putida kt2442, p. putida kctc 2407, p. putida bm01. [0097] the carbon source(s): [0098] one means for gaining access to the phas of the invention is to introduce one or more organic compounds into the culture medium, this or these organic compounds representing a carbon source preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and a mixture thereof. [0099] in one embodiment, the organic compound(s) will preferably be chosen from alcohols, carboxylic acids and a mixture thereof. [00100] the carbon source(s) may be classified as follows: 1) carbon source via one or more organic compounds introduced into the medium: one means for gaining access to the phas of the invention is to introduce one or more organic compounds into the culture medium, this organic compound being a carbon source preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof. [00101] according to a particular embodiment of the invention, the organic compound(s) are chosen from alcohols, in particular (c 5 -c 20 )alkanols, and/or carboxylic acids, in particular (c 5 -c 20 )alkanoic acids. [00102] the carbon source(s) may be classified into three groups: - group a: the organic compound may aid the growth of the productive strain and aid the production of pha structural linked to the organic compound. - group b: the organic compound may aid the growth of the strain but does not participate in the production of pha structural linked to the organic compound. - group c: the organic compound does not participate in the growth of the strain. [00103] such microbiological processes are known to those skilled in the art, notably in the scientific literature. mention may be made of: international journal of biological macromolecules 28, 23–29 (2000); the journal of microbiology, 45, no.2, 87-97, (2007). [00104] according to one variant, the integration of the substrate that is structurally linked to the reactive atom(s) or to the reactive group(s) of the phas of the invention is introduced directly into the medium as sole carbon source in a medium suitable for microbial growth. (example: group a for p. putida gpo1: alkenoic acid, notably terminal). [00105] according to another variant, the integration of the substrate that is structurally linked to the reactive atom(s), notably halogen, or to the reactive group(s) of the phas of the invention is introduced into the medium as carbon source with a second carbon source as co-substrate which is also structurally linked to the pha, in a medium suitable for microbial growth. (example: group b for p. putida gpo1: haloalkanoic acids which are preferably terminal, such as terminal bromoalkanoic acids). [00106] according to yet another variant, the integration of the substrate that is structurally linked to the reactive atom(s), notably halogen, or to the reactive group(s) of the phas of the invention may be introduced directly into the medium as carbon source with a second carbon source as co-substrate which is also structurally linked to the phas and a third carbon source as co-substrate which is not structurally linked to the phas, in a medium suitable for microbial growth. (example: group c glucose or sucrose). [00107] in one embodiment, the β-oxidation pathway inhibitor is acrylic acid, 2-butynoic acid, 2-octynoic acid, phenylpropionic acid, propionic acid, trans-cinnamic acid, salicylic acid, methacrylic acid, 4-pentenoic acid or 3-mercaptopropionic acid. [00108] in one embodiment of the first aspect, the functionalized fatty acid is a functionalized hexanoic acid, functionalized heptanoic acid, functionalized octanoic acid, functionalized nonanoic acid, functionalized decanoic acid, functionalized undecanoic acid, functionalized dodecanoic acid or functionalized tetradecanoic acid. [00109] the functionalization may be introduced by means of an organic compound chosen from precursors of the alcohol and/or carboxylic acid category, notably: - for functionalization of the pha(s) with a branched alkyl group: see, for example applied and environmental microbiology,.60, no.9, 3245-325 (1994); - for functionalization of the pha(s) with a linear alkyl group comprising a terminal cyclohexyl unit: see, for example doi.org/10.1016/s0141-8130(01)00144-1; - for functionalization of the pha(s) with an unsaturated alkyl group which is preferably terminal: see, for example doi.org/10.1021/bm8005616); - for functionalization of the pha(s) with a linear alkyl group comprising a halogen preferably at the end of the hydrocarbon-based chain (doi.org/10.1021/ma00033a002); - for functionalization of the pha(s) with a (hetero)aromatic alkyl group, for example phenyl, benzoyl, phenoxy, see, for example j. microbiol. biotechnol., 11, 3, 435-442 (2001); - for functionalization of the pha(s) with a linear alkyl group comprising a heteroatom notably at the end of the hydrocarbon-based chain, see, for example doi 10.1007/s00253-011-3099-4; - for functionalization of the pha(s) with a linear alkyl group comprising a cyano function notably at the end of the hydrocarbon-based chain, see, for example doi.org/10.1111/j.1574-6968.1992.tb05839.x; - for functionalization of the pha(s) with a linear alkyl group comprising an epoxy function notably at the end of the hydrocarbon-based chain, see, for example doi.org/10.1016/s1381-5148(97)00024-2; the review international microbiology 16:1-15 (2013) doi:10.2436/20.1501.01.175) also mentions the majority of the functionalized native phas. [00110] in a particular embodiment of the invention, the fatty acid from group a is chosen from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid. [00111] in a particular embodiment of the invention, the fatty acid from group b is chosen from halooctanoic acids such as 8-bromooctanoic acid and 11-bromoundecanoic acid. [00112] in a particular embodiment of the invention, the carbon source from group c is a monosaccharide, preferably glucose. 2) carbon source in the presence of oxidation inhibitor introduced into the medium: [00113] another aspect of the invention is the use of the pha-producing microbial strains in a medium that is suitable for microbial growth, said medium comprising: a substrate which is structurally linked to the pha(s); at least one carbon source which is not structurally linked to the pha(s); and at least one oxidation and notably β-oxidation pathway inhibitor. this allows the growth of the microbial cells to take place in said medium, the microbial cells synthesizing the pha polymer(s) of the invention; preferably copolymer particularly containing more than 95% of identical units, which has a comonomer ratio of unit (a) and of unit (b) which differs from that obtained in the absence of the β-oxidation pathway inhibitor. [00114] example of functionalization of pha copolymers according to the invention starting from a) a pha copolymer bearing an unsaturated hydrocarbon-based chain, according to scheme 1 below: [00115] [chem.8] : in which scheme 1: - r2, m and n are as defined previously; - y represents a group chosen from hal such as chlorine or bromine, hydroxyl, thiol, (di)(c1-c4)(alkyl)amino, r-x with r representing a group chosen from α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl; δ) a cosmetic active agent as defined previously; ε) (c1-c20)alkyl, (c2-c20)alkenyl, (c2-c20)alkynyl; and x representing a’) o, s, n(r a ) or si(r b )(r c ) or e) linear or branched (c 1 -c 20 )alkyl, with r a , r b and r c as defined previously; - q’ represents an integer inclusively between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8 such as 6, better still between 3 and 8, preferably between 4 and 6, such as 5. [00116] other reactions may be performed using double or triple unsaturations such as michael or diels-alder addition, radical addition, catalytic (notably with pd or ni) or non- catalytic hydrogenation, halogenation , notably with bromine, hydration or oxidation , which may or may not be controlled, and reaction on electrophiles as represented schematically below. [00117] according to a particular embodiment of the invention, the pha copolymers comprise a linear or branched, saturated hydrocarbon-based chain r 1 , substituted and/or interrupted with groups as defined previously for r 1 , comprising in total between 5 and 30 carbon atoms, preferably between 6 and 20 carbon atoms and more particularly between 7 and 11 carbon atoms, and a hydrocarbon-based chain of r 2 represents a linear or branched (c 3 -c 20 )alkenyl, particularly (c 5 -c 14 )alkenyl and more particularly (c 7 -c 10 )alkenyl radical, which is preferably linear and comprising only one unsaturation at the chain end, in particular –[cr 4 (r 5 )] q -c(r 6 )=c(r 7 )-r 8 with r 4 , r 5 , r 6 , r 7 and r 8 , which may be identical or different, representing a hydrogen atom or a (c 1 - c 4 )alkyl group such as methyl, preferably a hydrogen atom, and q represents an integer inclusively between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8 such as 6, such as –[ch 2 ] q -ch=ch 2 and q represents an integer inclusively between 3 and 8, preferably between 4 and 6, such as 5 comprising between 1% and 99%, preferentially between 2% and 50% and even more preferentially between 3% and 40% of unsaturations, and even more particularly between 3% and 30% of unsaturations, better still between 5% and 20% of unsaturations. [00118] a) copolymer pha with unsaturations may be chemically modified: via addition reactions, such as radical additions, michael additions, electrophilic additions, diels-alder, halogenation, hydration or hydrogenation reaction, and preferably hydrothiolation reaction with particles, chemical compounds or polymers. in particular, the hydrothiolation reactions may be performed in the presence of a thermal initiator, a redox initiator or a photochemical initiator and of an organic compound bearing a sulfhydryl group, notably chosen from: - linear, branched, cyclic or aromatic alkanethiols including 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane-, cyclopentane -thiol, preferably hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert- butylphenylmethane- or 2-furanmethane-thiol; - organosiloxane bearing a thiol function, such as (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, 2-(triethoxysilyl)ethanethiol or mercaptopropyl-isobutyl-poss; - thiol-based silicone oils, notably those described in the document doi: 10.1016/j.actbio.2015.01.020); - thiol-based oligomers or polymers bearing a reactive function, such as an amine, an alcohol, an acid, a halogen, a thiol, an epoxide, a nitrile, an isocyanate, a heteroatom, preferably cysteine, cysteamine, n-acetylcysteamine, 2-mercaptoethanol, 1-mercapto-2-propanol, 8-mercapto-1-octanol, thiolactic acid, thioglycolic acid, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid, polyethylene glycol dithiol, 3-mercaptopropionitrile, 1,3-propanedithiol, 4-cyano-1- butanethiol, 3-chloro-1-propanethiol, 1-thio-β-d-glucose tetraacetate; and - thiols which may be obtained from disulfide reduction, such as phenyl disulfide or furfuryl disulfide. [00119] examples of initiators that may be mentioned include: tert-butyl peroxy-2- ethylhexanoate, cumene perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2’-azobisisobutyronitrile, 2,2’-azobis(2-methylbutyronitrile), 2,2’-azobis(2,4- dimethylvaleronitrile), 2,2’-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis(tert- butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4- bis(tert-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl 4,4- bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, 1,3-bis(tert- butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5- dimethyl-2,5-di(benzoylperoxy)hexane, di-tert-butyl diperoxyisophthalate, 2,2-bis(4,4- di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxy-α-methylsuccinate, di-tert- butyl peroxydimethylglutarate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diethylene glycol bis(tert- butylperoxycarbonate), di-tert-butyl peroxytrimethyladipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane phenothiazine, tetracene, perylene, anthracene, 9,10- diphenylanthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10- dimethyloxyanthracene, 2,6-dimethylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, xanthopinacol, 1,2-benzanthracene, 9-nitroanthracene. each of these initiators may be used alone or in combination of others. - the chemical reactions mentioned previously are known to those skilled in the art. mention may notably be made of the following documents: synthesis and preparation of phas modified with polyethylene glycol dithiol: 10.1021/acs.biomac.9b00479; biomacromolecules, 19, 3536–3548 (2018); - synthesis and preparation of phas modified with mercaptohexanol: 10.1021/acs.biomac.8b01257; biomacromolecules, 20, 2, 645–652 (2019); - synthesis and preparation of phas modified with hydroxycinnamic acid sulfate, and zosteric acid: 10.1021/bm049962e; biomacromolecules, 5, 4, 1452–1456 (2004); - radical addition of methyl methacrylate to a phoun: 10.1002/1521- 3935(20010701)202:11<2281::aid-macp2281>3.0.co; 2-9; macromolecular chemistry and physics, vol.202, 11, 2281-2286 (2001); synthesis and preparation of phas modified with a polysilsesquioxane (poss): 10.1016/j.polymer.2005.04.020; polymer vol.46, 14, 5025-5031 (2005); - grafting of thio-beta-glucose to saturated side chains: 1022-1336/99/0202– 0091$17.50+.50/0; macromol. rapid commun., 20, 91–94 (1999) [00120] b) copolymer pha with unsaturations may also be chemically modified via oxidation reactions, which may or may not be controlled, for example with the permanganates of a concentrated or dilute alkaline agent, or ozonolysis, oxidation in the presence of a reducing agent, making it possible to obtain novel materials bearing hydroxyl, epoxide or carboxyl groups in the terminal position of the side chains: scheme 2: a few examples of chemical modifications via oxidation of pha bearing an unsaturation in the terminal position of the side chain [00121] the chemical reactions mentioned previously are known to those skilled in the art. mention may notably be made of the following documents: 10.1021/bm049337; biomacromolecules, vol. 6, 2, 891–896 (2005); 10.1016/s0032-3861(99)00347-x; polymer, vol. 41, 5, 1703-1709 (2000); 10.1021/ma9714528 and 10.1016/s1381- 5148(97)00024-2; macromolecules, 23, 15, 3705–3707 (1990); 10.1016/s0032- 3861(01)00692-9; polymer, vol. 43, 4, 1095-1101 (2002); 10.1016/s0032- 3861(99)00347-x; polymer, vol. 41, 5, 1703-1709 (2000); and 10.1021/bm025728h; biomacromolecules, vol.4, 2, 193–195 (2003). [00122] example of functionalization of pha copolymers according to the invention starting from b) a pha copolymer bearing a hydrocarbon-based chain containing an epoxide group, according to scheme 2 below: [00123] [chem.9] : [00124] in which scheme 2 y, m, n, q’ and r2 are as defined in scheme 1. [00125] the epoxide structure may be obtained via a conventional method known to those skilled in the art, whether via biotechnological processes or via chemical processes such as oxidation of unsaturation as mentioned previously. the peroxide group(s) may react with carboxylic acids, maleic anhydrides, amines, alcohols, thiols or isocyanates, all these reagents including at least one linear or branched, cyclic or acyclic, saturated or unsaturated c1-c20 hydrocarbon-based chain, or borne by an oligomer or polymer, in particular amino (poly)saccharides such as compounds derived from chitosan and (poly)sil(ox)anes; 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-(trimethoxysilyl)propylcarbamic acid, diethanolamine, or 3-mercapto-1-propanesulfonate of alkali metal or alkaline-earth metal salts such as sodium. the epoxide groups may also react with water. [00126] mention may notably be made of the following documents: - preparation of pha bearing charges starting with diethanolamine: 10.1021/bm8005616, biomacromolecules, vol.9, 8, 2091–2096 (2008); - preparation of pha bearing charges starting with sodium 3-mercapto-1- propanesulfonate: 10.1021/acs.biomac.9b00870 biomacromolecules, vol. 20, 9, 3324–3332 (2019); - preparation of pha including a native epoxide unit: 10.1016/s1381- 5148(97)00024-2); reactive and functional polymers, vol.34, 1, 65-77 (1997) [00127] example of functionalization of pha copolymers according to the invention starting from c) a pha copolymer bearing a hydrocarbon-based chain containing a nucleofugal group, according to scheme 3 below: [00128] [chem.10] : [00129] in which scheme 3 y, m, n, q’ and r 2 are as defined in scheme 1. m corresponds to an organic or inorganic nucleofugal group, which may be substituted with a nucleophilic group; preferably, said nucleophile is a heteroatom which is electron- donating via the +i and/or +m effect such as o, s or n. preferably, the nucleofugal group m is chosen from halogen atoms such as br, and mesylate, tosylate or triflate groups. this is a reaction known to those skilled in the art. mention may be made, for example, of the following document: 10.1016/j.ijbiomac.2016.11.118, international journal of biological macromolecules, vol.95, 796-808 (2017). [00130] example of functionalization of pha copolymers according to the invention starting from d) a pha copolymer bearing a hydrocarbon-based chain containing a cyano group, according to scheme 4 below: [00131] [chem.11] : [00132] in which scheme 4 y, m, n, q’ and r2 are as defined in scheme 1. [00133] in a first step i), the pha copolymer bearing a side chain containing a cyano or nitrile group reacts with an organo-alkali metal or organomagnesium compound y- mghal, y-li or y-na, followed by hydrolysis to give the pha copolymer bearing a side chain containing a group y grafted with a ketone function. the ketone function may be converted into a thio ketone by thionation, for example with s8 in the presence of amine, or with lawesson’s reagent. said thio ketone, after total reduction ii) (for example by clemmensen reduction) leads to the pha copolymer bearing a side chain containing a group y grafted with an alkylene group. alternatively, said thio ketone may undergo a controlled reduction iii) with a conventional reducing agent to give the pha copolymer bearing a side chain containing a group y grafted with a hydroxyalkylene group. the cyano group of the starting pha copolymer can react with water after hydration v) to give the amide derivative, or after hydrolysis iv) to the carboxyl derivative. the cyano group of the starting pha copolymer may also, after reduction vi), give the amine derivative or the ketone derivative. the pha copolymers bearing a hydrocarbon-based side chain containing a nitrile function are prepared via conventional methods known to those skilled in the art. mention may be made, for example, of the document: 10.1016/0378-1097(92)90311-b, fems microbiology letters, vol. 103, 2-4, 207-214 (1992). [00134] example of functionalization of pha copolymers according to the invention starting from e) a pha copolymer bearing a hydrocarbon-based chain at the chain end, according to scheme 5 below: [00135] [chem.12] : [00136] in which scheme 5 r 1 , r 2 , m, n and y are as defined previously, and r’1 represents a hydrocarbon-based chain chosen from i) linear or branched (c1-c20)alkyl, ii) linear or branched (c2-c20)alkenyl, iii) linear or branched (c2-c20)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being substituted with one or more atoms or groups chosen from: a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(c1-c4)(alkyl)amino, e) (thio)carboxyl, f) (thio)carboxamide – c(o)-n(ra)2 or –c(s)-n(ra)2, f) cyano, g) iso(thio)cyanate, h) (hetero)aryl such as phenyl or furyl, and i) (hetero)cycloalkyl such as anhydride, or epoxide, j) a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from uva and/or uvb screening agents, and anti-ageing active agents. [00137] these chain-end grafting agents on pha polymers are known to those skilled in the art. mention may be made, for example, of the following documents: - preparation of pha oligomers by thermal degradation: 10.1021/bm0156274; biomacromolecules, vol.3, 1, 219–224 (2002); - preparation of pha oligomers by transesterification: 10.1021/ma011420r, macromolecules, vol.35, 3, 684–689 (2002); - preparation of pha oligomers by hydrolysis: 10.1016/0032-3861(94)90590-8 polymer vol.35, 19, 4156-4162 (1994); - preparation of pha oligomers by methanolysis: 10.1021/bm060981t, biomacromolecules, vol.8, 4, 1255–1265 (2007). [00138] mention may also be made of other methods known to those skilled in the art: - synthesis and characterization of pha grafted with ascorbic acid: 10.1016/j.ijbiomac.2018.11.052; international journal of biological macromolecules, vol.123: 7 (2019); - preparation of phb-b-pho copolymers by polycondensation with divinyl adipate catalysed with a lipase: 10.1021/bm9011634, biomacromolecules, vol. 10, 12, 3176–3181 (2009); - synthesis of phb-b-pho copolymers coupled via a diisocyanate junction: 10.1021/ma012223v; macromolecules, vol.35, 13, 4946–4950 (2002); - preparation of pho oligomers on chitosan by condensation between the carboxylic acid end of the pho and the amine functions of the chitosan: 10.1002/app.24276; journal of applied polymer science, vol.103, 1, (2006); - transesterification of phas with propargyl alcohol in order to produce pha oligomers that are modifiable by “click” chemistry: 10.1016/j.reactfunctpolym.2011.12.005; reactive and functional polymers, vol. 72, 2, 160-167 (2012); - preparation of pho-b-pcl copolymer: 10.1002/mabi.200400104; macromolecular bioscience, vol.4, 11 (2004); - preparation of pho-b-peg copolymer: 10.1002/macp.201000562; macromolecular chemistry and physics; vol.212, 3, (2010); - epoxidation of chain-end unsaturation and chain-end grafting of acid: 10.14314/polimery.2017.317; polimery, vol.62, 4, 317-322 (2017); - grafting of organosiloxane unit at chain end onto pha: 10.1016/j.reactfunctpolym.2014.09.008; reactive and functional polymers, vol. 84, 53-59 (2014). [00139] the combination of grafted pha copolymers of the invention described previously, starting from f) a pha bearing a reactive atom or group, according to scheme 6: [00140] [chem.13] : [ 00141] in which scheme 6 r’ 1 , r 2 , m, n and y are as defined previously, and x’ represents a reactive atom or group that is capable of reacting with an electrophilic e or nucleophilic nu atom or group to create a σ covalent bond; if x’ is an electrophilic or nucleofugal group, then it can react with a reagent r’ 1 - nu; if x’ is a nucleophilic group nu, then it can react with r’ 1 - e to create a σ covalent bond; [00142] by way of example, the σ covalent bonds or bonding group that may be generated are listed in the table below, from condensation of electrophiles with nucleophiles: [00143] [table 1]: *the activated esters of general formula -co-lg, with lg representing a leaving group such as oxysuccinimidyl, oxybenzotiiazolyl oraryloxy, optionally substituted; **the acyl azides can rearrange to give isocyanate. [00144] it is also possible, starting with g) a pha functionalized on a side chain, to perform chain-end grafting in a second stage as described in scheme 7. the reciprocal is also true, in which the chain-end grafting may be performed in a first stage, followed by performing functionalization of a functionalizable side chain in a second stage. [00145] [chem. 14] : in which scheme 7 r’ 1 , r 2 , m, n and y are as defined previously, and [00146] all these chemical reactions are known to those skilled in the art. mention may be made, for example, of the following documents: - synthesis and preparation of ph as modified with thiol-ene followed by reaction on the new grafted function: 10.1021/ma0304426; macromolecules, vol. 37, 2, 385-389 (2004); grafting of peg and of pla onto phas functionalized with acids: 10.1002/marc.200900803 and 10.1002/mabi.200390033; - synthesis and preparation of phas modified with polyethylene glycol dithiol: 10.1021/acs.biomac.9b00479. b) the fatty medium [00147] the composition comprises as second ingredient a preferably oily fatty medium. [00148] the composition may also comprise water. preferably, the composition of the invention predominantly comprises on a weight basis one or more fatty substances versus the amount by weight of water. [00149] the term “fatty substance" means an organic compound that is insoluble in water at ordinary room temperature (25°c) and at atmospheric pressure (760 mmhg) (solubility of less than 5%, preferably 1% and even more preferentially 0.1%). they bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups. in addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. [00150] the fatty substance(s) of the invention are of natural or synthetic origin, preferably natural, more preferentially of plant origin. these fatty substances are preferably neither polyoxyethylenated nor polyglycerolated. they are different from fatty acids since salified fatty acids constitute soaps which are generally soluble in aqueous media. [00151 ] according to a particular embodiment of the invention, the composition comprises one or more fatty substances that are not liquid at 25°c and at atmospheric pressure. the wax(es) [00152] according to a particular embodiment, the composition of the invention comprises one or more waxes. [00153] the term “wax” means a lipophilic compound that is solid at room temperature (25°c), with a reversible solid/liquid change of state, having a melting point of greater than or equal to 30°c, which may be up to 200°c and notably up to 120°c. [00154] in particular, the wax(es) that are suitable for use in the invention may have a melting point of greater than or equal to 45°c and in particular of greater than or equal to 55°c. [00155] the composition according to the invention preferably comprises a content of wax(es) ranging from 3% to 20% by weight relative to the total weight of the composition, in particular from 5% to 15% and more particularly from 6% to 15%. [00156] according to a particular form of the invention, the composition of the invention is solid, in particular anhydrous. it may then be in stick form; use will be made of polyethylene microwaxes in the form of crystallites with an aspect ratio at least equal to 2, and with a melting point ranging from 70 to 110°c and preferably from 70 to 100°c, so as to reduce or even eliminate the presence of strata in the solid composition. these crystallites in needle form and notably the dimensions thereof may be characterized visually according to the following method. the pasty compound(s) [00157] according to a particular embodiment, the composition of the invention comprises one or more pasty compounds. [00158] for the purposes of the present invention, the term “pasty compound’ means a lipophilic fatty compound that undergoes a reversible solid/liquid change of state, having anisotropic crystal organization in the solid state, and including, at a temperature of 23°c, a liquid fraction and a solid fraction. [00159] preferably, the fatty medium comprises one or more liquid fatty substances; in particular, the liquid fatty substance(s) are chosen from non-silicone oils; preferably, the liquid fatty substance(s) are chosen from: ■ ester oils, carbonate oils; ■ apolar branched hydrocarbon-based oils containing from 8 to 14 carbon atoms, as a mixture with a monoalcohol containing from 2 to 6 carbon atoms in a monoalcohol/apolar branched hydrocarbon-based oil weight ratio preferably ranging from 1/99 to 10/90 the oil(s) [00160] preferably, a composition comprises one or more oils. [00161] the term “oil” means a hydrophobic (i.e. water-immiscible) fatty (i.e. non-aqueous) substance that is liquid at room temperature (25°c) and at atmospheric pressure (1 atm or 760 mmhg). [00162] the term “liquid fatty substances” notably means liquid fatty substance(s) preferably having a viscosity of less than or equal to 7000 centipoises at 20°c. [00163] the liquid fatty substance(s) of the invention more particularly have a viscosity of less than or equal to 2 pa.s, more particularly less than or equal to 1 pa.s, even more particularly less than or equal to 0.1 pa.s, and more preferentially less than or equal to 0.09 pa.s at a temperature of 25°c and at a shear rate of 1 s -1 . [00164] according to a particular embodiment of the invention, the liquid fatty substance(s) have a viscosity of between 0.001 pa.s and 2 pa.s, more particularly inclusively between 0.01 and 1 pa.s and even more particularly inclusively between 0.014 and 0.1 pa.s, more preferentially inclusively between 0.015 and 0.09 pa.s at a temperature of 25°c and at a shear rate of 1 s -1 . [00165] the pha copolymer(s) according to the invention are soluble in the liquid fatty substances at 25°c and at atmospheric pressure. [00166] according to the invention, the medium is said to be carbon-based if it comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or else from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of the carbon-based medium, of carbon-based compound, which is liquid at 25°c. [00167] preferably, the liquid fatty substance(s) have an overall solubility parameter according to the hansen solubility space of less than or equal to 20 (mpa) 1/2 , or a mixture of such compounds. [00168] the global solubility parameter δ according to the hansen solubility space is defined in the article “solubility parameter values” by grulke in the book “polymer handbook”, 3rd edition, chapter vii, pages 519-559, by the relationship δ = (dd2 + dp2 + dh 2 ) 1/2 in which: - d d characterizes the london dispersion forces derived from the formation of dipoles induced during molecular impacts, - d p characterizes the debye interaction forces between permanent dipoles, - d h characterizes the forces of specific interactions (such as hydrogen bonding, acid/base, donor/acceptor, etc.). [00169] the definition of solvents in the hansen three-dimensional solubility space is described in the article by hansen: “the three-dimensional solubility parameters”, j. paint technol.39, 105 (1967). [00170] among the liquid carbon-based compounds having an overall solubility parameter according to the hansen solubility space of less than or equal to 20 (mpa) 1/2 , mention may be made of liquid fatty substances, notably oils, which may be chosen from natural or synthetic, carbon-based, or hydrocarbon-based oils, which are optionally fluorinated, and optionally branched, alone or as a mixture. [00171] the liquid fatty substances are notably chosen from c6-c16 hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, and silicones. [00172] it is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 30 carbon atoms, which are optionally substituted, in particular, with one or more (in particular 1 to 4) hydroxyl groups. if they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds. [00173] as regards the c6-c16 alkanes, they are linear or branched, and possibly cyclic. examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane. the linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene. [00174] according to a particular embodiment, the fatty substance(s) used in the process of the invention are chosen from volatile linear alkanes. [00175] the term “one or more volatile linear alkanes” means, without distinction, “one or more volatile linear alkane oils”. [00176] a volatile linear alkane that is suitable for use in the invention is liquid at room temperature (about 25°c) and atmospheric pressure (101325 pa or 760 mmhg). [00177] the term “volatile linear alkane” that is suitable for use in the invention means a linear alkane that can evaporate on contact with the skin in less than one hour, at room temperature (25°c) and atmospheric pressure (101325 pa), which is liquid at room temperature, notably having an evaporation rate ranging from 0.01 to 15 mg/cm 2 /minute, at room temperature (25°c) and atmospheric pressure (101325 pa). [00178] preferably, the volatile linear alkanes that are suitable for use in the invention have an [00179] evaporation rate ranging from 0.01 to 3.5 mg/cm²/minute and better still from 0.01 to 1.5 mg/cm²/minute, at room temperature (25°c) and atmospheric pressure (101325 pa). [00180] more preferably, the volatile linear alkanes that are suitable for use in the invention have an evaporation rate ranging from 0.01 to 0.8 mg/cm 2 /minute, preferentially from 0.01 to 0.3 mg/cm 2 /minute and even more preferentially from 0.01 to 0.12 mg/cm 2 /minute, at room temperature (25°c) and atmospheric pressure (101325 pa). [00181] the evaporation rate of a volatile alkane in accordance with the invention (and more generally of a volatile solvent) may notably be evaluated by means of the protocol described in wo 06/013413, and more particularly by means of the protocol described below. [00182] 15 g of volatile hydrocarbon-based solvent are placed in a crystallizing dish (diameter: 7 cm) placed on a balance that is in a chamber of about 0.3 m 3 with regulated temperature (25°c) and hygrometry (50% relative humidity). [00183] the volatile hydrocarbon-based solvent is allowed to evaporate freely, without stirring it, while providing ventilation by means of a fan (papst-motoren, reference 8550 n, rotating at 2700 rpm) placed in a vertical position above the crystallizing dish containing the volatile hydrocarbon-based solvent, the blades being directed towards the crystallizing dish, 20 cm away from the bottom of the crystallizing dish. [00184] the mass of volatile hydrocarbon-based solvent remaining in the crystallizing dish is measured at regular time intervals. [00185] the evaporation profile of the solvent is then obtained by plotting the curve of the amount of product evaporated (in mg/cm 2 ) as a function of the time (in min). [00186] the evaporation rate is then calculated, which corresponds to the tangent to the origin of the curve obtained. the evaporation rates are expressed in mg of volatile solvent evaporated per unit area (cm 2 ) and per unit time (minutes). [00187] according to a preferred embodiment, the volatile linear alkanes that are suitable for use in the invention have a non-zero vapour pressure (also known as the saturation vapour pressure), at room temperature, in particular a vapour pressure ranging from 0.3 pa to 6000 pa. [00188] preferably, the volatile linear alkanes that are suitable for use in the invention have a vapour pressure ranging from 0.3 to 2000 pa and better still from 0.3 to 1000 pa, at room temperature (25°c). [00189] more preferably, the volatile linear alkanes that are suitable for use in the invention have a vapour pressure ranging from 0.4 to 600 pa, preferentially from 1 to 200 pa and even more preferentially from 3 to 60 pa, at room temperature (25°c). [00190] according to one embodiment, a volatile linear alkane that is suitable for use in the invention may have a flash point that is within the range from 30 to 120°c and more particularly from 40 to 100°c. the flash point is in particular measured according to the standard iso 3679. [00191] according to one embodiment, the volatile linear alkanes that are suitable for use in the invention may be linear alkanes including from 7 to 15 carbon atoms, preferably from 8 to 14 carbon atoms and better still from 9 to 14 carbon atoms. [00192] more preferably, the volatile linear alkanes that are suitable for use in the invention may be linear alkanes including from 10 to 14 carbon atoms and even more preferentially from 11 to 14 carbon atoms. a volatile linear alkane that is suitable for use in the invention may advantageously be of plant origin. [00193] according to a particular embodiment of the invention, the fatty medium of the composition is oily. more particularly, the composition comprises one or more oils, preferably non-silicone oils, notably hydrocarbon-based oils. [00194] the term “hydrocarbon-based oil” means an oil consisting of carbon and hydrogen atoms. [00195] preferably, the liquid fatty substances of the invention are chosen from hydrocarbons, fatty alcohols, fatty esters, silicones and fatty ethers, or mixtures thereof. more particularly, the fatty substances of the invention are not (poly)oxyalkylenated. [00196] the term “liquid hydrocarbon” means a hydrocarbon composed solely of carbon and hydrogen atoms, which is liquid at ordinary temperature (25°c) and at atmospheric pressure (760 mmhg; i.e.1.013×10 5 pa). [00197] more particularly, the liquid hydrocarbons are chosen from: - linear or branched, optionally cyclic, c 6 -c 16 alkanes. examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; - linear or branched hydrocarbons of mineral, animal or synthetic origin, containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes hydrogenated polyisobutene such as parleam®, and squalane. [00198] in a preferred variant, the liquid hydrocarbon(s) are chosen from liquid paraffins and liquid petroleum jelly. [00199] the term “liquid fatty alcohol” means a non-glycerolated and non-oxyalkylenated fatty alcohol that is liquid at ordinary temperature (25°c) and at atmospheric pressure (760 mmhg; i.e.1.013×10 5 pa). [00200] preferably, the liquid fatty alcohols of the invention include from 8 to 30 carbon atoms, more preferentially c 10 -c 22 , even more preferentially c 14 -c 20 , better still c 16 -c 18 . [00201] the liquid fatty alcohols of the invention may be saturated or unsaturated. [00202] the saturated liquid fatty alcohols are preferably branched. they may optionally comprise in their structure at least one aromatic or non-aromatic ring. preferably, they are acyclic. [00203] more particularly, the saturated liquid fatty alcohols of the invention are chosen from octyldodecanol, isostearyl alcohol and 2-hexyldecanol. [00204] according to another variant of the invention, the fatty substance(s) are chosen from liquid unsaturated fatty alcohols. these liquid unsaturated fatty alcohols contain in their structure at least one double or triple bond. preferably, the fatty alcohols of the invention bear in their structure one or more double bonds. when several double bonds are present, there are preferably two or three of them, and they may be conjugated or non-conjugated. [00205] these unsaturated fatty alcohols may be linear or branched. [00206] they may optionally comprise in their structure at least one aromatic or non- aromatic ring. preferably, they are acyclic. [00207] more particularly, the liquid unsaturated fatty alcohols of the invention are chosen from oleyl alcohol, linolyl alcohol, linolenyl alcohol and undecylenyl alcohol. [00208] oleyl alcohol is most particularly preferred. [00209] the term “liquid fatty ester” or “ester oil” means a compound comprising one or more ester groups derived from a fatty acid and/or from a fatty alcohol and that is liquid at ordinary temperature (25°c) and at atmospheric pressure (760 mmhg; i.e.1.013×10 5 pa). [00210] the esters are preferably liquid esters of saturated or unsaturated, linear or branched c 1 -c 26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched c 1 -c 26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms in the esters being greater than or equal to 10. [00211] preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched. [00212] among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, isopropyl palmitate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and c 10 -c 22 and preferably c 12 -c 20 alkyl (iso)stearates such as isopropyl isostearate. [00213] esters of c4-c22 dicarboxylic or tricarboxylic acids and of c1-c22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar c 4 -c 26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used. [00214] mention may notably be made of diethyl sebacate, diisopropyl sebacate, bis(2- ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2- ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate. [00215] the composition may also comprise, as liquid fatty ester, sugar esters and diesters of c6-c30 and preferably c12-c22 fatty acids. it is recalled that the term “sugar” means oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms. these sugars may be monosaccharides, oligosaccharides or polysaccharides. [00216] examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose. [00217] the sugar esters of fatty acids may be notably chosen from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated c 6 -c 30 and preferably c 12 -c 22 fatty acids. if they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds. [00218] the esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof. [00219] these esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, notably, oleopalmitate, oleostearate and palmitostearate mixed esters. [00220] more particularly, use is made of monoesters and diesters and notably sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate. [00221] an example that may be mentioned is the product sold under the name glucate® do by the company amerchol, which is a methylglucose dioleate. [00222] finally, use may also be made of natural or synthetic glycerol esters of mono-, di- or triacids. [00223] among these, mention may be made of plant oils. [00224] as oils of plant origin or synthetic triglycerides that may be used in the composition of the invention as liquid fatty esters, examples that may be mentioned include: - triglyceride oils of plant or synthetic origin, such as liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company stéarinerie dubois or those sold under the names miglyol® 810, 812 and 818 by the company dynamit nobel, jojoba oil and shea butter oil. [00225] use will preferably be made, as esters according to the invention, of liquid fatty esters derived from monoalcohols. [00226] isopropyl myristate or isopropyl palmitate is preferred. [00227] the liquid fatty ethers are chosen from liquid dialkyl ethers such as dicaprylyl ether. [00228] according to a preferred embodiment of the invention, the composition comprises one or more hydrocarbon-based oils containing from 8 to 16 carbon atoms. [00229] more particularly, the hydrocarbon-based oil(s) containing from 8 to 16 carbon atoms are chosen from: ■ branched c8-c16 alkanes, such as c8-c16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the isopar or permethyl trade names, ■ linear c8-c16 alkanes, for instance n-dodecane (c12) and n-tetradecane (c14) sold by sasol under the references, respectively, parafol 12-97 and parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (c 11 ) and of n-tridecane (c 13 ) obtained in examples 1 and 2 of patent application wo 2008/155059 from the company cognis, and mixtures thereof. [00230] the term “ester oil” means an oily compound containing one or more ester groups in its chemical structure. [00231] the ester oil(s) are particularly chosen from: ■ oils of plant origin, such as triglycerides consisting of fatty acid esters of glycerol in which the fatty acids may have varied chain lengths from c 4 to c 24 , these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides. the oils of plant origin may be chosen from wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, groundnut oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, coconut oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil and argan oil; shea butter; or alternatively caprylic/capric acid triglycerides such as those sold by the company stéarinerie dubois or those sold under the names miglyol 810 ® , 812 ® and 818 ® by the company dynamit nobel; ■ monoester oils of formula r 9 -c(o)-or 10 in which r 9 represents a linear or branched hydrocarbon-based chain including from 5 to 19 carbon atoms and r 10 represents a linear or branched, notably branched, hydrocarbon-based chain containing from 4 to 20 carbon atoms, on condition that r 9 + r 10 ^ 9 carbon atoms and preferably less than 29 carbon atoms, for instance palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; cetearyl octanoate (purcellin oil), isopropyl myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate or octyl octanoate; ■ esters of lactic acid and of c10-c20 alcohol, such as isostearyl lactate, 2-octyldodecyl lactate, myristyl lactate, c 12 -c 13 alkyl lactate (cosmacol® eli from sasol), cetyl lactate or lauryl lactate; ■ diesters of malic acid and of c10-c20 alcohol, such as diisostearyl malate, di(c12- c 13 )alkyl malate (cosmacol® emi from sasol), dibutyloctyl malate, diethylhexyl malate or dioctyldodecyl malate; ■ esters of pentaerythritol and of c8-c22 carboxylic acid (in particular tetraesters or diesters), such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate, pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate/tetracaprate, pentaerythrityl tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tetraisostearate, pentaerythrityl tetralaurate, pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or pentaerythrityl distearate; ■ diesters of the following formula (ii) r 11 -o-c(o)-r 12 -c(o)-o-r 13 , with r 11 and r 13 , which may be identical or different, representing a linear or branched, saturated or unsaturated (preferably saturated) c 4 to c 12 and preferentially c 5 to c 10 alkyl chain, optionally containing at least one saturated or unsaturated, preferably saturated, ring, and r 12 representing a saturated or unsaturated c 1 to c 4 , preferably c 2 to c 4 , alkylene chain, for instance an alkylene chain derived from succinate (in this case r 12 is a saturated c 2 alkylene chain), maleate (in this case r 12 is an unsaturated c 2 alkylene chain), glutarate (in this case r 12 is a saturated c 3 alkylene chain) or adipate (in this case r 12 is a saturated c 4 alkylene chain); in particular, r 11 and r 13 are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl and isononyl; mention may be made preferentially of dicaprylyl maleate or bis(2-ethylhexyl) succinate; ■ diesters of the following formula (iii) r 14 -c(o)-o-r 15 -o-c(o)-r 16 , with r 14 and r 16 , which may be identical or different, representing a linear or branched, saturated or unsaturated (preferably saturated) c 4 to c 12 and preferentially c 5 to c 10 alkyl chain and r 15 representing a saturated or unsaturated c 1 to c 4 and preferably c 2 to c 4 alkylene chain. mention may notably be made of 1,3-propanediol dicaprylate (r 14 as c 7 and r 16 as c 3 ), sold under the name dub zenoat by the company stéarinierie dubois, or dipropylene glycol dicaprylate; ■ the carbonate oils may be chosen from the carbonates of formula r 17 -o-c(o)-o-r 18 , with r 17 and r 18 , which may be identical or different, representing a linear or branched c 4 to c 12 and preferentially c 6 to c 10 alkyl chain; the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), sold under the name cetiol cc® by the company basf, bis(2-ethylhexyl) carbonate, sold under the name tegosoft dec® by the company evonik, dipropylheptyl carbonate (cetiol 4 aii from basf), dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate. [00232] in particular, the fatty substance(s) b) are chosen from: - plant oils formed by fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil or cereal germ oil; - linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon atoms; and notably isononyl isononanoate; and more particularly esters of formula r-c(o)-o-r’ in which r represents a higher fatty acid residue including from 7 to 19 carbon atoms and r’ represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; - hydrocarbons and notably volatile or non-volatile, linear, branched and/or cyclic alkanes, such as c 5 -c 60 isoparaffins, which are optionally volatile, such as isododecane, parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane or isopars; or else liquid paraffins, liquid petroleum jelly, or hydrogenated polyisobutylene; - ethers containing 6 to 30 carbon atoms; - ketones containing 6 to 30 carbon atoms; - aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; - polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and - mixtures thereof. [00233] preferably, the composition comprises, in the fatty medium, at least one oil chosen from: - plant oils formed by fatty acid esters of polyols, in particular triglycerides, - esters of formula rc(o)-or’ in which r represents a higher fatty acid residue including from 7 to 19 carbon atoms and r’ represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, - volatile or non-volatile, linear or branched c 8 -c 30 alkanes, - volatile or non-volatile, non-aromatic cyclic c 5 -c 12 alkanes, - ethers containing 7 to 30 carbon atoms, - ketones containing 8 to 30 carbon atoms, - aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups, and - mixtures thereof. [00234] preferably, when the copolymer is such that the alkyl group r 1 comprises from 6 to 9 carbon atoms, the fatty substance(s) b) are chosen from apolar hydrocarbon-based oils containing from 8 to 14 carbon atoms in the absence of monoalcohol containing from 2 to 6 carbon atoms. [00235] preferably, when the copolymer is such that the alkyl group r 1 comprises 9 carbon atoms, the fatty substance(s) b) are chosen from hydrogenated polyisobutylenes. [00236] in particular the molar percentage of units (a) is greater than the molar percentage of units (b). [00237] in particular, the fatty substance(s) are chosen from non-silicone oils; preferably, the liquid fatty substance(s) are chosen from: - ester oils, carbonate oils; and - branched apolar hydrocarbon-based oils containing from 8 to 14 carbon atoms; as a mixture with - a monoalcohol containing from 2 to 6 carbon atoms preferably in a monoalcohol/branched apolar hydrocarbon-based oil weight ratio ranging from 1/99 to 10/90. [00238] advantageously, the composition comprises one or more fatty substances, which are notably liquid at 25°c and at atmospheric pressure, preferably one or more oils, of the fatty medium in a content ranging from 2% to 99.9% by weight, relative to the total weight of the composition, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight, preferably ranging from 20% to 80% by weight. [00239] according to one embodiment of the invention, the composition comprises an aqueous phase. the composition is notably formulated as aqueous lotions or as water- in-oil or oil-in-water emulsions or as multiple emulsions (oil-in-water-in-oil or water-in- oil-in-water triple emulsion (such emulsions are known and described, for example, by c. fox in “cosmetics and toiletries” - november 1986 - vol.101 - pages 101-112)). [00240] the aqueous phase of the composition contains water and in general other water- soluble or water-miscible solvents such as polar and protic solvents as defined below (see additional solvents). [00241] the composition according to the invention preferably has a ph ranging from 3 to 9, depending on the support chosen. [00242] according to a particular embodiment of the invention, the ph of the composition(s) is neutral or even slightly acidic. preferably, the ph of the composition is between 6 and 7. the ph of these compositions may be adjusted to the desired value by means of acidifying or basifying agents usually used in cosmetics, or alternatively using standard buffer systems. [00243] the term “basifying agent” or “base” means any agent for increasing the ph of the composition in which it is present. the basifying agent is a brønsted, lowry or lewis base. it may be mineral or organic. particularly, said agent is chosen from a) aqueous ammonia, b) (bi)carbonate, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, d) oxyethylenated and/or oxypropylenated ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal silicates such as sodium metasilicates, h) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and i) the compounds of formula (f) below: [00244] [chem.15] : in which formula (f): - w is a divalent c1-c6 alkylene radical optionally substituted with one or more hydroxyl groups or a c 1 -c 6 alkyl radical, and/or optionally interrupted with one or more heteroatoms such as o or nr u ; - rx, ry, rz, rt and ru, which may be identical or different, represent a hydrogen atom or a c 1 -c 6 alkyl, c 1 -c 6 hydroxyalkyl or c 1 -c 6 aminoalkyl radical. [00245] examples of amines of formula (e) that may be mentioned include 1,3- diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine. [00246] the term “alkanolamine” means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched c 1 -c 8 alkyl groups bearing one or more hydroxyl radicals. [00247] among the mineral or organic hydroxides, mention may be made of those chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metai, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. the mineral or organic hydroxides a) and b) are preferred. [00248] among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids. [00249] the basifying agents and the acidifying agents as defined previously preferably represent from 0.001% to 20% by weight relative to the weight of the composition containing them and more particularly from 0.005% to 8% by weight of the composition. [00250] according to a preferred embodiment of the invention, the composition comprises an amount of water of less than or equal to 10% by weight relative to the total weight of the composition. even more preferentially, the composition comprises an amount of water of less than or equal to 5%, better still less than 2%, even better still less than 0.5%, and is notably free of water. where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may contain residual amounts thereof. [00251] even more preferentially, the composition does not comprise any water. [00252] advantageously, the composition according to the invention comprises a physiologically acceptable medium. in particular, the composition is a cosmetic composition. [00253] the term “physiologically acceptable medium” means a medium that is compatible with human keratin materials, for instance the skin, the lips, the nails, the eyelashes, the eyebrows or the hair. [00254] the term “cosmetic composition” means a composition that is compatible with keratin materials, which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using it. [00255] the term “keratin materials” means the skin (body, face, contour of the eyes, scalp), head hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips. [00256] the composition according to the invention may comprise a cosmetic additive chosen from water, fragrances, preserving agents, fillers, colouring agents, uv-screening agents, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers and thickeners. [00257] according to a particular embodiment of the invention, the composition comprises a) colouring agents chosen from pigments, direct dyes and mixtures thereof, preferably a) pigments. [00258] the term “pigment” means any pigment of synthetic or natural origin which gives colour to keratin materials. the solubility of the pigments in water at 25°c and at atmospheric pressure (760 mmhg) is less than 0.05% by weight and preferably less than 0.01%. [00259] they are white or coloured solid particles which are naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which are rendered insoluble by formulation in the form of a lake, where appropriate. more particularly, the pigments have little or no solubility in aqueous-alcoholic media. [00260] the pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in kirk-othmer’s encyclopedia of chemical technology and in ullmann’s encyclopedia of industrial chemistry. pigments that may notably be mentioned include organic and mineral pigments such as those defined and described in ullmann's encyclopedia of industrial chemistry "pigments, organic", 2005 wiley-vch verlag gmbh & co. kgaa, weinheim 10.1002/14356007.a20371 and ibid, "pigments, inorganic, 1. general" 2009 wiley-vch verlag gmbh & co. kgaa, weinheim10.1002/14356007.a20_243.pub3. [00261] these pigments may be in pigment powder or paste form. they may be coated or uncoated. [00262] the pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof. [00263] the pigment may be a mineral pigment. the term “mineral pigment” refers to any pigment that satisfies the definition in ullmann’s encyclopaedia in the chapter on inorganic pigments. among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide. [00264] the pigment may be an organic pigment. the term “organic pigment” refers to any pigment that satisfies the definition in ullmann’s encyclopaedia in the chapter on organic pigments. the organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. [00265] in particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the colour index under the references ci 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the colour index under the references ci 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the colour index under the references ci 61565, 61570, 74260, the orange pigments codified in the colour index under the references ci 11725, 15510, 45370, 71105, the red pigments codified in the colour index under the references ci 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in patent fr 2 679771. [00266] according to a particular embodiment of the invention, the pigment(s) used are pigment pastes of organic pigments such as the products sold by the company hoechst under the name: - cosmenyl yellow iog: yellow 3 pigment (ci 11710); - cosmenyl yellow g: yellow 1 pigment (ci 11680); - cosmenyl orange gr: orange 43 pigment (ci 71105); - cosmenyl red r: red 4 pigment (ci 12085); - cosmenyl carmine fb: red 5 pigment (ci 12490); - cosmenyl violet rl: violet 23 pigment (ci 51319); - cosmenyl blue a2r: blue 15.1 pigment (ci 74160); - cosmenyl green gg: green 7 pigment (ci 74260); - cosmenyl black r: black 7 pigment (ci 77266). [00267] the pigments in accordance with the invention may also be in the form of composite pigments, as described in patent ep 1184426. these composite pigments may be composed notably of particles including: - a mineral core, - at least one binder for fixing the organic pigments to the core, and - at least one organic pigment at least partially covering the core. [00268] the term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. the mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. among the organic dyes, mention may be made of cochineal carmine. [00269] examples of lakes that may be mentioned include the products known under the following names: d & c red 21 (ci 45380), d & c orange 5 (ci 45370), d & c red 27 (ci 45410), d & c orange 10 (ci 45425), d & c red 3 (ci 45430), d & c red 7 (ci 15850:1), d & c red 4 (ci 15510), d & c red 33 (ci 17200), d & c yellow 5 (ci 19140), d & c yellow 6 (ci 15985), d & c green (ci 61570), d & c yellow 10 (ci 77002), d & c green 3 (ci 42053) or d & c blue 1 (ci 42090). [00270] the mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. [00271] among the dyes, mention may be made of cochineal carmine. mention may also be made of the dyes known under the following names: d & c red 21 (ci 45 380), d & c orange 5 (ci 45370), d & c red 27 (ci 45410), d & c orange 10 (ci 45425), d & c red 3 (ci 45430), d & c red 4 (ci 15510), d & c red 33 (ci 17 200), d & c yellow 5 (ci 19140), d & c yellow 6 (ci 15985), d & c green (ci 61 570), d & c yellow 10 (ci 77002), d & c green 3 (ci 42053), d & c blue 1 (ci 42 090). [00272] an example of a lake that may be mentioned is the product known under the following name: d & c red 7 (ci 15850:1). [00273] the pigment(s) may also be pigments with special effects. [00274] the term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). they thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade. [00275] several types of pigments with special effects exist: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index, such as nacres or glitter flakes. [00276] examples of pigments with special effects that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye notably of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. they may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs. [00277] the nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint. [00278] as illustrations of nacres that may be used in the context of the present invention, mention may notably be made of the gold-coloured nacres sold notably by the company basf under the name gold 222c (cloisonne), sparkle gold (timica), gold 4504 (chromalite) and monarch gold 233x (cloisonne); the bronze nacres sold notably by the company merck under the names bronze fine (17384) (colorona) and bronze (17353) (colorona), by the company eckart under the name prestige bronze and by the company basf under the name super bronze (cloisonne); the orange nacres sold notably by the company basf under the names orange 363c (cloisonne) and orange mcr 101 (cosmica) and by the company merck under the names passion orange (colorona) and matte orange (17449) (microna); the brown- tinted nacres sold notably by the company basf under the names nu-antique copper 340xb (cloisonne) and brown cl4509 (chromalite); the nacres with a copper tint sold notably by the company basf under the name copper 340a (timica) and by the company eckart under the name prestige copper; the nacres with a red tint sold notably by the company merck under the name sienna fine (17386) (colorona); the nacres with a yellow tint sold notably by the company basf under the name yellow (4502) (chromalite); the red-tinted nacres with a golden tint sold notably by the company basf under the name sunstone g012 (gemtone); the black nacres with a golden tint sold notably by the company basf under the name nu-antique bronze 240 ab (timica); the blue nacres sold notably by the company merck under the name matte blue (17433) (microna), dark blue (117324) (colorona); the white nacres with a silvery tint sold notably by the company merck under the name xirona silver; and the golden-green pinkish-orange nacres sold notably by the company merck under the name indian summer (xirona), and mixtures thereof. [00279] in addition to nacres on a mica support, multilayer pigments based on synthetic substrates such as alumina, silica, sodium calcium borosilicate or calcium aluminium borosilicate, and aluminium, may be envisaged. [00280] mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (helicones hc from wacker) or interference holographic glitter flakes (geometric pigments or spectra f/x from spectratek). pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company quantum dots corporation. [00281] the variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects. [00282] the size of the pigment used in the cosmetic composition according to the present invention is generally between 10 nm and 200 µm, preferably between 20 nm and 80 µm and more preferably between 30 nm and 50 µm. [00283] the pigments may be dispersed in the product by means of a dispersant. [00284] the term "dispersant" refers to a compound which can protect the dispersed particles from agglomerating or flocculating. this dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. in particular, they may become physically or chemically attached to the surface of the pigments. these dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. said agent may be charged: it may be anionic, cationic, zwitterionic or neutral. [00285] according to a particular embodiment of the invention, the dispersants used are chosen from esters of 12-hydroxystearic acid more particularly and of c8 to c20 fatty acids and of polyols such as glycerol or diglycerol, such as poly(12- hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name solsperse 21000 by the company avecia, polyglyceryl-2 dipolyhydroxystearate (ctfa name) sold under the reference dehymyls pgph by the company henkel, or polyhydroxystearic acid such as the product sold under the reference arlacel p100 by the company uniqema, and mixtures thereof. [00286] as other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance solsperse 17000 sold by the company avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company dow corning under the references dc2-5185 and dc2-5225 c. [00287] the pigments used in the cosmetic composition according to the invention may be surface-treated with an organic agent. [00288] thus, the pigments that have been surface-treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described notably in cosmetics and toiletries, february 1990, vol.105, pages 53- 64, before being dispersed in the composition in accordance with the invention. these organic agents may be chosen, for example, from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and derivatives thereof; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; proteins; alkanolamines; silicone compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes and siloxysilicates; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds. [00289] the surface-treated pigments that are useful in the cosmetic composition according to the invention may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments. [00290] the surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is. [00291] preferably, the surface-treated pigments are coated with an organic layer. [00292] the organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments. [00293] the surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. this method is notably described in patent us 4578266. [00294] an organic agent covalently bonded to the pigments will preferably be used. [00295] the agent for the surface treatment may represent from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 10% by weight relative to the total weight of the surface-treated pigments. [00296] preferably, the surface treatments of the pigments are chosen from the following treatments: - a peg-silicone treatment, for instance the aq surface treatment sold by lcw; - a chitosan treatment, for instance the cts surface treatment sold by lcw; - a triethoxycaprylylsilane treatment, for instance the as surface treatment sold by lcw; - a methicone treatment, for instance the si surface treatment sold by lcw; - a dimethicone treatment, for instance the covasil 3.05 surface treatment sold by lcw; - a dimethicone/trimethyl siloxysilicate treatment, for instance the covasil 4.05 surface treatment sold by lcw; - a lauroyllysine treatment, for instance the ll surface treatment sold by lcw; - a lauroyllysine dimethicone treatment, for instance the ll/si surface treatment sold by lcw; - a magnesium myristate treatment, for instance the mm surface treatment sold by lcw; - an aluminium dimyristate treatment, such as the mi surface treatment sold by miyoshi; - a perfluoropolymethyl isopropyl ether treatment, for instance the fhc surface treatment sold by lcw; - an isostearyl sebacate treatment, for instance the hs surface treatment sold by miyoshi; - a disodium stearoyl glutamate treatment, for instance the nai surface treatment sold by miyoshi; - a dimethicone/disodium stearoyl glutamate treatment, for instance the sa/nai surface treatment sold by miyoshi; - a perfluoroalkyl phosphate treatment, for instance the pf surface treatment sold by daito; - an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the fsa surface treatment sold by daito; - a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the fs01 surface treatment sold by daito; - a lauroyllysine/aluminium tristearate treatment, for instance the ll-stal surface treatment sold by daito; - an octyltriethylsilane treatment, for instance the ots surface treatment sold by daito; - an octyltriethylsilane/perfluoroalkyl phosphate treatment, for instance the fots surface treatment sold by daito; - an acrylate/dimethicone copolymer treatment, for instance the asc surface treatment sold by daito; - an isopropyl titanium triisostearate treatment, for instance the itt surface treatment sold by daito; - a microcrystalline cellulose and carboxymethylcellulose treatment, for instance the ac surface treatment sold by daito; - a cellulose treatment, for instance the c2 surface treatment sold by daito; - an acrylate copolymer treatment, for instance the apd surface treatment sold by daito; - a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the pf + itt surface treatment sold by daito. - the composition in accordance with the present invention may furthermore comprise one or more pigments that are not surface-treated. - according to a particular embodiment of the invention, the pigment(s) are mineral pigments. - according to another particular embodiment of the invention, the pigment(s) are chosen from nacres. [00297] according to a particular embodiment of the invention, the dispersant is present with organic or inorganic pigments in particulate form of submicron size. [00298] the term “submicron” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (µm), in particular between 0.1 and 0.9 µm, and preferably between 0.2 and 0.6 µm. [00299] according to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersant:pigment) of between 0.5:1 and 2:1, particularly between 0.75:1 and 1.5:1 or better still between 0.8:1 and 1.2:1. [00300] according to a particular embodiment, the dispersant is suitable for dispersing the pigments and is compatible with a condensation-curable formulation. [00301] the term “compatible” means, for example, that said dispersant is miscible in the oily phase of the composition or of the dispersion containing the pigment(s), and it does not retard or reduce the curing. the dispersant is preferably cationic. [00302] the dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type. among the suitable dispersants that may be mentioned are: - amino silicones, i.e. silicones comprising one or more amino groups such as those sold under the names and references: byk lpx 21879 by byk, gp-4, gp-6, gp- 344, gp-851, gp-965, gp-967 and gp-988-1, sold by genesee polymers, - silicone acrylates such as tego® rc 902, tego® rc 922, tego® rc 1041, and tego® rc 1043, sold by evonik, - polydimethylsiloxane (pdms) silicones bearing carboxyl groups such as x- 22162 and x-22370 by shin-etsu, epoxy silicones such as gp-29, gp-32, gp-502, gp- 504, gp-514, gp-607, gp-682, and gp-695 by genesee polymers, or tego® rc 1401, tego® rc 1403, tego® rc 1412 by evonik. [00303] according to a particular embodiment, the dispersant(s) are of amino silicone type and are positively charged. [00304] mention may also be made of dispersants bearing chemical groups that are capable of reacting with the reagents of the oily phase and are thus capable of improving the 3d network formed from the amino silicones. for example, dispersants of epoxy silicone pigments can react chemically with the amino silicone prepolymer amino group(s) to increase the cohesion of the amino silicone film comprising the pigment(s). [00305] preferably, the pigment(s) are chosen from carbon black, iron oxides, notably black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and purple triarylmethane pigments, such as blue 1 lake, azo pigments, notably red azo pigments, such as d & c red 7, alkali metal salt of lithol red, such as the calcium salt of lithol red b, even more preferentially red iron oxides. [00306] the colouring agents may be chosen from direct dyes. [00307] the term "direct dye" means natural and/or synthetic dyes, other than oxidation dyes. these are dyes that will spread superficially on the fiber. [00308] they may be ionic or nonionic, preferably cationic or nonionic, i.e. as sole dyes. [00309] these direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes. [00310] examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes, alone or as mixtures. [00311] preferentially, the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group. [00312] according to a particular embodiment of the invention, the direct dyes comprise at least one quaternized cationic chromophore. [00313] as direct dyes according to the invention, mention may be made of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, notably nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes. [00314] for the cationic azo dyes, mention may be made particularly of those resulting from the cationic dyes described in kirk-othmer’s encyclopedia of chemical technology, “dyes, azo”, j. wiley & sons, updated on april 19, 2010. [00315] among the azo dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications wo 95/15144, wo 95/01772 and ep-714954. [00316] according to a preferred embodiment of the invention, the direct dye(s) are chosen from cationic dyes known as "basic dyes". [00317] among the azo dyes described in the colour index international 3rd edition, mention may be made notably of the following compounds: - basic red 22 - basic red 76 - basic yellow 57 - basic brown 16 - basic brown 17. [00318] among the cationic quinone dyes, those mentioned in the abovementioned colour index international are suitable for use and, among these, mention may be made, inter alia, of the following dyes: - basic blue 22 - basic blue 99. among the azine dyes that are suitable for use, mention may be made of those listed in the colour index international, for example the following dyes: - basic blue 17 - basic red 2. among the cationic triarylmethane dyes that may be used according to the invention, mention may be made, in addition to those listed in the colour index, of the following dyes: - basic green 1 - basic violet 3 - basic violet 14 - basic blue 7 - basic blue 26. [00319] mention may also be made of the cationic dyes described in us 5888252, ep 1133975, wo 03/029359, ep 860636, wo 95/01772, wo 95/15144 and ep 714 954. mention may also be made of those listed in the encyclopedia "the chemistry of synthetic dyes" by k. venkataraman, 1952, academic press, vol.1 to 7, in the "kirk-othmer encyclopedia of chemical technology", in the chapter "dyes and dye intermediates", 1993, wiley and sons, and in various chapters of "ullmann's encyclopedia of industrial chemistry", 7th edition, wiley and sons. [00320] preferably, the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type. [00321] according to a particular embodiment, the direct dyes are cationic azo dyes, described in ep 850636, fr 2788433, ep 920856, wo 99/48465, fr 2757385, ep 850637, ep 918053, wo 97/44004, fr 2570946, fr 2285851, de 2538 363, fr 2189006, fr 1560664, fr 1540423, fr 1567219, fr 1516943, fr 1 221122, de 4220388, de 4137005, wo 01/66646, us 5708151, wo 95/01772, wo 515144, gb 1195386, us 3524842, us 5879413, ep 1062940, ep 1133 976, gb 738585, de 2527638, fr 2275462, gb 1974-27645, acta histochem. (1978), 61(1), 48-52; tsitologiya (1968), 10(3), 403-5; zh. obshch. khim. (1970), 40(1), 195-202; ann. chim. (rome) (1975), 65(5-6), 305-14; journal of the chinese chemical society (taipei) (1998), 45(1), 209-211; rev. roum. chim. (1988), 33(4), 377-83; text. res. j. (1984), 54(2), 105-7; chim. ind. (milan) (1974), 56(9), 600-3; khim. tekhnol. (1979), 22(5), 548-53; ger. monatsh. chem. (1975), 106(3), 643-8; mrl bull. res. dev. (1992), 6(2), 21-7; lihua jianyan, huaxue fence (1993), 29(4), 233-4; dyes pigm. (1992), 19(1), 69-79; dyes pigm. (1989), 11(3), 163-72. [00322] preferably, the cationic direct dye(s) comprise(s) a quaternary ammonium group; more preferentially, the cationic charge is endocyclic. [00323] these cationic radicals are, for example, a cationic radical: - bearing an exocyclic (di/tri)(c1-c8)alkylammonium charge, or - bearing an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium. [00324] mention may be made of the hydrazono cationic dyes of formulae (iii) and (iv) and the azo cationic dyes of formulae (v) and (vi) below: [00325] [chem.15] : in which formulae (iii) to (vi): ▪ het + represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (c1-c8) alkyl group such as methyl; ▪ ar + represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(c 1 -c 8 )alkylammonium, such as trimethylammonium; ▪ ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (c 1 -c 8 )alkyl, ii) optionally substituted (c 1 -c 8 )alkoxy, iii) (di)(c 1 - c8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(c 1 -c 8 )alkylamino, v) optionally substituted n-(c 1 -c 8 )alkyl-n-aryl(c 1 - c8)alkylamino or alternatively ar represents a julolidine group; ▪ ar’’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (c1- c 8 )alkyl, hydroxyl, (di)(c 1 -c 8 )(alkyl)amino, (c 1 -c 8 )alkoxy or phenyl groups; ▪ ra and rb, which may be identical or different, represent a hydrogen atom or a (c1- c 8 )alkyl group, which is optionally substituted, preferentially with a hydroxyl group; ▪ or else the substituent ra with a substituent of het + and/or rb with a substituent of ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, ra and r b represent a hydrogen atom or a (c 1 -c 4 )alkyl group optionally substituted with a hydroxyl group; ▪ q- represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate. [00326] in particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (iii) to (vi) as defined previously. more particularly, the cationic direct dyes of formulae (iii) to (vi) bearing an endocyclic cationic charge described in patent applications wo 95/15144, wo 95/01772 and ep 714954. preferentially the following direct dyes: [00327] [chem.16] : in which formulae (iii-1) and (v-1): - r 1 represents a (c1-c4)alkyl group such as methyl; - r 2 and r 3 , which may be identical or different, represent a hydrogen atom or a (c1- c4)alkyl group, such as methyl; and - r 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (c 1 -c 8 )alkyl, optionally substituted (c 1 -c 8 )alkoxy, or (di)(c 1 - c8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, r 4 is a hydrogen atom, - z represents a ch group or a nitrogen atom, preferentially ch, - q- is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl. [00328] in particular, the dyes of formulae (iii-1) and (v-1) are chosen from basic red 51, basic yellow 87 and basic orange 31 or derivatives thereof: [00329] [chem.16] : with q- being an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl. [00330] according to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say that they contain at least one fluorescent chromophore as defined previously. [00331] fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2h-pyrrol-2-ylidene-kn)methyl]-1h-pyrrolato-kn}borons (bodipy ® ), diketopyrrolopyrroles, fluorindines, (poly)methines (notably cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes and xanthenes. [00332] mention may also be made of the fluorescent dyes described in ep 1133975, wo 03/029359, ep 860636, wo 95/01772, wo 95/15144 and ep 714954 and those listed in the encyclopedia "the chemistry of synthetic dyes" by k. venkataraman, 1952, academic press, vol.1 to 7, in the "kirk-othmer encyclopedia of chemical technology", in the chapter "dyes and dye intermediates", 1993, wiley and sons, and in various chapters of "ullmann’s encyclopedia of industrial chemistry", 7th edition, wiley and sons, and in the handbook — "a guide to fluorescent probes and labeling technologies", 10th ed., molecular probes/invitrogen – oregon 2005, circulated on the internet or in the preceding printed editions. [00333] according to a preferred variant of the invention, the fluorescent dye(s) are cationic and comprise at least one quaternary ammonium radical, such as those of formula (vii) below: [00334] [chem.17] : in which formula (vii): ▪ w+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (c 1 -c 8 )alkyl groups, optionally substituted notably with one or more hydroxyl groups; ▪ ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (c 1 -c 8 )alkyl groups, preferably of c 1 -c 4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (c1-c8)alkoxy groups such as methoxy; v) one or more hydroxy(c 1 -c 8 )alkyl groups such as hydroxyethyl, vi) one or more amino or (di)(c 1 -c 8 )alkylamino groups, preferably with the c 1 -c 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl; ▪ m’ represents an integer ranging from 1 to 4; in particular, m is 1 or 2; more preferentially 1; ▪ rc and rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (c 1 -c 8 )alkyl group, preferentially of c 1 -c 4 , or alternatively r c contiguous with w + and/or rd contiguous with ar form, with the atoms that bear them, a (hetero)cycloalkyl; particularly, r c is contiguous with w + and they form a (hetero)cycloalkyl such as cyclohexyl; ▪ q- is an organic or mineral anionic counterion as defined previously. [00335] among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. use may also be made of extracts or decoctions comprising these natural dyes and notably henna-based poultices or extracts. [00336] according to a particular embodiment of the invention, the amount of colouring agents, notably of pigments, ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the composition and dispersion comprising them. [00337] advantageously, the composition according to the invention is a makeup composition, in particular a lip makeup composition, a mascara, an eyeliner, an eyeshadow or a foundation. additional solvents [00338] according to a particular embodiment of the invention, the composition comprises one or more solvents, which are preferably polar and/or protic, other than water in the predominantly fatty medium. [00339] the solvent(s), which are preferably polar and/or protic, other than water are present in the composition in a weight percentage of between 0 and 10% relative to the total weight of the solvent mixture, preferentially between 0.5% and 8%, more particularly between 1% and 5%, such as 2% by weight, relative to the total weight of the composition. preferably, the solvent(s) are polar protic solvents such as alkanols, more preferentially c 2 -c 6 alkanols, such as ethanol. the adjuvants [00340] the composition according to the invention may also comprise one or more fillers, notably in a content ranging from 0.01% to 30% by weight and preferably ranging from 0.01% to 20% by weight relative to the total weight of the composition. the term “fillers” should be understood as meaning colourless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the composition, irrespective of the temperature at which the composition is manufactured. these fillers notably serve to modify the rheology or texture of the composition. [00341] the composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, softeners, sequestrants, fragrances, preserving agents, sunscreens, surfactants, antioxidants, agents for combating loss, antidandruff agents and propellants, or mixtures thereof. [00342] the composition according to the invention may be in the form of an anhydrous composition, a water-in-oil emulsion or an oil-in-water emulsion. [00343] the term “anhydrous composition” means a composition containing less than 2% by weight of water, or even less than 0.5% of water, and is notably free of water. where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may contain residual amounts thereof. [00344] the invention is illustrated in greater detail in the examples that follow. the amounts are indicated as weight percentages. examples [00345] the phas illustrated in the various examples were prepared in 3-litre chemostats and/or 5-litre fernbach flasks depending on whether or not a β-oxidation pathway inhibitor is used. the isolation of the phas is similar for all the examples obtained. [00346] in a first step, the microorganism generates the phas which are stored in intracellular granules, the proportion of which varies as a function of the applied conditions such as the temperature or the nature of the culture medium. the generation of pha granules may or may not be associated with the growth of the microorganism as a function of the nature of the microorganisms. during the second step, the biomass containing the phas is isolated, i.e. separated from the fermentation medium, and then dried. the phas are extracted from the biomass before being purified, if necessary. [00347] a mixture of saturated and unsaturated carbon sources is, for certain examples, necessary for the stability of the pha obtained. [00348] [table 2] [00349] [table 3] example 1: pha bearing a side chain r 1 representing a linear 10% unsaturated n-octenyl group and r 2 representing an n-pentyl group [00350] [chem.17] : [00351] the process for synthesizing the compound of example 1 is adapted from the article: fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by pseudomonas putida kt2440, z. sun, j.a. ramsay, m. guay, b.a. ramsay, applied microbiology biotechnology, 82, 657– 662, 2009. [00352] the microorganism used is pseudomonas putida kt2440 atcc® 47054™. the culture method is performed under fed-batch growth axenic conditions with a maintenance solution containing a mixture of carbon source at a rate µ = 0.15 h -1 in a 3 l chemostat containing 2.5 l of culture medium. the system is aerated with a flow of 0.5 vvm of air for a nominal dissolved oxygen (o d ) value at 30% of saturation. the ph is regulated with 15% aqueous ammonia solution. the temperature of the fermentation medium is regulated at 30°c. [00353] assembly for the fed-batch growth fermentation mode the fermentation medium is regulated in terms of temperature-pressure of dissolved oxygen and ph (not shown) [00354] see figure 1 the production process is performed using three different culture media. the first culture medium, defined cm1 “inoculum”, is used for the preparation of the preculture. the second culture medium, defined cm2 “batch”, is used for unfed batch growth of the microorganism with the primary carbon sources in the fernbach flasks. the third culture medium, defined cm3 “maintenance”, is used for the fed-batch or maintenance fermentation mode with the carbon sources of interest at a flow rate calibrated as a function of the growth of the microorganism. [00355] composition in grams per litre [00356] [table 4] [00357] the composition of the nutrient broth, as mass percentages, is 37.5% beef extract and 62.5% peptone. reference 233000 difco™. [00358] composition of the solution of microelements in grams per litre: [00359] [table 5] [00360] 100 ml of preculture are prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of “inoculum” culture medium at a ph adjusted to 6.8 with 2n naoh in a 250 ml fernbach flask and are then incubated at 30°c at 150 rpm for 24 hours. 1.9 l of cm2 “batch” culture medium placed in a presterilized 3 l chemostat are inoculated at od = 0.1 with the 100 ml of preculture. after 4 hours at 30°c at 850 rpm , the introduction of the maintenance medium is performed by applying the flow rate defined by equation 1. [00361] at the end of the introduction, the biomass is isolated by centrifugation and then washed three times with water. the biomass is dried by lyophilization before being extracted with ethyl acetate for 24 hours. the suspension is clarified by filtration on a gf/a filter (whatman®). the filtrate, the pha compound dissolved in the ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40 °c to constant mass. [00362] the pha may optionally be purified by successive dissolution and precipitation from an ethyl acetate/ethanol 70% methanol system, for example. [00363] the pha was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. example 2: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 100% grafted with thiolactic acid (compound of example 1 grafted with thiolactic acid tla): [00364] [chem.18] : [00365] 1 g of the compound of example 1 and 150 mg of thiolactic acid were dissolved in 20 ml of ethyl acetate at room temperature with stirring. 20 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00366] 20 ml of the reaction medium were then precipitated from a 200 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00367] the grafted pha of example 2 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. example 3: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 100% grafted with octanethiol (compound of example 1 grafted with n-octanethiol) [00368] [chem.19] : [00369] 0.5 g of the compound of example 1 and 125 mg of octanethiol were dissolved in 10 ml of ethyl acetate at room temperature with stirring. 15 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00370] the reaction medium was then precipitated from a 100 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00371] the grafted pha of example 3 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. example 4: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 75% grafted with 8-mercapto-1-octanol (compound of example 1 grafted with 8-mercapto-1-octanol) [00372] [chem.20] : [00373] 50 mg of the compound of example 1 and 10 mg of 8-mercapto-1-octanol were dissolved in 5 ml of ethyl acetate at room temperature with stirring. 2 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00374] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00375] the grafted pha of example 4 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 75% or 7.5% of functions in total. example 5: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 32% grafted with cysteamine (compound of example 1 grafted with cysteamine) [00376] [chem.21] : [00377] 0.5 g of the compound of example 1 and 54 mg of cysteamine were dissolved in a mixture of 10 ml of dichloromethane and 2 ml of ethanol at room temperature with stirring. 10 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00378] the reaction medium was then precipitated from a 100 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00379] the grafted pha of example 5 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 32% (see the spectrum below) or 3.2% of functions in total. example 6: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 73% grafted with cyclohexanethiol (compound of example 1 grafted with cht) [00380] [chem.22] : [00381] 100 mg of the compound of example 1 and 26 mg of cyclohexanethiol were dissolved in 5 ml of dichloromethane at room temperature with stirring. 5 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00382] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00383] the grafted pha of example 6 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 73% or 7.3% of functions in total. example 7: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 66% grafted with 2-furanmethanethiol (ft) (compound of example 1 grafted with ft) [00384] [chem.23] : [00385] 100 mg of the compound of example 1 and 26 mg of 2-furanmethanethiol were dissolved in 5 ml of dichloromethane at room temperature with stirring.5 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00386] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00387] the grafted pha of example 7 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 66% or 6.6% of functions in total. example 8: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 66% grafted with 1-thio-β-d-glucose tetraacetate (compound of example 1 grafted with tgt) [00388] [chem.24] : [00389] 100 mg of the compound of example 1 and 26 mg of 1-thio-β-d-glucose tetraacetate were dissolved in 5 ml of dichloromethane at room temperature with stirring. 5 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00390] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00391] the grafted pha of example 8 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 70% or 7% of functions in total. example 9: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 50% grafted with 2-phenylethanethiol (pt) (compound of example 1 grafted with pt) [00392] [00393] 100 mg of the compound of example 1 and 26 mg of 2-phenylethanethiol were dissolved in 5 ml of dichloromethane at room temperature with stirring.5 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00394] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00395] the grafted pha of example 9 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 50% or 5% of functions in total. example 10: poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 64% grafted with 4-tert-butylbenzyl mercaptan (tbm) (compound of example 1 grafted with tbm) [00396] [00397] 100 mg of the compound of example 1 and 26 mg of 4-tert-butylbenzyl mercaptan were dissolved in 5 ml of dichloromethane at room temperature with stirring. 5 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00398] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00399] the grafted pha of example 10 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 64% or 6.4% of functions in total. example 11: poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturations 100% grafted with thiolactic acid [00400] [00401] 0.1 g of the compound of example 1 and 15 mg of thiolactic acid were dissolved in 5 ml of chloroform at room temperature with stirring.5 mg of 2,2-dimethoxy- 2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00402] the reaction medium was then precipitated from a 50 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00403] the grafted pha of example 11 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 100%. example 12: poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturations 100% grafted with octanethiol [00404] preparation of example 1’: copolymer of pha bearing a side chain r 1 representing an n-hexyl group and r 2 representing an n-hexyl group [00405] [ch 29] [00406] the production process of example 1 is adapted to that of example 1’, replacing the n-octanoic acid carbon source of example 1 with n-nonanoic acid. [00407] the pha copolymer of example 1’ was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure, with a degree of unsaturation of 5%. [00408] 1 g of the pha copolymer of example 1’ and 150 mg of octanethiol were dissolved in 15 ml of ethyl acetate at room temperature with stirring. 20 mg of 2,2- dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00409] the reaction medium was then precipitated from a 500 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00410] the grafted pha of example 12 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 100%. example 13: poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturations 100% epoxidized [00411] [chem.30] : [00412] 20 g of the pha copolymer of example 1’ were dissolved in 80 ml of anhydrous dichloromethane. a suspension of 1.9 g of 77% m-cpba was prepared with 20 ml of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours. [00413] the reaction medium was then precipitated from a 500 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00414] the pha of example 13 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. epoxidation to 100%. example 14: poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturations 100% epoxidized [00415] 10 g of the pha copolymer identical to that of example 1’ but with a degree of unsaturation of 10% were dissolved in 40 ml of anhydrous dichloromethane. a suspension of 1.9 g of 77% m-cpba was prepared with 10 ml of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours. [00416] the reaction medium was then precipitated from a 500 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00417] the pha of example 14 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. epoxidation to 100%. example 15: poly(3-hydroxynonanoate-co-undecenoate) containing 30% unsaturations 100% epoxidized [00418] 10 g of the pha copolymer identical to that of example 1’ but with a degree of unsaturation of 30% were dissolved in 40 ml of anhydrous dichloromethane. a suspension of 6.2 g of 77% m-cpba was prepared with 10 ml of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours. [00419] the reaction medium was then precipitated from a 250 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00420] the pha of example 15 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. epoxidation to 100%. example 16: poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturations 100% grafted with 4-tert-butylbenzyl mercaptan (tbm) (compound of example 1’ grafted with tbm) [00421] [chem.31] : [00422] 2 g of the pha copolymer of example 1’ and 300 mg of 4-tert-butylbenzyl mercaptan were dissolved in 25 ml of ethyl acetate at room temperature with stirring. 25 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) were added to the mixture. the medium was then irradiated under a 100 w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. [00423] the reaction medium was then precipitated from a 500 ml mixture of 70/30 v/v ethanol/water. a viscous white precipitate was obtained. this step may be repeated. the product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a teflon plate and then dried under dynamic vacuum at 40°c to obtain a homogeneous film. [00424] the pha of example 16 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. grafting to 100%. example 17: pha bearing a side chain r 1 representing a 5% linear 8-bromo-n-octanoyl group and r 2 representing a n-hexyl group [00425] [chem.32] : [00426] the process for synthesizing the compound of example 1 is adapted from the article: fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by pseudomonas putida kt2440, z. sun, j.a. ramsay, m. guay, b.a. ramsay, applied microbiology biotechnology, 82, 657– 662, 2009. [00427] the microorganism used is pseudomonas putida kt2440 atcc® 47054™. the culture method is performed under fed-batch growth axenic conditions with a maintenance solution containing a mixture of carbon source at a rate µ = 0.15 h -1 in a 3 l chemostat containing 2.5 l of culture medium. [00428] the system is aerated with a flow of 0.5 vvm of air for a dissolved oxygen (od) value at 30% of saturation. the ph is regulated with a solution composed of ammonia and glucose with a final mass of respectively 15% and 40%. the temperature of the fermentation medium is regulated at 30°c. [00429] assembly for the fed-batch growth fermentation mode: [00430] the fermentation medium is regulated in terms of temperature-pressure of dissolved oxygen and ph (not shown) [00431] see figure 1 [00432] the production process is performed using three different culture media. the first culture medium, defined cm1 “inoculum”, is used for the preparation of the preculture. the second culture medium, defined cm2 “batch”, is used for unfed batch growth of the microorganism with the primary carbon sources in the fernbach flasks. the third culture medium defined cm3 “maintenance” is used for the batch, or maintenance, feeding of the fermentation with the carbon sources of interest at a flow rate calibrated as a function of the growth of the microorganism. [table 6] [00433] the composition of the nutrient broth, as mass percentages, is 37.5% beef extract and 62.5% peptone. reference 233000 difco™ . [table 7] [00434] 100 ml of preculture are prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of “inoculum” culture medium at a ph adjusted to 6.8 with 2n naoh in a 250 ml fernbach flask and then incubated at 30°c at 150 rpm for 24 hours.1.9 l of cm2 “batch” culture medium placed in a presterilized 3 l chemostat are inoculated at od = 0.1 with 100 ml of preculture. after 4 hours at 30°c at 850 rpm, the introduction of the maintenance medium is performed by applying the flow rate defined by equation 1. [00435] at the end of introduction, the biomass is isolated by centrifugation and then washed three times with water. the biomass is dried by lyophilization before being extracted with ethyl acetate for 24 hours. the suspension is clarified by filtration on a gf/a filter (whatman®). the filtrate, composed of pha dissolved in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°c to constant mass. [00436] the pha may optionally be purified by successive dissolution and precipitations in an ethyl acetate/ethanol 70% methanol system for instance. [00437] the pha was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure: 95 molar % of units (b) for which r 2 = n-hexyl (71%) and n-butyl (24%) and 5 molar % of units (a) for which r 1 = 8-bromo-n-octanyl (5.9%) and 6-bromo-n-hexyl (0.2%). evaluations [00438] in a first stage, a film is prepared on a contrast card with a film spreader (speed: 50 mm/s - cylinder: 100 µm). the film is left to dry for 24 hours at room temperature. once dry, the film has a thickness of about 40 µm. [00439] for the pha copolymers of examples 1 to 4 that are soluble in isododecane or an isododecane/ethanol mixture, evaluation of the cosmetic properties on a dry film was performed. [00440] in a first stage, a film is prepared on a contrast card with a film spreader (speed: 50 mm/s - cylinder: 100 µm). the film is left to dry for 24 hours at room temperature. once dry, the film has a thickness of about 40 µm. [00441] three evaluations are performed on the dry film: resistance to fats, gloss and tackiness measurement of the resistance to fats [00442] three drops of olive oil or sebum or water were deposited on the dry film present on the black part of the contrast card. each drop corresponds to about 10 µl of olive oil (use of a micropipette). [00443] the drop is left in contact with the dry film for two times: 5 minutes and 30 minutes. once the time has elapsed, the drop of olive oil or sebum or water is wiped off and observation of the deterioration of the polymer film is performed. if the film was damaged by the drop of olive oil or sebum or water, the polymer film is regarded as being non-resistant to olive oil or to sebum. [00444] evaluations of the polymers only soluble in isododecane and isododecane/ethanol for resistance to water, oil and sebum: [00445] [table 8] [00446] it is seen that the pha copolymers of the invention make it possible to obtain dry, homogeneous films that are particularly resistant to water, olive oil and sebum. measurement of the gloss [00447] measurement of the gloss with a glossmeter on the black part of the contrast card. the gloss is read at an angle of 20° (the most discerning angle). [00448] evaluations of the gloss on the polymers alone soluble in isododecane and isododecane/ethanol: [00449] [table 9]: [00450] the tack was evaluated in a sensory and qualitative manner by touching the dry film with a finger. [00451] it is seen that example 13 tested does not have a tacky feel. measure of the resistance vs water/oil and adhesive tape can also be evaluated mixing of the polymer dissolved in isododecane or isododecane/ethanol with the pigment for 2 minutes at 3500 rpm. the evaluations are performed on bioskin. in a first stage, a film of each formulation is deposited on a bioskin sample by means of a film spreader. the thickness of the wet film is 100 µm. the films are dried for 24 hours at room temperature. once the films are dry, the tests may be performed. resistance to olive oil/sebum 0.5 ml of olive oil or sebum is applied to the film of formulation. after 5 minutes, the olive oil or sebum is removed by wiping 15 times with cotton wool. the deterioration of the film following contact with the olive oil or the sebum is thus examined (see figure 2). resistance to adhesive tapes a strip of adhesive tape (of scotch® type) is applied to the film of formulation. a weight is applied to the strip of said tape for 30 seconds. the adhesive tape is then removed and mounted on a slide holder so as to observe the result. the adherence of the film to the support is thus evaluated (see figure 2). exemple 18 : poly(3-hydroxynonanoate-co-undécenoate) with 5% (phnun5) and grafted at 100% with 2-(trimethylsilyl)ethanthiol (phnun5-g-tms) in order to synthesize the intermediate mcl-pha with linear side chain r 1 = c8 alkenyle group and r 2 n-hexyl with unsaturated at 5% (phnun5) the process is identical than the one descloses in example 11. poly (3-hydroxynonanoate-co-undecenoate) is functionalized at 5% unsaturations with 2- (trimethylsilyl) ethanthiol (phnun5 grafted 2- (trimethylsilyl) ethanthiol) 1 g of (phnun5) and 300 mg of 2- (trimethylsilyl) ethanthiol (tms) are dissolved in 10 ml of ethyl acetate at room temperature with stirring. then 20 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) is added to the mixture. the medium is then irradiated under a 100w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. the reaction medium is then precipitated from a 100 ml mixture of 70/30 vv ethanol / water. a viscous white precipitate is obtained. the latter step is repeated if necessary. the product thus obtained is dissolved in a minimum of ethyl acetate, poured onto a teflon plate, then dried under dynamic vacuum at 40 °c, to obtain a homogeneous film. the pha grafted with 2-(trimethylsilyl) ethanthiol is fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure, 100% was grafted. example 19: poly (3-hydroxynonanoate-co-undecenoate) with 1% unsaturations grafted at 100% with thiolactic acid (phnun1 grafted with tla) preparation of mcl-pha with linear side chain r 1 = c 8 alkenyl and r 2 = n-hexyl and unsaturated at 1% (phnun1) the process for obtaining phnun1 is adapted from the article: applied microbiololy biotechnology, z. sun, et al., 82, 657–662. (2009). the microorganism used is pseudomonas putida kt2440 atcc® 47054 ™. the culture mode is carried out under axenic conditions in discontinuous growth fed with a maintenance solution containing a mixture of carbon source at a rate of μ = 0.15h-1 in a 3l chemostat containing 2.5l of culture medium. the flow rate of the maintenance feed pump is proportional to the growth of the microorganism according to equation 1: the production process is carried out using three separate culture media. the first culture medium defined mc1 “inoculum” is used for the preparation of the preculture. the second culture medium defined mc2 "bach" is used for the non-fed discontinuous growth of the microorganism with the primary carbon sources in the fernbachs flasks. the third culture medium defined mc3 "maintenance" is used for the batch feeding, or maintenance, of the fermentation with the carbon sources of interest at a rate calibrated according to the growth of the microorganism. the composition in grams per liter of the three media is described in table 10 : [table 10]: composition in grams per liter of culture media for preculture and maintenance. the composition of nutrient broth in percentage by mass is 37.5% beef extract and 62.5% peptone. reference 233000 difco ™. the composition of the solution of microelements in grams per liter is described in table 7. 100 ml of preculture is prepared by suspending a cryotube containing 1ml of the strain with 100 ml “inoculum” culture media at ph adjusted to 6.8 with 2n naoh in a 250 ml fernbach flask then incubate at 30 ° c at 150 rpm for 24 hours.1.9l of “batch” mc2 culture medium placed in a previously sterilized 3l chemostat are inoculated at od = 0.1 with the 100 ml of preculture. after 4 hours at 30 °c at 850 rpm, the introduction of maintenance is performed by applying the flow rate defined by equation 1. at the end of the introduction, the biomass is isolated by centrifugation and then washed three times with water. the biomass is dried by lyophilization before being extracted with ethyl acetate for 24 hours. the suspension is clarified by filtration through a gf / a filter (wattman®), the filtrate, composed of pha dissolved in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40 ° c to constant mass. the pha can optionally be purified by solubilization and successive precipitations such as an ethyl acetate / ethanol 70% methanol mixture. then 1 g of (phnun1) and 40 mg of thiolactic acid are dissolved in 10 ml of ethyl acetate at room temperature with stirring. 10 mg of 2,2-dimethoxy-2-phenylacetophenone (irgacure 651) is added to the mixture. the medium is then irradiated under a 100w uv lamp at 365 nm (reference) and with stirring for at least 10 minutes. the reaction medium is then precipitated from a 100 ml mixture of 70/30 vv ethanol / water. a viscous white precipitate was obtained. this step can be repeated. the product thus obtained is dissolved in a minimum of ethyl acetate, poured onto a teflon plate, then dried under dynamic vacuum at 40 ° c, to obtain a homogeneous film. pha of exemple 19 grafted with thiolactic acid was characterized spectrometric method and show that the signals characteristic of the unsaturations have completely disappeared. 100 % grafting. example 20: poly (3-hydroxynonanoate-co-undecenoate) at 1% grafted with thiolactic acid grafted with dansylcadaverine (phnun1-g-tla-g-dansylcadaverine) 1 g of the preceeding example 19, 12 mg of o-(1h-6-chlorobenzotriazol-1-yl)-1,1,3,3- tetramethyluronium hexafluorophosphate (hctu), 10 mg 4-methylmorpholine (nmm) and 12 mg of dansylcadaverine are dissolved in 10 ml of chloroform at room temperature with stirring for 24 h. the reaction medium is then precipitated from a 100 ml mixture of 70/30 vv ethanol / water. a viscous, slightly yellow colorless precipitate is obtained. this step is repeated if necessary. the product thus obtained is dissolved in a minimum of ethyl acetate, poured onto a teflon plate, then dried under dynamic vacuum at 40 °c, to obtain a homogeneous film. the pha is fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. evaluations of the polymers only soluble in isododecane and isododecane/ethanol for resistance to water, oil and sebum: [table 10] it is seen that the pha copolymers of the invention make it possible to obtain dry, homogeneous films that are particularly resistant to water, olive oil and sebum. moreover pha of the example 20 is evaluated for the resistance vs. water, and sebum under uv lamp. the latter experiment shows an intense and persistent flurescence of the film of example 20.
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105-610-060-776-640
|
US
|
[
"AU",
"WO",
"EP",
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A61K31/00,A61K35/44,A61K35/76,A61K38/18,A61K39/00,A61P35/02,C12N5/071,C12N5/0786,C12N15/113,G01N33/574
| 2004-08-10T00:00:00 |
2004
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[
"A61",
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methods of regulating differentiation and treating of multiple myeloma
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the present invention provides methods of regulating cellular differentiation, including differentiation of stem cells and trans-differentiation of monocytes/macrophages using agonists or antagonists of pleiotrophin or a pleiotrophin receptor, as well as related methods of treating cancers associated with pleiotrophin-regulated differentiation and angiogenesis, including, e.g., multiple myeloma.
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claims 1. a method of inhibiting differentiation of a cell, comprising administering an inhibitor of pleiotrophin to said cell. 2. the method of claim 1 , wherein said cell is a monocyte/macrophage. 3. the method of claim 1 , wherein said cell is a stem cell. 4. the method of claim 3 , wherein said stem cell is selected from the group consisting of: a bone marrow stem cell, a peripheral blood stem cell and an umbilical cord blood stem cell. 5. the method of claim 3, wherein said stem cell is selected from the group consisting of: an adult stem cell and an embryonic stem cell. 6 the method of claim 1, wherein said differentiation is trans- differentiation. 7. the method of claim 6, wherein said cell is a monocyte/macrophage. 8. the method of claim 1, wherein said inhibitor of pleiotrophin is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 9. the method of claim 8, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 10. the method of claim 9, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 11. the method of claim 9, wherein said polynucleotide is an expression vector or a knockout construct. 12. the method of claim 8, wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, and a pleiotrophin binding molecule. 13. the method of claim 12, wherein said fragment of pleiotrophin corresponds to amino acid residues 111-136 or amino acids 41-64. 14. the method of claim 8, wherein said pleiotrophin binding molecule is selected from the group consisting of: a soluble pleiotrophin receptor or fragment thereof, and an antibody, or a fragment or derivative thereof. 15. the method of claim 1 , wherein said administration occurs in vivo or ex vivo. 16. the method of claim 15, wherein said administration is accomplished using an expression vector. 17. the method of claim 15, wherein said administration is accomplished using a virus. 18. the method of claim 16, wherein said virus is a retrovirus, adenovirus, or lenti virus. 19. the method of claim 15, wherein said inhibitor of pleiotrophin is administered systemically or locally. 20. a method of inhibiting bone marrow angiogenesis, comprising administering an inhibitor of pleiotrophin to a bone marrow cell. 21. the method of claim 20, wherein said inhibitor of pleiotrophin is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 22. the method of claim 21, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 23. the method of claim 22, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 24. the method of claim 22, wherein said polynucleotide is an expression vector or a knockout construct. 25. the method of claim 21 , wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, and a pleiotrophin binding molecule. 26. the method of claim 25, wherein said fragment of pleiotrophin corresponds to amino acid residues 111-136 or amino acid residues 41-64. 27. the method of claim 21 , wherein said pleiotrophin binding molecule is selected from the group consisting of: a soluble pleiotrophin receptor or fragment thereof, and an antibody, or a fragment or derivative thereof. 28. the method of claim 20, wherein said administration occurs in vivo or ex vivo. 29. the method of claim 28, wherein said administration is accomplished using an expression vector. 30. the method of claim 28, wherein said administration is accomplished using virus. 31. the method of claim 29, wherein said virus is a retrovirus. 32. the method of claim 28, wherein said inhibitor of pleiotrophin is administered systemically or locally. 33. a method of treating a hematologic malignancy in a patient in need thereof, comprising administering an inhibitor of pleiotrophin and/or an inhibitor of a pleiotrophin receptor to said patient. 34. the method of claim 33, wherein said hematologic malignancy is selected from the group consisting of: a leukemia, a lymphoma, and a multiple myeloma. 35. the method of claim 34, wherein said hematologic malignancy is a multiple myeloma. 36. the method of claim 35, wherein said multiple myeloma is selected from the group consisting of: igg myeloma, iga myeloma, igd myeloma, ige myeloma, light chain myeloma, and nonsecretory myeloma. 37. the method of claim 33, wherein said inhibitor is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 38. the method of claim 37, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 39. the method of claim 38, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 40. the method of claim 38, wherein said polynucleotide is an expression vector or a knockout construct. 41. the method of claim 37 , wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, a pleiotrophin binding molecule, and a pleiotrophin receptor binding molecule. 42. a method of inhibiting a myeloma cell from proliferating in bone marrow, comprising administering an inhibitor of pleiotrophin and/or an inhibitor of a pleiotrophin receptor to said myeloma cell. 43. the method of claim 42, wherein said inhibitor is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 44. the method of claim 43, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 45. the method of claim 44, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 46. the method of claim 44, wherein said polynucleotide is an expression vector or a knockout construct. 47. the method of claim 43 , wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, a pleiotrophin binding molecule, and a pleiotrophin receptor binding molecule. 48. a method of inducing differentiation of a cell, comprising administering pleiotrophin or a functional fragment or variant thereof to said cell. 49. the method of claim 48, wherein said functional fragment or variant stimulates trans-differentiation of a monocyte/macrophage into an endothelial -like cell. 50. the method of claim 49, wherein said cell is a monocyte/macrophage. 51. the method of claim 48, wherein said cell is a multipotent cell. 52. the method of claim 51, wherein said multipotent cell is an adult stem cell. 53. the method of claim 48, wherein said differentiation is transdifferentiation and said cell is a monocyte/macrophage. 54. the method of claim 48, further comprising administering one or more heparin binding growth factors to said cell. 55. the method of claim 54, wherein said heparin binding growth factor is selected from the group consisting of: macrophage colony stimulating factor, vascular endothelial growth factor, and basic fibroblast growth factor. 56. a method of inducing bone marrow angiogenesis, comprising administering pleiotrophin or a functional fragment or variant thereof to bone marrow, wherein said functional fragment or variant stimulates the formation of blood vessels. 57. the method of claim 56, further comprising administering one or more heparin binding growth factors to said cell. 58. the method of claim 57 , wherein said heparin binding growth factor is selected from the group consisting of: macrophage colony stimulating factor, vascular endothelial growth factor, and basic fibroblast growth factor. 59. the method of claim 56, wherein said pleiotrophin or functional fragment or variant thereof is administered using an expression vector or virus that expresses said pleiotrophin or functional fragment or variant thereof. 60. the method of claim 59, wherein said virus is selected from the group consisting of: a retrovirus, an adenovirus and a lenti virus. 61. a method of identifying a functional fragment of pleiotrophin that induces trans-differentiation of a monocyte/macrophage into an endothelial-like cell, comprising: (a) administering a fragment of pleiotrophin to a monocyte/macrophage; (b) identifying a monocyte/macrophage of step (a) that has trans- differentiated into an endothelial-like cell; and (c) determining the fragment of step (a) that was administered to the cell identified by step (b), thereby identifying a functional fragment of pleiotrophin that induced trans-differentiation of a monocyte/macrophage into an endothelial cell. 62. a method of identifying a compound that inhibits pleiotrophin- induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans- differentiation; (c) identifying a monocyte/macrophage of step (b) that does not undergo trans-differentiation or undergoes reduced trans-differentiation as compared to a control cell; and (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that inhibits pleiotrophin-induced trans-differentiation. 63. a method of identifying a compound that promotes pleiotrophin- induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans- differentiation; (c) identifying a monocyte/macrophage of step (b) that undergoes increased trans-differentiation or more rapid trans-differentiation as compared to a control cell; and (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that promotes pleiotrophin-induced trans-differentiation. 64. a method of manufacturing a compound that inhibits pleiotrophin- induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans- differentiation; (c) identifying a monocyte/macrophage of step (b) that does not undergo trans-differentiation or undergoes reduced trans-differentiation as compared to a control cell; (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that inhibits pleiotrophin-induced trans-differentiation; (e) modifying the compound identified at step (d); and (f) testing the modified compound of step (e) for its ability to inhibit pleiotrophin-induced trans-differentiation; and (g) producing the modified compound of step (f) that inhibits pleiotrophin-induced trans-differentiation. 65. a method of manufacturing a compound that promotes pleiotrophin- induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans- differentiation; (c) identifying a monocyte/macrophage of step (b) that undergoes increased trans-differentiation or more rapid trans-differentiation as compared to a control cell; (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that promotes pleiotrophin-induced trans-differentiation; (e) modifying the compound identified at step (d); and (f) testing the modified compound of step (e) for its ability to promote pleiotrophin-induced trans-differentiation; (g) producing the modified compound of step (f) that promotes pleiotrophin-induced trans-differentiation. 66. a method of treating a hematological malignancy in a patient in need thereof, comprising introducing into said patient a compound that inhibits the trans- differentiation of a hematological cell. 67. the method of claim 66, wherein said hematological malignancy is multiple myeloma and wherein said compound inhibits the trans-differentiation of a monocyte/macrophage into an endothelial-like cell. 68. the method of claim 66, wherein said compound is an antibody directed to pleiotrophin or a pleiotrophin receptor, or an epitope thereof. 69. the method of claim 68, wherein said epitope includes at least a portion of a pleiotrophin functional domain associated with trans-differentiation. 70. the method of claim 66, wherein said compound is an antisense rna or an rna interference reagent directed to pleiotrophin or a pleiotrophin receptor. 71. a method of promoting wound healing, comprising administering pleiotrophin or a functional fragment or variant thereof to said wound, wherein said functional fragment or variant thereof is capable of inducing trans-differentiation of a monocyte/macrophage into an endothelial-like cell. 72. a method of promoting wound healing in a patient, comprising: (a) isolating bone marrow or peripheral blood monocyte/macrophages from said patient; (b) administering pleiotrophin or a functional fragment or variant thereof to said isolated monocytes and macrophages, thereby inducing trans-differentiation of said monocyte/macrophages into endothelial-like cells; and (c) transferring said endothelial cells of step (b) to the wound. 73. a method of inhibiting differentiation of a cell, comprising administering an inhibitor of a pleiotrophin receptor to said cell. 74. the method of claim 73, wherein said pleiotrophin receptor is selected from the group consisting of: cd 138, rtp β/ζ, syndecan 3, and alk. 75. the method of claim 73, wherein said cell is a monocyte/macrophage. 76. the method of claim 73, wherein said cell is a stem cell. 77. the method of claim 76, wherein said stem cell is selected from the group consisting of: a bone marrow stem cell, a peripheral blood stem cell, and an umbilical cord blood stem cell. 78. the method of claim 76, wherein said stem cell is selected from the group consisting of: an adult stem cell and an embryonic stem cell. 79 the method of claim 73, wherein said differentiation is trans- differentiation. 80. the method of claim 79, wherein said cell is a monocyte/macrophage . 81. the method of claim 73, wherein said inhibitor of a pleiotrophin receptor is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 82. the method of claim 81, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 83. the method of claim 82, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 84. the method of claim 83, wherein said polynucleotide is an expression vector or a knockout construct. 85. the method of claim 81 , wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, and a pleiotrophin receptor binding molecule. 86. the method of claim 81 , wherein said pleiotrophin receptor binding molecule is an antibody, or a fragment or derivative thereof. 87. the method of claim 73, wherein said administration occurs in vivo or ex vivo. 88. the method of claim 87, wherein said administration is accomplished using an expression vector. 89. the method of claim 87, wherein said administration is accomplished using a virus. 90. the method of claim 88, wherein said virus is a retrovirus, adenovirus, or lentivirus. 91. the method of claim 87, wherein said inhibitor of a pleiotrophin receptor is administered systemically or locally. 92. a method of inhibiting bone marrow angiogenesis, comprising administering an inhibitor of a pleiotrophin receptor to a bone marrow cell. 93. the method of claim 92, wherein said pleiotrophin receptor is selected from the group consisting of: cd138, rtpβ/ζ, syndecan 3, and alk. 94. the method of claim 92, wherein said inhibitor of a pleiotrophin receptor is selected from the group consisting of: a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, and an organic compound. 95. the method of claim 94, wherein said polynucleotide is selected from the group consisting of: an antisense rna, a ribozyme, and an rna interference reagent. 96. the method of claim 95, wherein said rna interference reagent is selected from the group consisting of: double-stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, and short hairpin rna. 97. the method of claim 94, wherein said polynucleotide is an expression vector or a knockout construct. 98. the method of claim 94, wherein said polypeptide is selected from the group consisting of: a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, and a pleiotrophin receptor binding molecule. 99. the method of claim 98, wherein said pleiotrophin receptor binding molecule is an antibody, or a fragment or derivative thereof. 100. the method of claim 92, wherein said administration occurs in vivo or ex vivo. 101. the method of claim 100, wherein said administration is accomplished using an expression vector. 102. the method of claim 100, wherein said administration is accomplished using virus. 103. the method of claim 102, wherein said virus is a retrovirus. 104. the method of claim 100, wherein said inhibitor of a pleiotrophin receptor is administered systemically or locally. 105. a method of diagnosing multiple myeloma, comprising: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient; and (b) comparing the amount detected in step (a) to a predetermined cut-off value or to an amount detected in a control biological sample, wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (a) as compared to the predetermined cut-off value or amount in the control biological sample of (b) indicates the presence of multiple myeloma. 106. the method of claim 105, wherein said biological sample is selected from the group consisting of: serum, bone marrow, and tissue. 107. the method of claim 105, wherein the mrna levels of said pleiotrophin or pleiotrophin receptor are determined. 108. the method of claim 107, wherein said detection is performed by polymerase chain reaction using primers specific for said pleiotrophin or pleiotrophin receptor. 109. the method of claim 105, wherein the polypeptide levels of said pleiotrophin or pleiotrophin receptor are determined. 110. the method of claim 109, wherein said detection is performed using an antibody specific for said pleiotrophin or pleiotrophin receptor. 111. a method of monitoring the progression or response to treatment of multiple myeloma, comprising: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient diagnosed with multiple myeloma at a first time point; (b) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from the patient at a second time point or following treatment; and (c) comparing the amount detected in step (a) to the amount detected in step (b), wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (b) indicates that said multiple myeloma is progressing, and wherein a decreased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (a) indicates that said multiple myeloma is entering remission or responding to treatment. 112. the method of claim 111, wherein said biological sample is selected from the group consisting of: serum, bone marrow, and tissue. 113. the method of claim 111, wherein the mrna levels of said pleiotrophin or pleiotrophin receptor are determined. 114. the method of claim 113, wherein said detection is performed by polymerase chain reaction using primers specific for said pleiotrophin or pleiotrophin receptor. 115. the method of claim 111, wherein the polypeptide levels of said pleiotrophin or pleiotrophin receptor are determined. 116. the method of claim 115, wherein said detection is performed using an antibody specific for said pleiotrophin or pleiotrophin receptor. 117. a kit for detecting, staging, or monitoring multiple myeloma in a patient, comprising a reagent suitable for determining ptn levels in a biological sample obtained from a patient. 118. the kit of claim 117, wherein said kit comprises an antibody specific for ptn. 119. the kit of claim 117, wherein said biological sample is serum.
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methods of regulating differentiation and treating multiple myeloma background of the invention field of the invention the present invention is directed generally to the area of cellular differentiation and, more specifically, to the regulation of pleiotrophin-mediated differentiation of stem cells and trans-differentiation of monocytes/macrophages. description of the related art angiogenesis is has long been appreciated as a critical process in the growth and metastasis of malignant tumors. indeed, tumor angiogenesis is recognized as a growth limiting step to tumor development, since tumor cells, like all cells, require oxygen and nutrients for survival and must, therefore, be located within approximately 100 to 200 μm of blood vessels. accordingly, much research has focused on therapeutic treatments targeting the angiogenic process, including the important role of monocytes/macrophages. tumor-associated macrophages (tams) are a significant component of inflammatory infiltrates in neoplastic tissues and are derived from monocytes that are recruited largely by monocyte chemotactic protein. tams produce a number of potent angiogenic and lymph-angiogenic growth factors, cytokines and proteases, all of which are mediators that potentiate neoplastic progression (7). the functional significance of macrophage recruitment to sites of neoplastic growth has been examined by crossing transgenic mice expressing polyoma virus middle t (pymt) driven by the mouse mammary tumor virus long terminal repeat, which are prone to development of mammary cancer, with mice containing a null mutation in the csf-i gene (csf l op ) (8). whereas the absence of csf-i during early neoplastic development is without apparent consequence, development of late-stage invasive carcinoma and pulmonary metastases are significantly attenuated. the key difference between pymt mice and pymt/csfl op mice is not in the apparent proliferative capacity of neoplastic epithelial cells, but in the failure to recruit mature macrophages into neoplastic tissue in the absence of csf-i. targeting csf-i expression to mammary epithelium in csf-i- null/pymt mice restores macrophage recruitment, primary tumor development and metastatic potential (9). a similar study showed that subcutaneous growth of lewis lung cancer cells is impaired in csf 1 op /csf 1 op mice (10). in this latter example, however, tumors displayed a decreased mitotic index and pronounced necrosis, apparently resulting from diminished angiogenesis and impaired tumor-stroma formation. these defects were corrected by treatment of tumor-bearing mice with recombinant csf-i (10). together, these genetic experiments provide a causal link between infiltrating macrophages and the malignant potential of endothelial cells. monocytes/macrophages also display significant paracrine activities in cancer. angiogenic factors released by macrophages recruit endothelial cells from two sources: pre-existing mature endothelial cells (angiogenesis) or circulating endothelial progenitor cells (postnatal vasculogenesis). endothelial progenitor cells have been isolated from adult human peripheral blood using magnetic bead selection of cd34+ hematopoietic cells (11). in vitro, the majority of the primary adherent cells differentiated into spindle- shaped cells within 7-10 days of culture on fibronectin and expressed markers of endothelial cell characteristics. kalka et al. (12) used the primary adherence on fibronectin to isolate endothelial progenitor cells from total human peripheral blood mononuclear cells and demonstrated the appearance of cells with an endothelial phenotype at a very high frequency after 7-10 days of culture. animal models of ischemia and tumor growth have shown the contribution of endothelial progenitor cells to active neovascularization (12-14). shi et al. (15) and nieda et al. (16), using cd34+ cells at a much higher purity (>93%) than asahara et al. (11), observed adherent endothelial cell colonies. recent studies with purified hematopoietic stem cells indicate that, at least in some cases, stem cells or their progeny can transdifferentiate into nonhematopoietic cells, a definitive proof of transdifferentiation is still lacking, mainly due to cell populations, rather than clonal cells, being used in the experiments. considering that as few as 100 hematopoietic stem cells are capable of complete repopulation of hematopoietic tissue of lethally irradiated mice (19), preparations containing a few thousand or even a few cell contaminants raise concern about the outcome of stem cell transdifferentiation studies. multiple myeloma is the second most prevalent blood cancer after non- hodgkin's lymphoma. it represents approximately 1% of all cancers and 2% of all cancer deaths. although the peak age of onset of multiple myeloma is 65 to 70 years of age, recent statistics indicate both increasing incidence and earlier age of onset. approximately 45,000 americans currently have myeloma, and the american cancer society estimates that approximately 14,600 new cases of myeloma are diagnosed each year in the united states. different therapeutic modalities for multiple myeloma have not changed the course of the disease significantly since the late 1960's. accordingly, there is aneed in the art for alternative and better treatments for multiple myeloma. multiple myeloma is characterized by clonal proliferation of malignant plasma cells. normally, plasma cells make up a very small portion (less than 1%) of cells in the bone marrow. myeloma cells, however, have adhesion molecules on their surface allowing them to target bone marrow. after they enter the bone marrow, these adhesion molecules allow them to attach to stromal cells and proliferate in response to cytokines secreted from both myeloma cells and stromal cells. these cytokines, such as interleukin 6 (il-6), stimulate the growth of myeloma cells and inhibit apoptosis, until myeloma cells comprise most of the cells present in the bone marrow in many cases. bone marrow angiogenesis is a constant hallmark of multiple myeloma (1). angiogenesis is a prominent feature of mm progression, and seems to be correlated with the prognosis and the resistance of mm to chemotherapy. numerous cell populations and cytokines appear involved in angiogenesis in multiple myeloma, and antiangiogenic therapy with thalidomide is effective in patients with refractory or relapsed disease. myeloma cells, themselves, produce growth factors that promote angiogenesis. it has been demonstrated that angiogenesis does not decrease significantly with conventional or high dose therapy in myeloma (2). as the tumors grow, myeloma cells invade the hard, outer part of the bone, the solid tissue. in most cases, the myeloma cells spread into the cavities of all the large bones of the body, forming multiple small lesions, hence the name, "multiple" myeloma. in some cases, however, the myeloma cells collect in a single bone and form a tumor called plasmacytoma. angiogenesis or the lack thereof has also been implicated in the pathological processes of a variety of diseases in addition to cancers, including ischemic and inflammatory diseases, such as atherosclerosis, diabetes, alzheimer's, asthma, and obesity. ischemic diseases are typically associated with insufficient angiogenesis, while prolonged and excessive angiogenesis is associated with a variety of inflammatory diseases. accordingly, there is a need for methods of regulating angiogenesis, in order to treat such diseases. relatedly, there is a need in the art for methods to regulate cellular differentiation, including trans-differentiation and differentiation of stem cells into endothelial-like cells associated with angiogenesis, in order to treat diseases associated with altered or aberrant cell differentiation, including, e.g., multiple myeloma. brief summary of the invention the present invention provides methods and compositions useful in regulating cellular differentiation and proliferation, as well as treating associated diseases and disorders, including, e.g., multiple myeloma. in a first embodiment, the invention provides a method of inhibiting differentiation of a cell, comprising administering an inhibitor of pleiotrophin or a pleiotrophin receptor to said cell. in particular embodiments, the cell is a monocyte/macrophage or a stem cell, including, e.g., a bone marrow stem cell, a peripheral blood stem cell or an umbilical cord blood stem cell. the stem cell stem may be an adult stem cell or an embryonic stem cell. in one embodiment, the differentiation is trans- differentiation. in another embodiment, the invention includes a method of inhibiting bone marrow angiogenesis, comprising administering an inhibitor of pleiotrophin or a pleiotrophin receptor to a bone marrow cell. in a related embodiment, the invention further includes a method of inhibiting differentiation of a stem cell, comprising administering an inhibitor of pleiotrophin or a pleiotrophin receptor to said stem cell. in various embodiments, the stem cell is a bone marrow stem cell, a peripheral blood stem cell or an umbilical cord blood stem cell. in addition, the stem cell may be an adult stem cell or an embryonic stem cell. in another embodiment, the invention includes a method of treating a hematologic malignancy in a patient in need thereof, comprising administering an inhibitor of pleiotrophin or a pleiotrophin receptor to said patient. in various embodiments, the malignancy is a leukemia, a lymphoma, or a multiple myeloma, including, e.g., igg myeloma, iga myeloma, igd myeloma, ige myeloma, light chain myeloma, or nonsecretory myeloma. in yet another related embodiment, the invention includes a method of inhibiting a monocyte/macrophage from transdifferentiating into an endothelial progenitor- like cell, comprising administering an inhibitor of pleiotrophin or a pleiotrophin receptor to said monocyte/macrophage. in particular embodiments of methods related to inhibiting ptn-induced differentiation, angiogenesis, and multiple myeloma, the inhibitor inhibits ptn signaling by targeting the ptn receptor. thus, in particular embodiments, the inhibitor is a soluble ptn receptor or fragment thereof, or an antibody or small molecule that binds to a ptn receptor, which antagonizes ptn signaling, e.g., by competing with ptn for binding to the receptor. the invention also includes, in a related embodiment, a method of inhibiting a myeloma cell from proliferating in bone marrow, comprising administering an inhibitor or pleiotrophin or a pleiotrophin receptor to said myeloma cell. in another embodiment, the invention includes a method of inducing differentiation of a cell, comprising administering pleiotrophin or a functional fragment or variant thereof to said cell. in one embodiment, the functional fragment or variant stimulates trans-differentiation of a monocyte/macrophage into an endothelial-like cell. in one embodiment, the cell is a monocyte/macrophage or a stem cell. in a specific embodiment, the differentiation is transdifferentiation, and the cell is a monocyte/macrophage. in a further embodiment, the invention includes a method of inducing bone marrow angiogenesis, comprising administering pleiotrophin or a functional fragment or variant thereof to bone marrow, wherein the functional fragment or variant stimulates the formation of blood vessels. in a related embodiment, the invention includes a method of inducing differentiation of a multipotent cell into an endothelial-like cell, comprising administering pleiotrophin or a functional fragment or variant thereof to the cell. in one embodiment, the multipotent cell is an adult stem cell. in another embodiment, the invention provides a method of inducing differentiation of a monocytic cell into an endothelial-like cell, comprising administering pleiotrophin or a functional fragment or variant thereof to the monocytic cell. in further embodiments of the methods of inducing differentiation or angiogenesis, the methods comprise administering a ptn receptor to the cell or patient, either alone or in combination with administration of pleiotrophin or a functional fragments or variant thereof. in other embodiments related to inducing differentiation or angiogenesis, including related therapeutic processes, such as wound healing, the methods comprise administering an activator of a ptn receptor. in particular embodiments, the activator is an antibody or small molecule that binds to a ptn receptor and induces ptn recpetor-mediated signaling. in related embodiments of the methods of inducing differentiation or angiogenesis, the methods further comprise administering ptn and/or a ptn receptor (or a functional fragment or derivative of either or both) in combination with one or more growth factors, differentiation factors, and/or angiogenesis factors (or any molecule that induces differentiation or angiogenesis). in particular embodiments, the growth factor is a heparin binding growth factor. in certain embodiments, the heparin binding growth factor is vascular endothelial growth factor, basic fibroblast growth factor, or macrophage colony stimulating factor (mcsf). in related embodiments, the methods further comprise administering a factor that induces or promotes differentiation or angiogenesis. in a related embodiment, the invention provides a method of identifying a functional fragment of pleiotrophin that induces trans-differentiation of a monocyte/macrophage into an endothelial-like cell, comprising: (a) administering a fragment of pleiotrophin to a monocyte/macrophage; (b) identifying a monocyte/macrophage of step (a) that has trans-differentiated into an endothelial-like cell; and (c) determining the fragment of step (a) that was administered to the cell identified by step (b), thereby identifying a functional fragment of pleiotrophin that induced trans- differentiation of a monocyte/macrophage into an endothelial cell. in a related embodiment, the invention includes a method of identifying a compound that inhibits pleiotrophin-induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans-differentiation; (c) identifying a monocyte/macrophage of step (b) that does not undergo trans-differentiation or undergoes reduced trans-differentiation as compared to a control cell; and (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that inhibits pleiotrophin- induced trans-differentiation. a related embodiment of the invention includes a method of identifying a compound that promotes pleiotrophin-induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans-differentiation; (c) identifying a monocyte/macrophage of step (b) that undergoes increased trans-differentiation or more rapid trans-differentiation as compared to a control cell; and (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that promotes pleiotrophin-induced trans-differentiation. yet another embodiment of the invention includes a method of manufacturing a compound that inhibits pleiotrophin-induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans-differentiation; (c) identifying a monocyte/macrophage of step (b) that does not undergo trans-differentiation or undergoes reduced trans-differentiation as compared to a control cell; (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that inhibits pleiotrophin-induced trans-differentiation; (e) modifying the compound identified at step (d); and (f) testing the modified compound of step (e) for its ability to inhibit pleiotrophin-induced trans-differentiation; and (g) producing the modified compound of step (f) that inhibits pleiotrophin-induced trans-differentiation. similarly, the invention also provides, in a related embodiment, a method of manufacturing a compound that promotes pleiotrophin-induced trans-differentiation, comprising: (a) providing a compound to a monocyte/macrophage; (b) administering pleiotrophin or a functional fragment or variant thereof to the monocyte/macrophage of step (a) for a time sufficient to induce trans-differentiation; (c) identifying a monocyte/macrophage of step (b) that undergoes increased trans-differentiation or more rapid trans-differentiation as compared to a control cell; (d) determining the compound of step (a) that was provided to the cell identified by step (c), thereby identifying a compound that promotes pleiotrophin-induced trans-differentiation; (e) modifying the compound identified at step (d); and (f) testing the modified compound of step (e) for its ability to promote pleiotrophin-induced trans-differentiation; (g) producing the modified compound of step (f) that promotes pleiotrophin-induced trans-differentiation. in further embodiment, the invention includes a method of treating a hematological malignancy in a patient in need thereof, comprising introducing into said patient a compound that inhibits the trans-differentiation of a hematological cell. in particular embodiment, the hematological malignancy is multiple myeloma and the compound inhibits the trans-differentiation of a monocyte/macrophage into an endothelial- like cell. in one embodiment, the compound is an antibody directed to pleiotrophin or an epitope thereof. in a related embodiment, the epitope includes at least a portion of a pleiotrophin functional domain associated with trans-differentiation. in another embodiment, the compound is an antisense rna or an rna interference reagent directed to pleiotrophin. a further embodiment of the invention provides a method of promoting wound healing, comprising administering pleiotrophin or a functional fragment or variant thereof to said wound, wherein said functional fragment or variant thereof is capable of inducing trans-differentiation of a monocyte/macrophage into an endothelial-like cell. a related embodiment of the invention provides a method of promoting wound healing in a patient, comprising: (a) isolating bone marrow or peripheral blood monocyte/macrophages from said patient; (b) administering pleiotrophin or a functional fragment or variant thereof to said isolated monocytes and macrophages, thereby inducing trans-differentiation of said monocyte/macrophages into endothelial-like cells; and (c) transferring said endothelial cells of step (b) to the wound. in various embodiments of all methods and compositions of the invention, an inhibitor of pleiotrophin is a polynucleotide, a polypeptide, a peptide nucleic acid, an antibody, a virus, an inorganic compound, or an organic compound. in particular embodiments, the polynucleotide is an antisense rna, a ribozyme, or an rna interference reagent. particular rna interference reagents used in certain embodiments include double- stranded rna, double-stranded dna, rna:dna hybrids, short interfering rna, or short hairpin rna. in a related embodiment, a polynucleotide inhibitor is an expression vector or a knockout construct. in specific embodiments, the polypeptide is a fragment of pleiotrophin, a dominant-negative mutant of pleiotrophin, or a pleiotrophin binding molecule. in one embodiment, the pleiotrophin binding molecule is a soluble pleiotrophin receptor or fragment thereof. in one embodiment, the pleiotrophin fragment corresponds to amino acid residues 111-136 or amino acids 41 -64. in other embodiments, the pleiotrophin binding molecule is a pleiotrophin receptor, or fragment thereof, an antibody, or a fragment thereof, or a small organic compound. in related embodiments of methods of the invention, administration of pleiotrophin or an inhibitor or inducer thereof occurs in vivo or ex vivo. in one embodiment, administration is accomplished using an expression vector. in particular embodiment, administration is accomplished using virus, including, e.g., a retrovirus, adenovirus, or lentivirus. in addition, in another embodiment pleiotrophin or an inhibitor or inducer thereof is administered systemically or locally. in further related embodiments, the present invention provides methods for detecting multiple myeloma, and monitoring disease progression and response to treatment. in one embodiment, the invention includes a method of diagnosing multiple myeloma, comprising: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient; and (b) comparing the amount detected in step (a) to a predetermined cut-off value or to an amount detected in a control biological sample, wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (a) as compared to the predetermined cut-off value or amount in the control biological sample of (b) indicates the presence of multiple myeloma. in a related embodiment, the present invention includes a method of monitoring the progression or response to treatment of multiple myeloma, comprising: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient diagnosed with multiple myeloma at a first time point; (b) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from the patient at a second time point or following treatment; and (c) comparing the amount detected in step (a) to the amount detected in step (b), wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (b) indicates that said multiple myeloma is progressing, and wherein a decreased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (a) indicates that said multiple myeloma is entering remission or responding to treatment. in various embodiments of methods of detecting pleiotrophin or a pleiotrophin receptor, a biological sample is selected from the group consisting of: serum, bone marrow, and tissue. in particular embodiments, mrna levels are determined, while in other embodiments, polypeptide levels are determined. in one embodiment, detetion is performed using one or more primers specific for said pleiotrophin or pleiotrophin receptor. in another embodiment, detection is performed using an antibody specific for said pleiotrophin or pleiotrophin receptor. brief description of the several views of the drawings figure 1 is a graphical representation of the results of elisa analysis of ptn serum levels in multiple myeloma patients as compared to healthy controls. figure 2 depicts real time pcr quantification of the expression of selected endothelial markers (left) for monocytes/macrophages stimulated with ptn and m-csf. the designation 1 indicates that the cells were untreated with ptn and m-csf, and the designation 2 indicates that the cells were treated with ptn and m-csf. cells were obtained from volunteers as indicated: dc indicates volunteer 1 (male); hm indicates volunteer 2 (male); and rs indicates volunteer 3 (female). figure 3 depicts real time pcr quantification of endothelial markers (left) for bone marrow cd34 stimulated with ptn and m-csf and monocyte/macrophage markers (right). treatments are as indicated: (a) csf+ptn, (b) control+ptn, (c) m-csf, and (d) control. flk-i , tie-2, and vwf are endothelial markers, and cd68 & c-fms are macrophage markers. gapdh is a control. figure 4 shows a photograph of an ethidium bromide-stained gel demonstrating gene expression in monocytic cells by rt-pcr analysis after thpl cells were co-cultured with ptn from patient serum or multiple myeloma cell lines. lane 1 is a ladder marker; lane 2 is thpl (monocyte); lane 3 is thpl +pma (macrophage); lane 4 is normal human serum co-cultured with thp 1 ; lane 5 is multiple myeloma patient serum co- cultured with thpl; lane 6 is rpmi-8226 cells co-cultured with thpl; lane 7 is u266 cells cultured with thpl ; lane 8 is endothelial cells; lane 9 is multiple myeloma patient serum co-cultured with thpl + antihuman igg; lane 10 is u266 cells cultured with hpl+antihuman igg; lane 11 is multiple myeloma patient serum co-cultured with thp 1+ anti-ptn; lane 12 is u266 cells cultured with thp 1+ anti-ptn; and lanes 13 and 14 are normal human serum co-cultured with thpl. fig. 5 shows the results of rt-pcr analysis of antibody blocking ptn function on expression of the endothelial marker genes, tie-2, flk- 1 , and vwf, as well as control gapdh. lane 1 is a ladder marker; lane 2 is cells stimulated with thp 1 +pma; lane 3 is cells stimulated with thpl +pma and co-cultured with u266; lane 4 is cells treated with thp 1 +pma and co-cultured with high level mm serum; lane 5 is cells treated with thpl +pma + anti-ptn antibody and co-cultured with u266; lane 6 is cells treated with thp1+pma+ anti-ptn and co-cultured with high level mm serum; lane 7 is human endothelial cells figure 6 illustrates ptn expression levels in multiple myeloma patients. fig. 6a depicts rt-pcr analysis results of ptn expression in the bone marrow of multiple myeloma patients. ptn indicates ptn levels, while gapdh indicate control gapdh levels. figure 6b depicts rt-pcr analysis of ptn expression in the bone marrow of patients diagnosed with various stages of multiple myeloma, including refractory, relapsed, indolent, and active, as well as control samples from normal patients, a plasma cell leukemia patients, and a multiple myeloma cell line, as indicated. ptn levels are shown in the top panel, and control gapdh levels are shown in the bottom panel. figure 7 provides the results of immunostaining using antibodies specific for endothelial cell markers in control mcsf and mcsf + ptn treated cd34+ cells. figure 8 provides rt-pcr results demonstrating endothelial and monocytes gene expression in monocytic and non-monocytic cells as determined by rt-pcr analysis. rna was isolated and separated by agarose gel electrophoresis. figure 8a illustrates expression of the endothelial genes, flk-i, tie-2, and vwf, as well as control gapdh. samples are as indicated: ladder marker (lane 1), mouse raw (lane 2), human thp-i (lane 3), human u937 (lane 4) monocytic cells, nih 3t3 cells (lane 5), human coronary artery smooth muscle cells (lane 6), human coronary artery endothelial cells (lane 7), rpmi 8226 mm cell line (lane 8), human dermal fibroblasts (lane 9), and thp-i cells transduced with sense ptn (lane 10). human dermal fibroblasts were used as negative controls, and human coronary artery endothelial cells (obtained from cell applications, inc.) were used as a positive control. figure 8b illustrates expression of the monocytic cell markers, c-fms and cd-68, as well as control gapdh. samples are as indicated: ladder marker (lane 1), thp-i cells (lane 2), thp-i cells induced to differentiate into macrophage-like cells by treatment with 25 ng/ml pma (lane 3), thp-i cells infected with gfp control vector (lane 4), thp-i cells transduced with ptn sense strand and treated with pma (lane 5), thp-i cells transduced with ptn antisense strand and treated with pma (lane 6), and human coronary endothelial cells (lane 7). figure 8c illustrates expression of the endothelial genes, fik-i, tie-2, and vwf, as well as control gapdh when thpl monocytes are cultured with mm cells or serum from mm patients, untreated or treated with anti-ptn antibodies or control igg. samples are as indicated. figure 9 provides a comparison of the sequence and structural similarities between ptn and midkine. figure 9a is an alignment of the amino acid sequence of ptn and midkine. amino acids conserved between the two proteins are marked by boxes, while those also conserved in drosophila miple, a drosophila homolog of midkine, are shaded. arrowheads indicate exon-intron boundaries, and bars indicate the location of disulfide bridges. figure 9b depicts the conserved protein structure of ptn and midkine, including heparain binding sites. the amino acid numbering refers to ptn. figure 10 is a graphical representation of mtt assays measuring anti-ptn antibody inhibition of multiple myeloma. figure 1oa depicts the effect of anti-ptn antibodies on the growth rate of multiple myeloma cell line rpmi 8226 in low serum conditions at 24 h (left panel) and 48 h (right panel). figure 1ob depicts the effect of anti- ptn antibodies on the growth rate of multiple myeloma cell line u266 in low serum at 24 h (left panel) or 48 h (right panel). figure 11 is a graphical representation of the effect of anti-ptn antibodies on the growth rate of multiple myeloma tumors in a mouse model of multiple myeloma. figure 1 ia illustrates human igg levels following treatment with anti-ptn antibodies (3 or 10 mg/kg) or control vehicle. figure 1 ib illustrates tumor volume following treatment with anti-ptn antibodies (3 or 10 mg/kg) or control vehicle. figure 12 shows monocytic and endothelial gene expression in cd 14+ cells treated with ptn and mcsf or vegf, as determined by rt-pcr of samples serially diluted as indicated. figure 12a shows rt-pcr results from cells treated with mcsf+ptn (left panel) or vegf+ptn (right panel). figure 12b compares results obtained using cd 14+ cells treated with the combination of mcsf, ptn, and vegf (left panel) to results obtained using human coronary artery endothelial cells (right panel). genes examined are indicated. figure 13 is an electron micrograph of tube-like structures formed from human monocytes from human monocytes treated with ptn and mcsf (top panel) or mcsf+ptn+vegf (bottom panel). figure 14 is a diagram depicting the differentiation of stem cells and monocytes into endothelial-like cells upon treatment with mcsf and ptn. figure 15 provides graphical representations of ptn receptors on normal and mm cells. figure 15a provides flow cytometry results obtained when cells were stained for the ptn receptors cd 138 and rptpβ/ζ. cell lines examined included mm cell lines (rpmi 8226, u266, and lagλ-1), mm patient cells (pcl 1016 and 1153), and normal donor cells (pbmc 1-4). figure 15b provides flow cytometry results obtained when expression of the receptors, syndecan and alk, was compared between thp-i and u937 cells. figure 16 is a diagram depicting ptn signal transduction pathways in monocytes and mm cells. figure 17 is a graph depicting the correlation of ptn serum levels with mm disease progression and remission. figure 18 provides graphs demonstrating ptn serum levels in numerous mm patients. figure 18a shows the increase in ptn serum levels as the disease progresses, and figure 18a shows the decline in ptn serum levels as the disease enters remission. figure 19 is a graph demonstrating ptn levels in the supernatants of cultured bone marrow cells derived from normal donors or patients with active multiple myeloma. figure 20 graphically illustrates the effect of transduction with ptn antisense (mhbgf-as) or ptn sense (mhbgf-sen) on rpmi-8226 cell growth. total cell numbers at 24 and 48 hours following transduction are indicated. detailed description of the invention the present invention is based, in large part, on the unexpected discovery that pleiotrophin (ptn), a secreted factor produced by multiple myeloma (mm) cells, other cancer cells, and bone marrow stromal cells, induces monocyte/macrophages to transdifferentiate into endothelial-like cells. in addition, the present invention establishes that ptn also induces pluripotent stem cells to differentiate into endothelial-like cells. aspects of the present invention are also based, in part, upon the related discovery of ptn receptors present on mm cells, including, e.g. , cd 138, rtp β/ζ, syndecan 3, and alk. as discovered according to the present invention, levels of ptn and ptn receptors are markedly elevated in mm patients as compared to the normal control group, indicating that ptn-mediated cellular differentiation plays a fundamental role in multiple myeloma. in addition, the invention is related to the surprising finding that ptn has vasculogenic activity for bone marrow stem cells, which maps to a discrete functional domain of ptn. these findings establish ptn as a key molecule regulating cellular processes, e.g., trans-differentiation and angiogenesis, associated with tumorigenesis, including mm. in addition, the invention demonstrates that tumor growth and development, and related angiogenesis, is inhibited by treatment with agents that inhibit or reduce ptn activity. accordingly, the invention provides novel therapeutic strategies {e.g. , gene therapy, peptide therapy, monoclonal antibody therapy, etc.) to regulate differentiation and angiogenesis and treat associated diseases, including, for example, multiple myeloma (mm). based upon the discoveries of the present invention, these methods include providing an inhibitor of a ptn signal transduction pathway to reduce differentiation and/or angiogenesis, and providing an activator of a ptn signal transduction pathway to increase differentiation and/or angiogenesis. inhibitors of a ptn signal transduction pathway may target any cellular component of such a pathway; however, in particular embodiments, an inhibitor reduces the activity or expression of ptn or a ptn receptor. similarly, an activator of a ptn signal transduction pathway may increase expression or activity of any cellular component of such a pathway ; however, in particular embodiments, an activator increases the expression or activity of ptn or a ptn receptor. in specific embodiments, the targeted ptn receptor is a ptn recpetor identified as being expressed on mm cells and/or over-expressed on tumor cells as compared to normal control cells. pleiotrophin (ptn) is a 15 kda heparin-binding cytokine that has been described as a mitogen for endothelial cells, epithelial cells, and fibroblasts. ptn is a member of the midkine family of heparin-binding growth factors, which also includes the protein, midkine. the homology between the human ptn and midkine proteins is shown in figure 9 a, and their conserved protein structure is shown in figure 9b. expression of the ptn gene is tightly regulated in a temporally and cell type-specific manner during development. during embryogenesis, ptn is most highly expressed in the nervous, respiratory, and reproductive systems, and bone. the expression of ptn and the related protein, midkine, is highly restricted in adult tissues. expression of ptn and midkine in adult tissue is restricted to select populations of neurons and glia. while aspects of the present invention are described herein using ptn, it is understood that the methods of the invention may also be practiced using inhibitors or activators of midkine or a midkine receptor or signal transduction pathway. a number of putative receptors have been identified for both pleiotrophin and midkine. pleiotrophin receptors include, e.g., syndecan 1 (cd138), syndcan 3, anaplastic lymphoma kinase (alk), receptor protein tyrosine kinase phosphatase β/ζ (rptpβ/ζ), heparin, heparin sulfate, chondroitin, and chondroitin sulfate. midkine receptors include, e.g. , syndecan 1 , syndecan 3, alk, rptp β/ζ, α 4 βi integrin, heparin, and heparin sulfate. ptn has been shown to bind each of these receptors (except α 4 βi integrin) with higher affinity than midkine. ptn is also believed to be an α 4 β] integrin ligand. while these have been identified as able to bind either or both of ptn and midkine, the role of specific receptors in ptn associated disease, including ptn, had not previously been established. aberrant expression of ptn and/or midkine is associated with a variety of diseases and disorder, including cancer and inflammation. for example, both ptn and midkine have been associated with carcinomas, neuroblastoma, ischemic nephritis, alzheimer's disease, and osteoporosis; ptn has been associated with melanoma; and midkine has been associated with wiim' s tumor, malignant peripheral nerve sheath tumor, neointima formation upon balloon injury, retinal degeneration, delayed neuronal cell death after ischemia, and human immunodeficiency virus/ aids. ptn mrna is re-expressed in a significant proportion of samples from different human tumors and in about one-fourth of over 40 human tumor cell lines of different origins. cells transformed by ptn develop into highly vascularized, aggressive tumors when implanted into the nude mouse and characteristically have significant disarray of the cytoskeletal structure. it has been demonstrated that serum concentrations of ptn were elevated in 65-90% of lung cancer patients (4). ptn mean serum concentrations were 11 -fold higher in a tumor patient group as compared to a healthy control group. furthermore, ptn serum levels correlated positively with stage of disease and inversely with response to therapy. in sharp contrast, plasma concentrations of other angiogenic factors such as vegf were elevated in only 25-30% of lung cancer patients by an average of only two-fold. there was no apparent correlation between plasma vascular vegf concentration and stage of disease (4). it has been suggested that ptn may be an early indicator of cancer and might be of use in monitoring the efficacy of therapy (4). in vitro studies revealed that, unlike normal human cells, ptn mrna was expressed in a vast majority of cultured cancer cells (5). together, these in vivo and in vitro data suggest that ptn is a member of the network of growth factors involved in proliferation, angiogenesis, and metastasis of tumors. it is thought that ptn promotes tumor growth by stimulating angiogenesis (6). however, the mechanism by which ptn stimulates angiogenesis remained entirely unknown until the surprising findings associated with the present invention, which establish for the first time that ptn induces trans- differentiation of monocytes into endothelial-like cells. a. methods of regulating differentiation and treating associated disorders the present invention provides methods for regulating differentiation and related cellular processes (e.g., angiogenesis), based upon the discovery that ptn plays a fundamental role in these processes. in general, the methods of the invention comprise providing an inhibitor of ptn or a ptn signal transduction pathway, to a cell, tissue, or subject to reduce differentiation; or providing ptn, or an activator of ptn or a ptn signal transduction pathway, to increase differentiation. in particular embodiments, the methods of the invention comprise providing an inhibitor of a ptn receptor, or downstream signaling molecule, to a cell, tissue or subject to reduce differentiation, or providing an activator of a ptn receptor or activator thereof, to increase differentiation. in particular embodiments, activators and inhibitors are agonists or antagonists of one or more ptn receptors, respectively. in general, it is understood that inhibitors act by reducing the expression of a polypeptide or by reducing the functional activity of a polypeptide, directly or indirectly. in contrast, activators act by increasing the expression or functional activity of a polypeptide, directly or indirectly. thus, delivery of an activator includes delivery of the polypeptide itself, either as an isolated or purified polypeptide, or by means of an expression vector. in certain embodiments, the expression or functional activity of a polypeptide, e.g. , ptn or a ptn receptor, is reduced or increased by at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, in the presence of an inhibitor or activator, respectively, as compared to normal levels in the same or a similar cell type. in particular embodiments, an inhibitor or activator of ptn or a ptn receptor is a molecule that inhibits or increases, respectively, expression of a gene encoding ptn or a ptn receptor. for example, an activator of ptn or a ptn receptor includes a ptn or ptn receptor expression vector. in particular embodiments, ptn includes either ptn or midkine. in particular embodiments, the ptn receptor is cd 138, rtp β/ζ, syndecan 3, or alk, although it may be any known ptn or midkine receptor, including those specifically described herein. gene expression may be determined using routine methodologies, including rt-pcr, as described herein. in other embodiments, an inhibitor or activator of ptn or a ptn receptor reduces or increases a functional activity of ptn or a ptn receptor. examples of such functional activities include the ability of ptn to bind a ptn receptor, and the ability of a ptn receptor to bind ptn. such binding activity may be readily examined using routine methods available in the art. in another example, a functional activity is the ability of ptn to induce differentiation of a monocytes or pluripotent cell, which may be readily determined using methods known in the art and described herein. inhibitors and activators of ptn and ptn polynucleotides, polypeptides and fragments and variants thereof, as well as ptn receptors, ptn receptor polynucleotides, polypeptides and fragments and variants thereof, may be administered to a cell or tissue via any means available in the art, including, e.g., transfection, infection, electroporation, scrape-loading, transduction, or in culture media. in certain embodiments, inhibitors of ptn or ptn receptors, are introduced to a patient or subject systemically or locally. in particular embodiments, they are introduced to a patient by injection and/or using viral- based vectors. of course, the skilled artisan would appreciate that the method by which a compound is introduced into a cell, tissue or subject depends upon whether it is being administered in vitro, ex vivo, or in vivo. appropriate routes of delivery are known in the art. 1. methods of regulating differentiation the present invention demonstrates that ptn induces cellular differentiation. accordingly, the invention provides methods of inducing or inhibiting differentiation of a cell, including ptn-induced differentiation, hi particular embodiments, the methods of inhibiting differentiation of a cell comprise administering an inhibitor of either ptn or a ptn receptor to the cell. in contrast, methods of promoting differentiation comprise administering either or both of ptn and/or a ptn receptor, or a functional fragment or variant thereof, to a cell, hi related embodiments, methods of promoting differentiation comprise administering an activator of either ptn and/or a ptn receptor to a cell. the methods of the invention may be used to promote or inhibit differentiation of any cell capable of undergoing differentiation, de-differentiation, or trans- differentiation (collectively referred to herein as "differentiation"), including, e.g., monocyte/macrophages and bone marrow stem cells. in various embodiments, the methods may be practiced on pluripotent, multipotent or differentiated cells. the methods may be used to inhibit or induce differentiation of a cell in vitro, ex vivo, or in vivo. in addition, the methods may be used to inhibit or induce differentiation of cells of any organism, particularly mammalian cells, including, e.g. , human cells. in particular, the methods of the invention may be used to induce or inhibit growth and/or differentiation of tumor cells, including, e.g., mm cells. as used herein, the term "monocyte/macrophage" is used to collectively include both or either monocytes or macrophages, which are related cells of the mononuclear phagocytic system, originating in the bone marrow. it is understood that maturation from a monocyte into a macrophage is a gradual process, and that many cells within peripheral blood are at various stage of the process. accordingly, the term monocyte/macrophage encompasses monocytes, macrophages, and cells at various points in the maturation process. "monocytes" are agranular (despite small lysosomes) mononuclear leukocytes that circulate in blood for 1-2 days before migrating into tissue and becoming macrophages. "macrophages" are monocyte-derived large mononuclear phagocytic cells arising from hematopoietic stem cells in the bone marrow and mainly localized in the tissues, which perform an array of immune response functions, including nonspecific phagocytosis and pinocytosis, antigen presentation to t cells to initiate specific immune responses, and secretion of lymphokines (cytokines). macrophages can be activated by a variety of stimuli and assume many different forms, including epithelioid cells, multinucleate giant cells, microglia, kupffer cells, alveolar macrophages, and osteoclasts. as used herein, the term "endothelial-like cell" refers to both endothelial cells and cells expressing one or more endothelial cell specific marker genes but not fully differentiated into an endothelial cell. the term "stem cell" refers to multipotent cells capable of differentiating into specialized cells, which can serve as a continuous source of new tissue and blood cells. 2. methods of regulating angiogenesis and vasculogenesis given the association between ptn' s role in angiogenesis and ptn' s role in differentiation that is established by the present invention, the invention further provides methods of inhibiting or promoting angiogenesis and vasculogenesis associated with ptn. for example, the present invention establishes that bone marrow angiogenesis and vasculogenesis is induced by ptn expression by infiltrating monocyte/macrophages. accordingly, the invention establishes that angiogenesis and vasculogenesis may be inhibited by administering an inhibitor of ptn or a ptn signal transduction pathway to a cell. thus, in particular embodiments, the invention provides methods of inhibiting angiogenesis and vasculogenesis by providing an inhibitor of either ptn or a ptn receptor to a cell or tissue, including, e.g., monocyte/macrophages and bone marrow cells. the invention further establishes that angiogenesis and vasculogenesis . may be increased, promoted, or enhanced by administering an ptn or a ptn signal transduction pathway component, or an activator thereof, to a cell. thus, in particular embodiments, the invention provides methods of increasing or promoting angiogenesis and vasculogenesis by providing either ptn and/or a ptn receptor (or an activator of either molecule) to a cell or tissue, including, e.g., monocyte/macrophages and bone marrow cells. however, given the fundamental role of ptn-induced differentation established by the present invention, it is understood that the methods of the invention are not limited to regulating angiogenesis and vasculogenesis of the bone marrow, but are applicable to all cells and tissues capable of undergoing angiogenesis and vasculogenesis, including both solid and liquid tumors, developing tissues, regenerating organs, and the cerebral vasculature, for example. 3. methods of treating disease and injury a variety of diseases and disorders are associated with differentiation, angiogenesis, and vasculogenesis, including tumors, ischemic and inflammatory diseases, e.g., atherosclerosis and diabetes, alzheimer's disease, asthma, and obesity. ischemic diseases are typically associated with insufficient angiogenesis, while prolonged and excessive angiogenesis is associated with a variety of tumors and inflammatory diseases. angiogenesis and vasculogenesis also play a significant role in wound repair. revascularization at sites of injury is necessary for new tissue growth and wound repair. examples of injuries in which revascularization is critical include amputation and subsequent reattachment, surgical-induced injuries, burns, peripheral vascular disease, coronary heart disease, and stroke-induced ischemic injuries. as noted above, angiogenesis plays an important role in tumor growth and metastasis. while the role of angiogenesis in solid tumor growth has long been recognized, the important role of angiogenesis in liquid tumor growth has only more recently been appreciated. angiogenesis has now been demonstrated to play an important role in liquid tumors, including, but not limited to malignant myeloma. accordingly, the present invention provides methods of treating both solid and liquid tumors comprising administering an inhibitor of ptn, a ptn receptor, and/or a component of a ptn signal transduction pathway to a patient in need thereof. the present invention provides methods of treating diseases and injuries that are associated with increased angiogenesis or vasculogenesis, comprising providing an inhibitor of either ptn, a ptn receptor, or another component of a ptn signal transduction pathway, to a patient in need thereof. it is understood that inhibitors of ptn (or any other component of a ptn signaling pathway) may inhibit ptn directly, e.g., by inhibiting ptn activity or expression, or may inhibit ptn indirectly by, e.g., inhibiting binding of ptn to a receptor or interfering with the ptn signaling cascade. the present invention further provides methods of treating diseases and injuries that exhibit a therapeutic benefit from increased angiogenesis or vasculogenesis by providing a ptn polynucleotide or polypeptide, or a functional variant or fragment or either, to a patient in need thereof. such methods may also be practiced, e.g., by overexpressing ptn receptor, or a functional variant or fragment thereof in diseased or injured cells or tissues. in certain embodiments, the methods described herein are used to treat any type of cancer. in particular, these methods are applied to cancers of the blood and lymphatic systems, including lymphomas, leukemia, and myelomas. examples of specific cancers that may be treated according to the invention include, but are not limited to, hodgkin's and non-hodgkin's lymphoma (nhl), including any type of nhl as defined according to any of the various classification systems such as the working formulation, the rappaport classification and, preferably, the real classification. such lymphomas include, but are not limited to, low-grade, intermediate-grade, and high-grade lymphomas, as well as both b -cell and t-cell lymphomas. the methods described herein are also used to treat any form of leukemia, including adult and childhood forms of the disease. for example, any acute, chronic, myelogenous, and lymphocytic form of the disease can be treated using the methods of the present invention. in preferred embodiments, the methods are used to treat acute lymphocytic leukemia (all). more information about the various types of leukemia can be found, inter alia, from the leukemia and lymphoma society of america {see, e.g., www.leukemia.org). the methods are further used to treat any type of myeloma. a patient's myeloma is often referred to by the type of immunoglobulin or light chain (kappa or lambda type) produced by the cancerous plasma cell. the frequency of the various immunoglobulin types of myeloma parallels the normal serum concentrations of the immunoglobulins. the most common myeloma types are igg and iga. igg myeloma accounts for about 60% to 70% of all cases of myeloma and iga accounts for about 20% of cases. few cases of igd and ige myeloma have been reported. although a high level of m protein in the blood is a hallmark of myeloma disease, about 15% to 20% of patients with myeloma produce incomplete immunoglobulins, containing only the light chain portion of the immunoglobulin (also known as bence jones proteins, after the chemist who discovered them). these patients are said to have light chain myeloma, or bence jones myeloma. in these patients, m protein is found primarily in the urine, rather than in the blood. these bence jones proteins may deposit in the kidney and clog the tiny tubules that make up the kidney' s filtering system, which can eventually cause kidney damage and result in kidney failure. additional forms of myeloma have also been described. a rare form of myeloma called nonsecretory myeloma affects about 1 % of myeloma patients. in this form of the disease, plasma cells do not produce m protein or light chains. recurrent myeloma is multiple myeloma that has persisted or returned (recurred/relapsed) following treatment with radiation, chemotherapy and/or stem cell transplant. additionally, solid tumors are also treated using the methods described herein, including, but not limited to, neuroblastomas, prostate cancers, small cell lung cancer, colon cancer, ovarian cancer, non-small cell lung cancer, brain tumors, and breast cancer. in certain embodiments, the invention is used in tissue engineering, including the production of artificial blood vessels. for example, in a particular embodiment, monocyte/macrophages are isolated from blood and treated with ptn to promote differentiation into endothelial-like cells. these cells are then used in a variety of different therapeutic applications. for example, the produced endothelial-like cells may be used to line artificial blood vessels, may be applied to sites of tissue injury, e.g. , burns, or applied to wounds to promote healing and tissue regrowth. in another embodiment, inhibitors of ptn are applied directly to a site of injury or wound, in order to inhibit or decrease scar and/or keloid formation. in a related embodiment, ptn is applied to a wound site following reattachment of an amputated or severed limb or digit, in order to promote vascularization of the reattached tissue. in a further embodiment, stents are coated with ptn or a functional fragment or variant thereof, in order to promote endothelial cell regrowth following stent- induced injury of blood vessels. alternatively, stents may be coated with endothelial-like cells produced by isolating monocyte/macrophages from a patient' s serum and treating the isolated cells with ptn to induce differentiation into endothelial-like cells. the methods of the invention are also used to treat vascular and heart diseases. the formation of neovessels is understood to play a role in atherosclerotic vascular remodeling, and angiogenesis and vasculogenesis of atherosclerotic placques, including coronary atherosclerotic placques, supports their growth. accordingly, the invention provides methods of reducing atherosclerotic placque growth by providing an inhibitor of ptn or a ptn receptor to blood vessels and sites of placque formation. in one embodiment, the inhibitor is associated with a solid support, such as a stent or balloon, which may be placed at a site of atherosclerosis. peripheral arterial disease is a chronic condition in which arteries that supply blood to the legs become blocked by a buildup of plaque. the restricted blood flow causes a painful, potentially life-threatening condition called claudication, which is similar to angina experienced by people with certain types of heart disease. peripheral vascular disease is frequently associated with pathological blood vessel occlusion. the method of the present invention include inducing therapeutic angiogenesis by providing ptn to tissues having occluded vessels in order to promote growth of new vessels and collateral circulation, e.g., in chronically occluded lower extremity arterial vessels. in certain embodiments, the methods of the invention are practiced using a pharmaceutical formulation of a ptn inhibitor or a ptn polynucleotide, polypeptide, or functional fragments or variant thereof. accordingly, pharmaceutical formulations of the compound or molecule being administered will often further comprise one or more buffers (e.g., neutral buffered saline or phosphate buffered saline), carbohydrates (e.g., glucose, mannose, sucrose or dextrans), mannitol, proteins, polypeptides or amino acids such as glycine, antioxidants, bacteriostats, chelating agents such as edta or glutathione, adjuvants (e.g., aluminum hydroxide), solutes that render the formulation isotonic, hypotonic or weakly hypertonic with the blood of a recipient, suspending agents, thickening agents and/or preservatives. alternatively, compositions of the present invention may be formulated as a lyophilizate. the pharmaceutical compositions described herein may be presented in unit-dose or multi-dose containers, such as sealed ampoules or vials. such containers are typically sealed in such a way to preserve the sterility and stability of the formulation until use. in general, formulations may be stored as suspensions, solutions or emulsions in oily or aqueous vehicles. alternatively, a pharmaceutical composition may be stored in a freeze-dried condition requiring only the addition of a sterile liquid carrier immediately prior to use. the development of suitable dosing and treatment regimens for using the particular compositions described herein in a variety of treatment regimens, including e.g., oral, parenteral, intravenous, intranasal, and intramuscular administration and formulation, is well known in the art. administration of an inhibitor of ptn or a ptn polynucleotide or polypeptide, or functional fragment or variant thereof, or activator or inhibitor thereof, may be accomplished by any appropriate means, including, for example, topical, oral, nasal, mucosal, intravenous, intracranial, intraperitoneal, subcutaneous and intramuscular administration. 4. combination therapies the methods of the present invention, including the delivery of ptn inhibitors and/or activators, may be practiced alone or in combination with the delivery of one or more additional therapeutic agents or treatments. accordingly, a ptn inhibitor or activator may be administered to a subject before, during or after treatment with one or more additional therapeutic agents or treatments. this additional treatment may include any type of treatment, including the administration of a therapeutic agent, e.g., a chemotherapeutic drug, surgical treatment, bone marrow transplantation, radiation therapy, or the implantation of a medical device. a variety of chemotherapeutic agents are known and available in the art, and the invention includes using an inhibitor or inducer of ptn in combination with any of these. in certain embodiments, the combination therapy is used to treat multiple myeloma and comprises treatment with an inhibitor of ptn in combination with a chemotherapeutic agent used to treat multiple myeloma. a combination of the alkylating drug melphalan and the steroid prednisone is often the initial treatment for multiple myeloma. alkylating drugs hinder the growth and division of cells by interfering with dna replication. steroids, such as prednisone, are often used in combination with alkylating agents because they have been shown to enhance the treatment results. other drugs frequently used to treat multiple myeloma include, but are not limited to, arsenic trioxide and ascorbic acid. accordingly, in certain embodiments, an inhibitor of ptn is used in combination with one or more other drugs used to treat multiple myeloma. patients who do not respond to mp and its alternatives, and patients who relapse after mp treatment, often react well to a combination chemotherapy regimen known as vad. vad stands for vincristine, doxorubicin and high-dose dexamethasone. vad-resistant cases may benefit from a combination of vad and cyclophosphamide. if mp, vad, or similar therapies prove ineffective, patients may be prescribed thalidomide. approximately fifty percent of multiple myeloma cases that do not respond to mp and vad respond to thalidomide. clinical trials are investigating the effectiveness of using thalidomide as a primary treatment, in combination with chemotherapy, and with oral steroids. in certain embodiments, the invention provides methods of combination therapy that include a ptn inhibitor or inducer combined with anti-tumor agents such as monoclonal antibodies including, but not limited to, oncolym™ (techniclone corp. tustin, ca) or rituxan™ (idec pharmaceuticals), bexxar™ (coulter pharmaceuticals, palo alto, ca), or idec- y2b8 (idec pharmaceuticals corporation). in another embodiment, the methods of the invention are practiced in combination with treatment with an angiolytic, a drug that selectively targets tumor vasculature to create hemorrhage within the tumor and tumor cell death. examples of angiolytic drugs include exherin™, an n-cadherin antagonist and v-cadherin antagonists. 5. combinations with other differentiation or angio genesis factors the invention further contemplates providing an activator or inhibitor of ptn (or a ptn signal transduction pathway), including, e.g., ptn or a ptn receptor polynucleotide or polypeptide, or functional fragment or variant thereof, to a cell or patient, in combination with one or more additional factor that inhibits or promotes differentiation or angiogenesis. additional factors may act in concert, e.g., synergistically or additively, with the inhibitor or activator of ptn or a ptn receptor, to inhibit or promote differentiation or angiogenesis. additional factors may be administered before, after, or at the same time as the activator or inhibitor of ptn or a ptn receptor. additional factors may be administered in a variety of different forms, e.g., as a polypeptide or a polynucleotide encoding the polypeptide, and by any means available in the art, including those described herein for administering a ptn activator or inhibitor, including ptn polynucleotides, polypeptides, and antibodies to ptn. in certain embodiments, the administration of one or more additional factors in combination with a ptn molecule, receptor, or functional fragment or variant thereof, causes differentiation to occur more rapidly or to a more fully differentiated state or angiogenesis to occur more rapidly or to a greater extent than observed upon treatment with a ptn molecule, receptor, or functional fragment or variant thereof, alone. for example, in one embodiment, administration of an additional factor that promotes differentiation in combination with a ptn molecule or functional fragment or variant thereof induces monocyte/macrophages to express a larger number of or a higher level of endothelial cell markers than treatment with a ptn molecule or functional fragment or variant alone. accordingly, the invention includes a method of inducing differentiation of a cell, e.g., trans-differentiation of a monocyte/macrophage into an endothelial-like or endothelial cell, comprising administering a ptn molecule or functional fragment or variant thereof in combination with one or more additional factors that promotes differentiation. a variety of factors capable of inducing or inhibiting differentiation or angiogenesis have been described and are known in the art. the invention contemplates the use of any of such factors in any of the methods of the invention. for example, various classes of trophic factors have been defined in the art, including, e. g. , adhesion molecules, bone morphogenetic proteins, cytokines, eph receptor tyrosine kinases, epidermal growth factors, fibroblast growth factors, glial-derived neurotrophic factor, heparin binding growth factors, insulin-like growth factors, neurotrophins, semaphorins, transforming growth factor beta, and tyrosine kinase receptor ligands. in certain embodiments, a factor that induces or promotes differentiation is a heparin binding growth factor. heparin binding growth factors include, e.g., vascular endothelial growth factor, pleiotrophin, and midkine. vascular endothelial cell growth factors are further described in achen, m. g. and stacker, s. a., int j exp pathol. 1998 oct;79(5):255-65. other factors that may be used to induce or promote differentiation include, e.g., myeloid differentiation factor 88, granulocyte colony stimulating factor, granulocyte-macrophage colony stimulating factor, hepatocyte growth factor, insulin-like growth factor, macrophage colony stimulating factor (mcsf), platelet derived growth factor, transforming growth factor, angiopoietin 1 and 2, and ligands for tie-2, including those described in pomyje et al, 2001, melanoma res 11 : 639-643. in specific embodiments, either or both of ptn or a ptn receptor is provided in combination with mcsf and/or vegf. in another related embodiment, either or both of ptn or a ptn receptor is provided in combination with both mcsf and vegf. in one specific embodiment, the invention includes a method of promoting or inducing trans-differentiation of a monocyte/macrophages into an endothelial-like or endothelial cell, comprising administering to the cells a ptn molecule or functional fragment or variant thereof in combination with a heparin binding growth factor. in one embodiment, the heparin binding growth factor is vascular endothelial growth factor. in another embodiment, the heparin binding growth factor is midkine. in a further embodiment, the growth factor is mcsf. combinations of growth factors may also be used according to the invention. endothelial differentiation-related factor (edf)-i has been identified as a protein involved in the repression of endothelial cell differentiation (dragoni, l, et al., (1998) j. biol. chem. 273, 31119-31124). accordingly, in another embodiment, the invention provides a method of inhibiting differentiation along the endothelial cell pathway by administering to a cell an inhibitor of ptn or a ptn receptor, in combination with edf-i. ptn binding to rptp β/ζ leads to the accumulation of β-catenin and downstream activation of nf-κb, il-6 and proliferative gene including c-myc and cyclin dl . ptn signaling through alk (the path predicted to be involved in transdifferentiation and ptn activation of endothelial cells) activates the irs-i, pi3'k/akt and downstream nf-κb, jak/stat3 and mapk pathways. inhibition of any of, or a combination of, these intermediates inhibits ptn-stimulated angiogenesis. a variety of heparin binding growth factors, cytokines and chemokines have been identified that induce angiogenesis, including, e.g. , fibroblast growth factors, vascular endothelial growth factor, placental growth factor, heparin-binding egf-like growth factor, hepatocyte growth factor, transforming growth factor-beta, interferon-gamma, platelet- derived growth factor, platelet factor-4, interleukin-8, macrophage inflammatory protein-1 , interferon-γ-inducible protein- 10, and hiv-tat transactivating factor. other factors that induce angiogenesis included, e.g., tumor angiogenesis factor and vascular endothelial growth factor-a. vascular endothelial growth factor-a (vegf) 5 belonging to the platelet- derived growth factor (pdgf)a^egf family of growth factors, is a key regulator of angiogenesis. vegf is a heparin-binding glycoprotein of about 45 kda molecular weight that stimulates proliferation, migration, and proteolytic activity of endothelial cells. vegf is also necessary for the survival of endothelial cells due to its ability to inhibit apoptosis and capillary regression. without wishing to be bound by one particular theory, it is understood that through its capacity to induce nitric oxide, vegf may mediate vasodilatation and increase blood flow that precede angiogenesis. vegf is also a potent mediator of increased vascular permeability; hence its other name, vascular permeability factor (senger et al. 1983). to date, six human vegf mrna species, encoding vegf isoforms of 121, 145, 165, 183, 189 and 206 amino acids, are produced by alternative splicing of the vegf mrna. an important biological property that distinguishes the different vegf isoforms is their heparin and heparan-sulphate-binding ability. vegf 121 is the most soluble isoform and does not bind to heparin or extracellular matrix (ecm), whereas vegf 189 and vegf 206 are almost completely sequestered in the ecm. vegf 165 is a heparin-binding protein, and 50-70% of vegf 165 remains bound to cell surface and ecm. vegf 121 , vegf 145 and vegf 165 induce angiogenesis in vivo, but vegf 145 is found mainly to be expressed in cells derived from reproductive organs, as is apparently also vegf 206 . vegf proteins may become available to target cells as freely diffusible proteins (vegfi 21 or vegf 165 ) or following protease activation and cleavage. basic fibroblast growth factor (bfgf; also called fgf-2) is a well- documented angiogenic growth factor and induces endothelial cell replication, migration and extracellular proteolysis. bfgf is produced by several normal and tumor cells, endothelial cells included, and has autocrine activities on angiogenesis. bfgf may promote angiogenesis both by a direct effect on endothelial cells and indirectly by the upregulation of vegf in endothelial cells, and bfgf and vegf have a synergistic effect in the induction of angiogenesis both in vitro and in vivo. also, induction of bfgf induced angiogenesis is partly dependent on the activation of vegf (tille et al. 2001). bfgf belongs to the fgf superfamily, which contains at least twenty distinct fgfs. accordingly, in related embodiments, the invention includes a method of inducing or promoting angiogenesis comprising administering to a cell or patient a ptn molecule or functional fragment or variant thereof in combination with one or more factors that promote angiogenesis. in one embodiment, a factor is vegf, while in another related embodiment, a factor is fgf. in a further embodiment, both vegf and fgf are administered in combination with a ptn molecule or functional fragment or variant thereof. in other embodiments, the factor is mcsf or vegf, or both. factors that inhibit angiogenesis have also been identified and may be used according to the invention, e.g., in combination with an inhibitor of ptn to inhibit or reduce angiogenesis. such factors include, but are not limited to, angiostatin, endostatin, fumagillin analogue tnp-470, mammastatin, the monoclonal antibody bevacizumab (avastin), thalidomide, and matrix metalloproteinase inhibitors. other factors that may be used according to the invention include inhibitors of alk signaling intermediates, including but not limited to, bortezomib, rapamycin (and its analogs), histone deacetylase (hdac) inhibitors and monoclonal antibodies against vegfr. other additional chemical inhibitors particularly useful for in vitro studies include, e.g. , ly294002, u0126, and pp2. the invention, thus, includes methods of reducing or inhibiting angiogenesis, comprising administering to a cell or patient an inhibitor of ptn in combination with one or more angiogenesis inhibitors. the methods described herein may be readily adapted for the therapeutic treatment of patients, in order to reduce or alleviate diseases and disorders associated with differentiation or angiogenesis, including, e.g., multiple myeloma, as described supra. accordingly, the invention further includes methods of treating diseases and disorders associated with angiogenesis and vasculogenesis, comprising administering to a patient in need thereof an inhibitor of ptn, or a ptn molecule or functional fragment or variant thereof, in combination with one or more other factors that either inhibit or promote differentiation or angiogenesis. generally, an inhibitor of ptn is administered in combination with another inhibitor of differentiation or angiogenesis, and a ptn molecule or functional fragment or variant thereof is administered in combination with another inducer of differentation or angiogenesis. 6. methods of diagnosing and staging multiple myeloma as discovered according to the present invention, ptn and ptn receptors levels are increased in multiple myeloma. accordingly, the invention further includes methods of diagnosing multiple myeloma, as well as monitoring the response of multiple myeloma to treatment, based upon the level of ptn or a ptn receptor observed in a biological sample obtained from a patient, including, e.g., a patient's bloodstream, serum, bone marrow, or tissue. in general, multiple myeloma is diagnosed by the presence of at least two-fold, at least five-fold, at least ten-fold, or higher levels of ptn as compared to those in a normal control subject. in general, methods of diagnosing multiple myeloma comprise: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient; and (b) comparing the amount detected in step (a) to a predetermined cut-off value or to an amount detected in a control biological sample, wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (a) as compared to the predetermined cut-off value or amount in the control biological sample of (b) indicates the presence of multiple myeloma. a variety of methods of determining ptn or ptn receptor levels are known and available in the art. in certain embodiments, these involve the use of a ptn binding agent, such as a ptn specific antibody, or a ptn receptor binding agent. there are a variety of assay formats known to those of ordinary skill in the art for using a binding agent to detect polypeptide markers in a sample. see, e.g. , harlow and lane, antibodies: a laboratory manual, cold spring harbor laboratory, 1988. in a related embodiment, the present invention includes a method of monitoring the progression or response to treatment of multiple myeloma, comprising: (a) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from a patient diagnosed with multiple myeloma at a first time point; (b) detecting an amount of pleiotrophin or a pleiotrophin receptor in a biological sample obtained from the patient at a second time point or following treatment; and (c) comparing the amount detected in step (a) to the amount detected in step (b), wherein an increased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (b) indicates that said multiple myeloma is progressing, and wherein a decreased amount of said pleiotrophin or pleiotrophin receptor in the biological sample of (b) as compared to the amount in the biological sample of (a) indicates that said multiple myeloma is entering remission or responding to treatment. in various embodiments of methods of detecting pleiotrophin or a pleiotrophin receptor, a biological sample is selected from the group consisting of: serum, bone marrow, and tissue. in particular embodiments, mrna levels are determined, while in other embodiments, polypeptide levels are determined. in one embodiment, detetion is performed using one or more primers specific for said pleiotrophin or pleiotrophin receptor. in another embodiment, detection is performed using an antibody specific for said pleiotrophin or pleiotrophin receptor. in one embodiment, the presence or absence of multiple myeloma in a patient may be determined by (a) contacting a biological sample obtained from a patient with a ptn binding agent; (b) detecting in the sample a level of ptn polypeptide that binds to the binding agent; and (c) comparing the level of ptn polypeptide with a predetermined cut-off value or with the value obtained from a normal control subject. in certain embodiments, the cut-off value for the detection of a multiple myeloma is the average mean signal obtained when the immobilized antibody is incubated with samples from patients without multiple myeloma. in general, a sample generating a signal that is three standard deviations above the predetermined cut-off value is considered positive for multiple myeloma. in an alternate preferred embodiment, the cut-off value is determined using a receiver operator curve, according to the method of sackett et al., clinical epidemiology: a basic science for clinical medicine, little brown and co., 1985, p. 106-7. briefly, in this embodiment, the cut-off value may be determined from a plot of pairs of true positive rates (/. e. , sensitivity) and false positive rates (100%-specificity) that correspond to each possible cut-off value for the diagnostic test result. the cut-off value on the plot that is the closest to the upper left-hand corner (j. e. , the value that encloses the largest area) is the most accurate cut-off value, and a sample generating a signal that is higher than the cut-off value determined by this method may be considered positive. alternatively, the cut-off value may be shifted to the left along the plot, to minimize the false positive rate, or to the right, to minimize the false negative rate. in general, a sample generating a signal that is higher than the cut-off value determined by this method is considered positive for multiple myeloma. in one embodiment, the assay involves the use of a ptn binding agent immobilized on a solid support to bind to and remove the ptn polypeptide from the remainder of the sample. the bound ptn polypeptide may then be detected using a detection reagent that contains a reporter group and specifically binds to the binding agent/polypeptide complex. such detection reagents may comprise, for example, a binding agent that specifically binds to the ptn polypeptide or an antibody or other agent that specifically binds to the binding agent, such as an antiimmunoglobulin, protein g 5 protein a or a lectin. in a related embodiment, the assay is performed in a flow-through or strip test format, wherein the ptn binding agent, e.g. , antibody, is immobilized on a membrane, such as nitrocellulose. in the flow-through test, ptn polypeptides within the sample bind to the immobilized binding agent as the sample passes through the membrane. a second, labeled binding agent then binds to the ptn binding agent-polypeptide complex as a solution containing the second binding agent flows through the membrane. the detection of bound second binding agent may then be performed as described above. in the strip test format, one end of the membrane to which binding agent is bound is immersed in a solution containing the sample. the sample migrates along the membrane through a region containing second binding agent and to the area of immobilized binding agent. concentration of second binding agent at the area of immobilized antibody indicates the presence of multiple myeloma. the invention provides similar methods for staging or monitoring the progression of multiple myeloma, as well as determining response to treatment. since ptn levels correlate with disease, levels associated with particular stages are determined and compared to those observed in a patient's serum to determine the stage of the patient's disease. similarly, disease progression and response to treatment or therapy is monitored by comparing ptn levels in a patient's serum (or other biological sample) at different time points during the course of the disease or before and after a treatment regimen. according to the present invention, ptn serum levels are elevated in multiple myeloma patients, and the levels of ptn correlate with disease stage, i.e., ptn levels are higher in progressed mm and become lower in response to treatment or entering remission. thus, the present invention provides a rapid and reliable method of diagnosing, staging, and monitoring progression or response to treatment of multiple myeloma disease, using a serum sample obtained from the patient's bloodstream. in one embodiment, the method is practiced by elisa assay using an antibody specific for ptn. the invention further provides kits for detecting, staging, or monitoring multiple myeloma, which comprise reagents suitable or determining ptn levels in a biological, e.g., serum, sample obtained from a patient. in one embodiment, the kit includes reagents for performing elisa, such as an antibody specific for ptn. said kits may further include instructions for use thereof. b . inhibitors of ptn and ptn receptors methods of the invention directed to inhibiting differentiation and related cellular processes, e.g., angiogenesis, are practiced using an agent that inhibits ptn and/or inhibits a ptn receptor or other component of a ptn signal transduction pathway. in certain embodiments such an agent specifically reduces or inhibits ptn' s ability to induce differentiation of monocyte/macrophages activity, directly, or by interfering with a ptn signaling cascade. in particular embodiments, such inhibitors are polynucleotides, polypeptides, peptides, peptide nucleic acids, antibodies and fragments thereof, viruses, inorganic compounds and organic compounds. the invention includes inhibitors of ptn- mediated trans-differentiation and angiogenesis. 1. polynucleotide inhibitors in certain embodiments, polynucleotide inhibitors are antisense rna, ribozymes, or rna interference reagents designed to specifically target ptn or a ptn receptor, according to methods known and available in the art. the terms "dna" and "polynucleotide" are used essentially interchangeably herein to refer to a dna molecule that has been isolated free of total genomic dna of a particular species. "isolated," as used herein, means that a polynucleotide is substantially away from other coding sequences, and that the dna molecule does not contain large portions of unrelated coding dna, such as large chromosomal fragments or other functional genes or polypeptide coding regions. of course, this refers to the dna molecule as originally isolated, and does not exclude genes or coding regions later added to the segment by the hand of man. as will be understood by those skilled in the art, the polynucleotide compositions of this invention can include genomic sequences, extra-genomic and plasmid- encoded sequences and smaller engineered gene segments that express, or may be adapted to express, proteins, polypeptides, peptides and the like. such segments may be naturally isolated, or modified synthetically. polynucleotides of the invention may be single- stranded (coding or antisense) or double-stranded, and may be dna (genomic, cdna or synthetic) or rna molecules. a. antisense in one embodiment, a ptn or ptn receptor inhibitor is an antisense rna directed to ptn polynucleotides, ptn receptor polynucleotides, or other components of the ptn signaling cascade. antisense oligonucleotides have been demonstrated to be effective and targeted inhibitors of protein synthesis, and, consequently, can be used to specifically inhibit protein synthesis by a targeted gene. the efficacy of antisense oligonucleotides for inhibiting protein synthesis is well established. for example, the synthesis of polygalactauronase and the muscarine type 2 acetylcholine receptor are inhibited by antisense oligonucleotides directed to their respective irirna sequences (u. s. patent 5,739,119 and u. s. patent 5,759,829). further, examples of antisense inhibition have been demonstrated with the nuclear protein cyclin, the multiple drug resistance gene (mdgl), icam-i , e-selectin, stk-i , striatal gaba a receptor and human egf (jaskulski et ah, science. 1988 jun 10;240(4858): 1544-6; vasanthakumar and ahmed, cancer commun. 1989;l(4):225-32; peris etal, brain res moi brain res. 1998 jun 15;57(2):310- 20; u. s. patent 5,801,154; u.s. patent 5,789,573; u. s. patent 5,718,709 and u.s. patent 5,610,288). furthermore, antisense constructs have also been described that inhibit and can be used to treat a variety of abnormal cellular proliferations, e.g. cancer (u. s. patent 5,747,470; u. s. patent 5,591,317 and u. s. patent 5,783,683). therefore, in certain embodiments, the present invention relates to methods of providing oligonucleotide sequences that comprise all, or a portion of, any sequence that is capable of specifically binding to a ptn target polynucleotide sequence, or a complement thereof. in another embodiment, the oligonucleotide sequence comprises all, or a portion of, any sequence that is capable of specifically binding to a ptn receptor polynucleotide sequence, or a complement thereof. in one embodiment, the antisense oligonucleotides comprise dna or derivatives thereof. in another embodiment, the oligonucleotides comprise rna or derivatives thereof. the antisense oligonucleotides may be modified dnas comprising a phosphorothioated modified backbone. also, the oligonucleotide sequences may comprise peptide nucleic acids or derivatives thereof. in each case, preferred compositions comprise a sequence region that is complementary, and more preferably, completely complementary to one or more portions of a ptn target gene or polynucleotide sequence. methods of producing antisense molecules are known in the art and can be readily adapted to produce an antisense molecule that targets ptn or a ptn receptor. selection of antisense compositions specific for a given sequence is based upon analysis of the chosen target sequence and determination of secondary structure, t m , binding energy, and relative stability. antisense compositions may be selected based upon their relative inability to form dimers, hairpins, or other secondary structures that would reduce or prohibit specific binding to the target mrna in a host cell. highly preferred target regions of the mrna include those regions at or near the aug translation initiation codon and those sequences which are substantially complementary to 5 ' regions of the mrna. these secondary structure analyses and target site selection considerations can be performed, for example, using v.4 of the oligo primer analysis software and/or the blastn 2.0.5 algorithm software (altschul et al, nucleic acids res. 1997, 25(17):3389-402). the use of an antisense delivery method employing a short peptide vector, termed mpg (27 residues), is also contemplated. the mpg peptide contains a hydrophobic domain derived from the fusion sequence of hiv gp41 and a hydrophilic domain from the nuclear localization sequence of sv40 t-antigen (morris et al., nucleic acids res. 1997 jui 15;25(14):2730-6). it has been demonstrated that several molecules of the mpg peptide coat the antisense oligonucleotides and can be delivered into cultured mammalian cells in less than 1 hour with relatively high efficiency (90%). further, the interaction with mpg strongly increases both the stability of the oligonucleotide to nuclease and the ability to cross the plasma membrane. b. ribozymes according to another embodiment of methods of the invention, ribozyme molecules are used to inhibit expression of a ptn target gene or polynucleotide sequence, a ptn receptor gene, or another component of the ptn signaling cascade. ribozymes are rna-protein complexes that cleave nucleic acids in a site-specific fashion. ribozymes have specific catalytic domains that possess endonuclease activity (kim and cech, proc natl acad sci u s a. 1987 dec;84(24):8788-92; forster and symons, cell. 1987 apr 24;49(2):211-20). for example, a large number of ribozymes accelerate phosphoester transfer reactions with a high degree of specificity, often cleaving only one of several phosphoesters in an oligonucleotide substrate (cech et al, cell. 1981 dec;27(3 pt 2):487- 96; michel and westhof, j moi biol. 1990 dec 5;216(3):585-610; reinhold-hurek and shub, nature. 1992 may 14;357(6374):173-6). this specificity has been attributed to the requirement that the substrate bind via specific base-pairing interactions to the internal guide sequence ("igs") of the ribozyme prior to chemical reaction. at least six basic varieties of naturally-occurring enzymatic rnas are known presently. each can catalyze the hydrolysis of rna phosphodiester bonds in trans (and thus can cleave other rna molecules) under physiological conditions. in general, enzymatic nucleic acids act by first binding to a target rna. such binding occurs through the target binding portion of a enzymatic nucleic acid which is held in close proximity to an enzymatic portion of the molecule that acts to cleave the target rna. thus, the enzymatic nucleic acid first recognizes and then binds a target rna through complementary base- pairing, and once bound to the correct site, acts enzymatically to cut the target rna. strategic cleavage of such a target rna will destroy its ability to direct synthesis of an encoded protein. after an enzymatic nucleic acid has bound and cleaved its rna target, it is released from that rna to search for another target and can repeatedly bind and cleave new targets. the enzymatic nature of a ribozyme may be advantageous over many technologies, such as antisense technology (where a nucleic acid molecule simply binds to a nucleic acid target to block its translation), since the concentration of ribozyme necessary to affect inhibition of expression is lower than that of an antisense oligonucleotide. this advantage reflects the ability of the ribozyme to act enzymatically. thus, a single ribozyme molecule is able to cleave many molecules of target rna. in addition, the ribozyme is a highly specific inhibitor, with the specificity of inhibition depending not only on the base pairing mechanism of binding to the target rna, but also on the mechanism of target rna cleavage. single mismatches, or base-substitutions, near the site of cleavage can completely eliminate catalytic activity of a ribozyme. similar mismatches in antisense molecules do not prevent their action (woolf et al, proc natl acad sci u s a. 1992 aug 15;89(16):7305-9). thus, the specificity of action of aribozyme is greater than that of an antisense oligonucleotide binding the same rna site. the enzymatic nucleic acid molecule may be formed in a hammerhead, hairpin, a hepatitis δ virus, group i intron or rnasep rna (in association with an rna guide sequence) or neurospora vs rna motif, for example. specific examples of hammerhead motifs are described by rossi et al. nucleic acids res. 1992 sep 11;20(17):4559-65. examples of hairpin motifs are described by hampel et al. (eur. pat. appl. publ. no. ep 0360257), hampel and tritz, biochemistry 1989 jun 13;28(12):4929- 33; hampel et al, nucleic acids res. 1990 jan 25;18(2):299-304 and u. s. patent 5,631,359. an example of the hepatitis δ virus motif is described by perrotta and been, biochemistry. 1992 dec 1;31(47): 11843-52; an example ofthe rnasep motifis described by guerrier-takada et al, cell. 1983 dec;35(3 pt 2):849-57; neurospora vs rna ribozyme motifis described by collins (saville and collins, cell. 1990 may 18;61(4):685- 96; saville and collins, procnatl acad sci u s a. 1991 oct l;88(19):8826-30; collins and olive, biochemistry. 1993 mar 23 ;32(11):2795-9); and an example ofthe group i intron is described in (u. s. patent 4,987,071). important characteristics of enzymatic nucleic acid molecules used according to the invention are that they have a specific substrate binding site which is complementary to one or more ofthe target gene dna or rna regions, and that they have nucleotide sequences within or surrounding that substrate binding site which impart an rna cleaving activity to the molecule. thus the ribozyme constructs need not be limited to specific motifs mentioned herein. methods of producing a ribozyme targeted to ptn are known in the art. ribozymes may be designed as described in int. pat. appl. publ. no. wo 93/23569 and int. pat. appl. publ. no. wo 94/02595, each specifically incorporated herein by reference and synthesized to be tested in vitro and in vivo, as described therein. ribozyme activity can be optimized by altering the length ofthe ribozyme binding arms or chemically synthesizing ribozymes with modifications that prevent their degradation by serum ribonucleases (see e.g., int. pat. appl. publ. no. wo 92/07065; int. pat. appl. publ. no. wo 93/15187; int. pat. appl. publ. no. wo 91/03162; eur. pat. appl. publ. no. 92110298.4; u. s. patent 5,334,711 ; and int. pat. appl. publ. no. wo 94/13688, which describe various chemical modifications that can be made to the sugar moieties of enzymatic rna molecules), modifications which enhance their efficacy in cells, and removal of stem ii bases to shorten rna synthesis times and reduce chemical requirements. c. rnai molecules rna interference methods using rnai molecules also may be used to disrupt the expression of a gene or polynucleotide of interest, including a ptn gene, a ptn receptor gene, or another gene associated with the ptn signaling cascade. while the first described rnai molecules were rna:rna hybrids comprising both an rna sense and an rna antisense strand, it has now been demonstrated that dna sense:rna antisense hybrids, rna sense:dna antisense hybrids, and dna:dna hybrids are capable of mediating rnai (lamberton, j. s. and christian, a.t., (2003) molecular biotechnology 24:111-119). accordingly, the invention includes the use of rnai reagents comprising any of these different types of double-stranded molecules. in addition, it is understood that rnai reagents may be used and introduced to cells in a variety of forms. accordingly, as used herein, rnai reagents encompasses any and all reagents capable of inducing an rnai response in cells, including, but not limited to, double-stranded polynucleotides comprising two separate strands, i. e. a sense strand and an antisense strand, polynucleotides comprising a hairpin loop of complementary sequences, which forms a double-stranded region, e.g., shrnai molecules, and expression vectors that express one or more polynucleotides capable of forming a double-stranded polynucleotide alone or in combination with another polynucleotide. in one particular embodiment, a dsrna molecule that targets and induces degradation of a ptn or ptn receptor polynucleotide is introduced to a cell. while the exact mechanism is not essential to the invention, it is believed the association of the dsrna to the target gene is defined by the homology between the dsrna and the actual and/or predicted mrna transcript. it is believed that this association will affect the ability of the dsrna to disrupt the target gene. dsrna methods and reagents are described in pct applications wo 99/32619, wo 01/68836, wo 01/29058, wo 02/44321, wo 01/92513, wo 01/96584, and wo 01/75164, which are hereby incorporated by reference in their entirety. in one embodiment of the invention, rna interference (rnai) may be used to specifically inhibit target expression of ptn, a ptn receptor, including, e.g., a monocyte/macrophage or stem cell receptor for ptn, or another component of the ptn signaling cascade. double-stranded rna-mediated suppression of gene and nucleic acid expression may be accomplished according to the invention by introducing dsrna, sirna or shrna into cells or organisms. dsrnas less than 30 nucleotides in length do not appear to induce nonspecific gene suppression, as described supra for long dsrna molecules. indeed, the direct introduction of sirnas to a cell can trigger rnai in mammalian cells (elshabir, s.m., et al. nature 411:494-498 (2001)). furthermore, suppression in mammalian cells occurred at the rna level and was specific for the targeted genes, with a strong correlation between rna and protein suppression (caplen, n. etal, proc. natl. acad. sci. usa 98:9746-9747 (2001)). in addition, it was shown that a wide variety of cell lines, including hela s3, cos7, 293,nih/3t3, a549, ht-29, cho- ki and mcf-7 cells, are susceptible to some level of sirna silencing (brown, d. et al. technotes 9(l):l-7, available at http://www.ambion.com/techlib/tn/91/912.html (9/1/02)). rnai reagents targeting ptn, a ptn receptor, or another component of the ptn signaling cascade can be readily prepared according to procedures known in the art. structural characteristics of effective sirna molecules have been identified. elshabir, s.m. et al. (2001) nature 411 :494-498 and elshabir, s.m. et al. (2001), embo 20:6877- 6888. accordingly, one of skill in the art would understand that a wide variety of different sirna molecules may be used to target a specific gene or transcript. in certain embodiments, sirna molecules according to the invention are 16 - 30 or 18 - 25 nucleotides in length, including each integer in between. in one embodiment, an sirna is 21 nucleotides in length. in certain embodiments, sirnas have 0-7 nucleotide 3' overhangs or 0-4 nucleotide 5' overhangs. in one embodiment, an sirna molecule has a two nucleotide 3' overhang. in one embodiment, an sirna is 21 nucleotides in length with two nucleotide 3' overhangs (i.e. they contain a 19 nucleotide complementary region between the sense and antisense strands). in certain embodiments, the overhangs are uu or dtdt 3 ' overhangs. generally, sirna molecules are completely complementary to one strand of a target dna molecule, since even single base pair mismatches have been shown to reduce silencing. in other embodiments, sirnas may have a modified backbone composition, such as, for example, 2'-deoxy- or 2'-o-methyl modifications. however, in preferred embodiments, the entire strand of the sirna is not made with either 2' deoxy or 2'-o-modified bases. in one embodiment, sirna target sites are selected by scanning the target mrna transcript sequence for the occurrence of aa dinucleotide sequences. each aa dinucleotide sequence in combination with the 3' adjacent approximately 19 nucleotides are potential sirna target sites. in one embodiment, sirna target sites are preferentially not located within the 5 ' and 3 ' untranslated regions (utrs) or regions near the start codon (within approximately 75 bases), since proteins that bind regulatory regions may interfere with the binding of the sirnp endonuclease complex (elshabir, s. et al. nature 411 :494- 498 (2001); elshabir, s. et al. embo j. 20:6877-6888 (2001)). in addition, potential target sites may be compared to an appropriate genome database, such as blastn 2.0.5, available on the ncbi server at www.ncbi.nlm, and potential target sequences with significant homology to other coding sequences eliminated. short hairpin rnas may also be used to inhibit or knockdown gene or nucleic acid expression according to the invention. short hairpin rna (shrna) is a form of hairpin rna capable of sequence-specifically reducing expression of a target gene. short hairpin rnas may offer an advantage over sirnas in suppressing gene expression, as they are generally more stable and less susceptible to degradation in the cellular environment. it has been established that such short hairpin rna-mediated gene silencing (also termed shagging) works in a variety of normal and cancer cell lines, and in mammalian cells, including mouse and human cells. paddison, p. et al, genes dev. 16(8):948-58 (2002). furthermore, transgenic cell lines bearing chromosomal genes that code for engineered shrnas have been generated. these cells are able to constitutively synthesize shrnas, thereby facilitating long-lasting or constitutive gene silencing that may be passed on to progeny cells. paddison, p. et al, proc. natl. acad. sci. usa 99(3): 1443-1448 (2002). shrnas contain a stem loop structure. in certain embodiments, they may contain variable stem lengths, typically from 19 to 29 nucleotides in length, or any number in between. in certain embodiments, hairpins contain 19 to 21 nucleotide stems, while in other embodiments, hairpins contain 27 to 29 nucleotide stems. in certain embodiments, loop size is between 4 to 23 nucleotides in length, although the loop size may be larger than 23 nucleotides without significantly affecting silencing activity. shrna molecules may contain mismatches, for example g-u mismatches between the two strands of the shrna stem without decreasing potency. in fact, in certain embodiments, shrnas are designed to include one or several g-u pairings in the hairpin stem to stabilize hairpins during propagation in bacteria, for example. however, complementarity between the portion of the stem that binds to the target mrna (antisense strand) and the mrna is typically required, and even a single base pair mismatch is this region may abolish silencing. 5' and 3' overhangs are not required, since they do not appear to be critical for shrna function, although they may be present (paddison et al (2002) genes & dev. 16(8):948-58). 2. polypeptide and small molecule inhibitors methods of the invention are also practiced using polypeptide and small molecule inhibitors. these inhibitors may target ptn, a ptn receptor, or another component of the ptn signaling cascade, and can interfere with ptn activity by any of a variety of means including, e.g., inhibiting ptn binding to a ptn receptor or inhibiting downstream signaling events leading to ptn-induced differentiation or angiogenesis. a. mutation and dominant negative inhibitors in certain embodiments, the activity of ptn is altered is by mutating a gene encoding the ptn molecule, a gene encoding a ptn receptor, or a gene encoding another component of the ptn signaling cascade. a variety of methods of mutating an endogenous gene are known and available in the art, including, e.g., insertional mutagenesis and knockout methods. accordingly, the invention includes methods of knocking out one or more alleles of a ptn gene. it is understood that knockout vectors according to the invention include any vector capable of disrupting expression or activity of a ptn gene, including, in certain embodiments, both gene trap and targeting vectors. it is understood that the methods described herein, while specifically referring to the ptn gene for exemplary purposes, may also be used according to the invention to target a ptn receptor gene, or a gene encoding another component of the ptn signaling cascade. in preferred methods, targeting vectors are used to selectively disrupt a ptn gene. knockout vectors of the invention include those that alter gene expression, for example, by disrupting a regulatory element of a ptn gene, including, e.g., inserting a regulatory element that reduces gene expression or deleting or otherwise reducing the activity of an endogenous element that positively affects transcription of the target gene. in other embodiments, knockout vectors of the invention disrupt, e. g. , delete or mutate, the 5 ' region, 3' region or coding region of a gene. in some embodiments, knockout vectors delete a region or the entirety of the coding region of a ptn gene. in certain embodiments, knockout vectors delete a region of a ptn gene, while in other embodiments, they insert exogenous sequences into a ptn gene. in addition, in certain embodiments, including those using replacement vectors, knockout vectors both remove a region of a gene and introduce an exogenous sequence. targeting vectors of the invention include all vectors capable of undergoing homologous recombination with an endogenous ptn gene, including replacement vectors. targeting vectors include all those used in methods of positive selection, negative selection, positive-negative selection, and positive switch selection. targeting vectors employing positive, negative, and positive-negative selection are well known in the art and representative examples are described in joyner, a.l., gene targeting: a practical approach, 2nd ed. (2000) and references cited therein. in other embodiments, the activity of a molecule is altered by overexpression of a dominant negative inhibitor of ptn or ptn receptor. dominant negative inhibitors of ptn are typically mutant forms of ptn, which reduce or block the activity of wild type ptn, e.g., by competing for binding to a ptn binding partner but failing to fully activate the ptn signaling pathway. typically, dominant negative inhibitors of ptn have a reduced ability to induce differentiation and/or angiogenesis, as compared to wild type ptn. examples of dominant negative ptn mutants include, e.g. , mutants that are incapable of binding to a ptn receptor, and specific functional or binding domains of ptn, including, e.g., a receptor binding domain. in one embodiment, a dominant negative form of pttsf comprises amino acid residues 1 11-136 or amino acid residues 41-64 of the ptn polypeptide. in addition, other domains described in the examples provided herein may also be used according to the methods of the invention. examples of dominant negative ptn receptor mutants include, e.g. , soluble ptn binding domains that bind ptn, thereby inhibiting ptn from binding to native cell surface receptor. b. ptn and ptn receptor binding molecules in other embodiments, ptn inhibitors are molecules that bind to ptn or a ptn receptor, thereby inhibiting ptn function, e.g. , by interfering with ptn binding to a receptor. the invention includes the use of a variety of ptn binding molecules, including, e.g., a ptn receptor or fragment thereof, an antibody or fragment thereof, an inorganic compound, and a small organic compound. the invention further includes a variety of ptn receptor binding molecules, including antibody and small molecule antagonists of a ptn receptor. in particular embodiments, an inhibitor of a ptn receptor specifically binds one ptn receptor, while in other embodiments, an inhibitor of a ptn receptor binds two or more ptn receptor, e.g., by binding to a common or related ptn binding domain of the receptors. in particular embodiments, an inhibitor of a ptn receptor binds to ptn receptor that is overexpressed in mm cells as compared to normal control cells. ptn binding molecules that function as inhibitors include soluble forms or fragments of ptn receptors. in particular embodiments, the receptor is cd138, rtpβ/ζ, syndecan 3, or alk the anaplastic lymphoma kinase (alk) has been identified as a receptor for ptn (stoica, e.g., et al, j biol chem. 2001 may 18 ;276(20): 16772-9). ptn binds to the alk extracellular domain (ecd) with an apparent kd of 32 +/- 9 pm. this receptor binding was inhibited by an excess of ptn, by the alk ecd, and by anti-ptn and anti- ecd antibodies. ptn added to alk-expressing cells induced phosphorylation of both alk and of the downstream effector molecules irs-i, she, phospholipase c-gamma, and phosphatidylinositol 3 -kinase. furthermore, the growth stimulatory effect of ptn on different cell lines in culture coincided with the endogenous expression of alk mrna, and the effect of ptn was enhanced by alk overexpression, suggesting that alk is a receptor that transduces ptn-mediated signals and that the ptn-alk axis plays a significant role during development and during disease processes. accordingly, alk or the alk ecd is a ptn inhibitor included within the present invention. other identified ptn receptors include ldl receptor related protein and ptp ζ. the use of these and other identified or yet to be identified ptn receptors or fragments thereof as ptn inhibitors is further included within the methods of the present invention. cd 138 is a transmembrane heparan sulfate proteoglycan macromolecule, also known as syndecan-1. the cd138 molecule interacts with extracellular matrix proteins, cell surface molecules and soluble proteins. it is expressed on normal and malignant human plasma cells and on basolateral surfaces of endothelial cells, but not on virgin/naive b cells, memory b cells, t cells or monocytes. in certain embodiments, a ptn inhibitor used according to the present invention is a soluble ptn receptor or fragment thereof, wherein said receptor or fragment is capable of binding ptn and, thus, interfering with its ability to bound endogenous cell surface receptors. antibodies, or antigen-binding fragments thereof, specific for ptn or a ptn receptor are also activators or inhibitors of ptn according to the methods described herein. an antibody, or antigen-binding fragment thereof, is said to "specifically bind," "immunogically bind," and/or is "immunologically reactive" to a polypeptide of the invention if it reacts at a detectable level (within, for example, an elisa assay) with the polypeptide, and does not react detectably with unrelated polypeptides under similar conditions. antibodies are considered to specifically bind to a target polypeptide when the binding affinity is at least 1x10 "7 m or, preferably, at least 1x10 "8 m. antibodies may be prepared by any of a variety of techniques known to those of ordinary skill in the art. see, e.g., harlow and lane, antibodies: a laboratory manual, cold spring harbor laboratory, 1988. in general, antibodies can be produced by cell culture techniques, including the generation of monoclonal antibodies via conventional techniques known in the art, or via transfection of antibody genes into suitable bacterial or mammalian cell hosts, in order to allow for the production of recombinant antibodies. monoclonal antibodies specific for an antigenic polypeptide of interest may be prepared, for example, using the technique of kohler and milstein, eur. j. immunol. 6:511-519, 1976, and improvements thereto. antibodies used in the methods of the invention include, but are not limited to, monoclonal antibodies, chimeric antibodies, humanized antibodies, primatized® antibodies, single chains, fab fragments and scfv fragments. methods of making chimeric and humanized antibodies are well known in the art, (see, e.g., u.s. pat. no. 4,816,567, international application no. wo84/03712, respectively). the fab or f(ab') 2 fragments may be wholly animal or human derived, or they may be in chimeric form, such that the constant domains are derived from the constant regions of human immunoglobulins and the variable regions are derived from the parent murine mab. alternatively, the fv, fab, or f(ab') 2 may be humanized, so that only the complementarity determining regions (cdr) are derived from an animal mab, and the constant domains and the framework regions of the variable regions are of human origin. these chimeric and humanized fragments are less immunogenic than their wholly animal counterparts, and thus more suitable for in vivo use, especially over prolonged periods. in particular embodiments, an antibody serves as an activator of ptn signal transduction by binding to a component of a ptn signal transduction pathway, leading to downstream signaling. for example, an antibody to a ptn receptor can be used as an activator to induce downstream signaling events. alternatively, an antibody serves as an inhibitor of ptn signal transduction by binding to a component of a ptn signal transduction pathway, thereby inhibiting downstream signaling. for example, an antibody to ptn may block ptn binding to a ptn receptor, or an antibody to a ptn receptor may block ptn binding but fail to activate downstream signaling itself. c. inducers of ptn methods of the invention directed to inducing differentiation comprise introducing ptn or a functional fragment or variant thereof to a cell. accordingly, these methods typically involve introducing a polypeptide to a cell, either directly or by providing a dna construct that expresses the polypeptide. other related methods of the invention include stimulating a ptn receptor using a ptn polypeptide or a fragment thereof, or an antibody capable of stimulating ptn receptor signaling. as used herein, the term "polypeptide" is used in its conventional meaning, i.e., as a sequence of amino acids. the polypeptides are not limited to a specific length of the product; thus, peptides, oligopeptides, and proteins are included within the definition of polypeptide, and such terms may be used interchangeably herein unless specifically indicated otherwise. this term also does not refer to or exclude post-expression modifications of the polypeptide, for example, glycosylations, acetylations, phosphorylations and the like, as well as other modifications known in the art, both naturally occurring and non-naturally occurring. a polypeptide may be an entire protein, or a subsequence thereof. particular polypeptides of interest in the context of this invention are amino acid subsequences comprising functional domains of ptn, including fragments capable of inducing differentiation of monocyte/macrophages, as well as dominant negative mutants, as described above. the present invention includes the use of polypeptide fragments comprising at least about 5, 10, 15, 20, 25, 50, 75 or 100 contiguous amino acids, or more, including all intermediate lengths, of a polypeptide described herein, including, e.g., ptn and receptors thereof. in another aspect, the present invention includes the use of variants of the polypeptide compositions described herein. for example, the invention contemplates the use of ptn variants, including variants possessing one or more of ptn's functions, such as being capable of inducing differentiation of monocyte/macrophages. a polypeptide "variant," as the term is used herein, is a polypeptide that typically differs from a polypeptide specifically disclosed herein in one or more substitutions, deletions, additions and/or insertions. such variants may be naturally occurring or may be synthetically generated, for example, by modifying one or more of the above polypeptide sequences of the invention. polypeptide variants will typically exhibit at least about 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% or more identity (determined as described below), along its length, to a polypeptide sequences set forth herein. in many instances, a variant will contain conservative substitutions. a "conservative substitution" is one in which an amino acid is substituted for another amino acid that has similar properties, such that one skilled in the art of peptide chemistry would expect the secondary structure and hydropathic nature of the polypeptide to be substantially unchanged. when comparing polypeptide sequences, two sequences are said to be "identical" if the sequence of amino acids in the two sequences is the same when aligned for maximum correspondence, as described below. comparisons between two sequences are typically performed by comparing the sequences over a comparison window to identify and compare local regions of sequence similarity. a "comparison window" as used herein, refers to a segment of at least about 20 contiguous positions, usually 30 to about 75, 40 to about 50, in which a sequence may be compared to a reference sequence of the same number of contiguous positions after the two sequences are optimally aligned. alignment of sequences for comparison may be conducted by a variety of methods, including, e.g. , the local identity algorithm of smith and waterman (1981) add. apl. math 2:482, by the identity alignment algorithm of needleman and wunsch (1970) j. moi. biol. 48:443, by the search for similarity methods of pearson and lipman (1988) proc. natl. acad. sci. usa 85: 2444, by computerized implementations of these algorithms (gap, bestfit, blastn 2.0.5, fasta, and tfasta in the wisconsin genetics software package, genetics computer group (gcg), 575 science dr., madison, wi), or by inspection. another example of algorithms that are suitable for determining percent sequence identity and sequence similarity is the blastn 2.0.5 algorithm, which are described in altschul et al. (1977) nucl. acids res. 25:3389-3402 and altschul et al. (1990) j. moi. biol. 215:403-410, respectively. blastn 2.0.5 can be used, for example, with the parameters described herein, to determine percent sequence identity for the polynucleotides and polypeptides of the invention. software for performing blastn 2.0.5 analyses is publicly available through the national center for biotechnology information. as used herein, ptn includes pleiotrophin polypeptide and polynucleotide sequences from any species, as well as homo logs thereof. in addition, ptn polypeptides include variants and fragments of ptn. ptn polynucleotides include any polynucleotide that encodes a ptn polypeptide, including such variants and fragments. the human pleiotrophin prescursor polypeptide sequence is provided at swissprot database accession no. p21246, and the mature processed ptn polypeptide sequence is provided in figure 9a. the invention further includes the use of small inorganic and small organic molecules capable of enhancing ptn 's ability to promote differentiation. such molecules may be identified according to routine screening procedures available in the art, e.g. , using commercially available libraries of such compounds. d. expression constructs and viral vectors as described above, in certain embodiments, ptn activity is altered through the use of recombinantly engineered constructs that express ptn or a ptn receptor, functional fragments or variants thereof, or an inhibitor of ptn. in certain embodiments, expression constructs are transiently present in a cell, while in other embodiments, they are stably integrated into a cellular genome. furthermore, it is understood that due to the inherent degeneracy of the genetic code, other dna sequences that encode substantially the same or a functionally equivalent amino acid sequence or variant thereof may be produced and these sequences may be used to express a given polypeptide. methods well known to those skilled in the art may be used to construct expression vectors containing sequences encoding a polynucleotide or polypeptide of interest, e.g., ptn or a fragment, mutant or variant thereof, and appropriate transcriptional and translational control elements. these methods include in vitro recombinant dna techniques, synthetic techniques, and in vivo genetic recombination. such techniques are described, for example, in sambrook, j. et al. (1989) molecular cloning, a laboratory manual, cold spring harbor press, plainview, n. y., and ausubel, f. m. et al. (1989) current protocols in molecular biology, john wiley & sons, new york. n. y. in one embodiment, expression constructs of the invention comprise polynucleotide sequences encoding all or a region of a ptn gene. regulatory sequences present in an expression vector include those non- translated regions of the vector, e.g., enhancers, promoters, 5' and 3' untranslated regions, which interact with host cellular proteins to carry out transcription and translation. such elements may vary in their strength and specificity. depending on the vector system and cell utilized, any number of suitable transcription and translation elements, including constitutive and inducible promoters, may be used. in mammalian cells, promoters from mammalian genes or from mammalian viruses are generally preferred, and a number of viral-based expression systems are generally available. for example, in cases where an adenovirus is used as an expression vector, sequences encoding a polypeptide of interest may be ligated into an adenovirus transcription/translation complex consisting of the late promoter and tripartite leader sequence. insertion in a non-essential el or e3 region of the viral genome may be used to obtain a viable virus which is capable of expressing the polypeptide in infected host cells (logan, j. and shenk, t. (1984) proc. natl. acad. sci. 81:3655-3659). in addition, transcription enhancers, such as the rous sarcoma virus (rsv) enhancer, may be used to increase expression in mammalian host cells. specific initiation signals may also be used to achieve more efficient translation of sequences encoding a polypeptide of interest. such signals include the atg initiation codon and adjacent sequences. exogenous translational elements and initiation codons may be of various origins, both natural and synthetic. the efficiency of expression may be enhanced by the inclusion of enhancers which are appropriate for the particular cell used, such as those described in the literature (scharf, d. et al. (1994) results probl. cell differ. 20:125-162). in certain embodiments, the invention provides for the conditional expression of ptn or fragment or variant thereof, or an inhibitor of ptn activity. a variety of conditional expression systems are known and available in the art for use in both cells and animals, and the invention contemplates the use of any such conditional expression system to regulate the expression or activity of ptn. in certain embodiments of the invention, the use of prokaryotic repressor or activator proteins is advantageous due to their specificity for a corresponding prokaryotic sequence not normally found in a eukaryotic cell. one example of this type of inducible system is the tetracycline-regulated inducible promoter system, of which various useful version have been described (see, e.g. shockett and schatz, proc. natl. acad. sci. usa 93:5173-76 (1996) for a review). in one embodiment of the invention, for example, expression of a molecule can be placed under control of the rev-tet system. components of this system and methods of using the system to control the expression of a gene are well-documented in the literature, and vectors expressing the tetracycline-controlled transactivator (tta) or the reverse tta (rtta) are commercially available (e.g. ptet-off, ptet-on and ptta-2/3/4 vectors, clontech, palo alto, ca). such systems are described, for example, in u.s. patents no. 5650298, no. 6271348, no. 5922927, and related patents, which are incorporated by reference in their entirety. in particular embodiments, ptn inhibitors or ptn polypeptides, or fragments or variants thereof, are provided to a cell using a viral or bacteriophage vector. a wide variety of viral expression systems are known and available in the art, all of which may be used according to the invention. therefore, in certain embodiments, polynucleotide inhibitors of ptn or polynucleotides encoding inhibitors of ptn or ptn, or a fragment or variant thereof, are introduced into suitable mammalian host cells or patients using any of a number of known viral-based systems. in one illustrative embodiment, retroviruses provide a convenient and effective platform for gene delivery systems. a selected nucleotide sequence can be inserted into a vector and packaged in retroviral particles using techniques known in the art. the recombinant virus can then be isolated and delivered to a subject. a number of illustrative retroviral systems have been described (e.g., u.s. pat. no. 5,219,740; miller and rosman (1989) biotechniques 7:980-990, miller, a. d. (1990) human gene therapy 1:5-14; scarpa et al. (1991) virology 180:849- 852; burns et al. (1993) proc. natl. acad. sci. usa 90:8033-8037; and boris-lawrie and temin (1993) cur. opin. genet. develop. 3:102-109. in addition, a number of illustrative adenovirus-based systems have also been described. unlike retroviruses which integrate into the host genome, adenoviruses persist extrachromosomally thus minimizing the risks associated with insertional mutagenesis (haj-ahmad and graham (1986) j. virol. 51:261 -21 a; bett et al. (1993) j. virol. 67:5911-5921; mittereder et al. (1994) human gene therapy 5:717-729; sethetal. (1994) j. virol. 68:933-940; barr et al. (1994) gene therapy 1:51-58; berkner, k. l. (1988) biotechniques 6:616-629; and rich etal. (1993) human gene therapy 4:461-476). various adeno-associated virus (aav) vector systems have also been developed for polynucleotide delivery. aav vectors can be readily constructed using techniques well known in the art. see, e.g., u.s. pat. nos. 5,173,414 and 5,139,941; international publication nos. wo 92/01070 and wo 93/03769; lebkowski et al. (1988) molec. cell. biol. 8:3988-3996; vincent et al. (1990) vaccines 90 (cold spring harbor laboratory press); carter, b. j. (1992) current opinion in biotechnology 3:533-539; muzyczka, n. (1992) current topics in microbiol, and immunol. 158:97-129; kotin, r. m. (1994) human gene therapy 5:793-801 ; shelling and smith (1994) gene therapy 1 : 165- 169; and zhou et al. (1994) j. exp. med. 179:1867-1875. additional viral vectors useful for delivering the polynucleotides encoding polypeptides of the present invention by gene transfer include those derived from the pox family of viruses, such as vaccinia virus and avian poxvirus. by way of example, vaccinia virus recombinants expressing the novel molecules can be constructed as follows. the dna encoding a polypeptide is first inserted into an appropriate vector so that it is adjacent to a vaccinia promoter and flanking vaccinia dna sequences, such as the sequence encoding thymidine kinase (tk). this vector is then used to transfect cells, which are simultaneously infected with vaccinia. homologous recombination serves to insert the vaccinia promoter plus the gene encoding the polypeptide of interest into the viral genome. the resulting tk.sup.(-) recombinant can be selected by culturing the cells in the presence of 5-bromodeoxyuridine and picking viral plaques resistant thereto. in particular embodiments, viral vectors are adenovirus, adeno-associated virus, or lentivirus. in certain embodiments, the methods of the invnetion utilize lentiviruses. like other retroviruses, lentiviruses are enveloped viruses that carry a core of rna encoding their genetic information. lentiviruses are unique in that lentiviruses are the only retroviruses able to integrate into the chromosome of non-dividing cells. recombinant self-inactivating lentiviral vectors expressing angiostatin and endostatin have previously been shown to have antiangiogenic activities (shichinohe t., cancer gene ther. 2001 nov;8(l l):879-89), and similar methods are used according to the invention to deliver ptn inhibitors or ptn polynucleotide, polypeptides, or functional fragments or variants thereof. lentiviruses have also been shown to successfully deliver rna or dna into hematopoeitc stem cells (uchida, n., et al., pnas usa 1998; 95:11939-11944) and have been used to successfully deliver rnai molecules to cells (schomber, t. et al., blood 103:4511-4513 (2004)). accordingly, methods of constructing and delivery polynucleotides and polypeptides using lentiviruses are well-established in the art. additional illustrative information on these and other known viral-based delivery systems can be found, for example, in fisher-hoch et al., proc. natl. acad. sci. usa 86:317-321, 1989; flexner et si., arm. ny. acad. sci. 569:86-103, 1989; flexner et al., vaccine 5:17-21, 1990; u.s. patent nos. 4,603,112, 4,769,330, and 5,017,487; wo 89/01973; u.s. patent no. 4,777,127; gb 2,200,651; ep 0,345,242; wo 91/02805; berkner, biotechniques 6:616-621, 1988; rosenfeld et al., science 252:431-434, 1991; kolls et al., proc. natl. acad. sci. usa 91:215-219, 1994; kass-eisler et al., proc. natl. acad. sci. usa 90:11498-11502, 1993; guzman et al., circulation 55:2838-2848, 1993; and guzman et al., cir. res. 73:1202-1207, 1993. e. methods of identifying and manufacturing inhibitors and inducers of ptn the invention further provides methods of identifying and producing inhibitors and inducers (including antagonists and agonists) of ptn expression and/or activity, including inhibitors and inducers having therapeutic properties. in certain embodiments, inhibitors and inducers modulate one or more of ptn' s functional properties, such as, e.g. , ptn's ability to induce differentiation of monocyte/macrophages to endothelial-like cells or ptn's ability to promote angiogenesis and/or vasculogenesis. in general, inhibitors and inducers are identified by screening candidate molecules, including, e.g., all of the different types of molecules described above. any assay suitable for determining ptn function or activity may be utilized, including, but not limited to, binding assays and biological functional assays. candidate molecules may be screened individually, e.g., when a specific molecule is predicted to function as an inhibitor or inducer. alternatively, a library of compounds or molecules may be screened. examples of such libraries, which are readily available commercially, include recombinant expression libraries, libraries of small inorganic compounds, and libraries of small organic compounds. an inhibitor of ptn is identified as a molecule or compound that reduces one or more of ptn's activities, e.g., ability to induce differentiation of monocyte/macrophages or ability to promote angiogenesis, by at least 10%, at least 25%, at least 50%, at least 75% or 100%. in general, the invention contemplates two different types of inducers, including (1) molecules that increase the functional activity of ptn; and (2) molecules that increase expression levels of ptn, including, e.g., a ptn expression construct. an inducer of ptn is identified as a molecule or compound that increases one or more of ptn's activities by at least two-fold, at least five-fold, at least ten-fold or more. in the context of overexpression of ptn, an inducer is a molecule or compound that increases expression of ptn at least two-fold, at least five-fold, at least ten-fold or more. in one embodiment, inducers or inhibitors are identified by their ability to bind to ptn or a functional fragment thereof. routine binding assays suitable for screening candidate molecules and compounds are well known in the art and include, e.g. , gst pulldown assays using recombinantly-produced gst-ptn fusion polypeptides, affinity chromatography, phage display, immunoprecipitation assays under low stringency conditions suitable for precipitating ptn complexes using antibodies to ptn, elisa assays, and radioimmunoassays. in particular embodiments, screening assays are performed using high throughput techniques. for example, binding assays may be performed using microtitre dishes with multiple wells, such as a 96-well dish. in one embodiment, inhibitors or inducers are identified by placing monocyte/macrophages into the wells of a microtitre dish, adding a different molecule or compound to be tested into individual wells, and determining in which wells the monocyte/macrophages undergo differentiation into endothelial-like cells, via any of a variety of techniques, including, e.g., rt-pcr using primers specific for endothelial cell markers, as described herein. automated systems for performing rt-pcr on microtitre plates is available. inhibitors and inducers of ptn and other components of the ptn signaling pathway may be manufactured, e.g. , by identifying such a molecule as described above and producing said identified molecule. in addition, identified molecules may be derivatized using standard procedures availabel in the art and further screened or tested to identify a molecule having improved function as an inhibitor or inducer of ptn or ptn signaling. example 1 comparison of pleiotrophin serum levels in multiple myeloma patients and healthy control subjects ptn serum levels from multiple myeloma (mm) patients (n= 50) were compared to ptn serum levels in healthy control subjects (n=20) using elisa assay. the result showed that the serum concentration of ptn of mm patients averaged 5.6pg (range 1.6pg to 22pg). in the healthy control group, the ptn serum level averaged 2.4pg from 0 to 4pg. paired t-test was used for paired comparison of normal and mm patients. the p value was < 0.02. patients may be classified into one of three myeloma categories (mgus, asymptomatic, and symptomatic). monoclonal gammopathy of undetermined significance (mgus) is a common condition where a monoclonal protein is present. however, there are no symptoms, other criteria for myeloma diagnosis are absent, and no cause for the increased protein can be identified. mgus occurs in about 1% of the general population and in about 3% of normal individuals over 70 years of age. mgus itself is harmless but over many years approximately 16% of individuals with mgus will progress to a malignant plasma cell disorder. patients with asymptomatic multiple myeloma have a monoclonal protein and slightly increased numbers of plasma cells in the bone marrow. they may have mild anemia and/or a few bone lesions, but do not exhibit the renal failure and frequent infections that characterize active multiple myeloma. in these patients the myeloma is static and may not progress for months or years. asymptomatic multiple myeloma includes both smoldering multiple myeloma (smm) and indolent multiple myeloma (imm). patients who present with symptomatic multiple myeloma typically have a monoclonal protein and increased numbers of plasma cells in the bone marrow. interestingly, elisa analysis of serum from normal donors and a spectrum of mm indicated that patients diagnosed with symptomatic multiple myeloma had the greatest increase in ptn levels as compared to normal patients, while patients diagnosed with mgus or indolent myeloma had less of a comparative increase in ptn levels. irnmunohistochemical staining also showed an increase in ptn production in multiple myeloma patients with active disease as compared to a patient in remission or a normal donor. in addition, ptn was highly expressed in mutiple myeloma cells lines (u266 mm and rpmi 8226 mm) but not a monocytic cell line (thpl monocyte). rt- pcr analysis of total rna from the multiple myeloma cell lines rpmi 8226 and u266, and their drug resistant variants (8226/dox, 8226/lr, u266/dox, u266/lr) demonstrated elevated ptn mrna as compared to the monocytic cell line thp 1. doxorubicin resistant multiple myeloma variants (8226/dox and u266/dox) exhibited lower levels of ptn mrna than parental mm cell lines (8226 and u266). together, these data indicate that ptn levels are elevated to the largest extent in multiple myeloma patients having advanced and active disease, and demonstrate that ptn levels may be used to diagnosis, stage, and monitor disease progression and remission. example 2 effect of pleiotrophin on the phenotype of monocytic cells previous studies have concentrated on the paracrine role of monocytes/macrophages, in which these cells impact their surrounding cellular environment by releasing a wide spectrum of angiogenic factors and cytokines. to determine the autocrine effect of secreted monocyte/macrophage-derived factors such as ptn on the phenotype of monocytes/macrophages, expression levels of monocyte/macrophage markers were examined in cells stimulated with ptn. monocyte/macrophage cells were isolated from volunteer donors (two males and one female) and then either left untreated or treated with recombinant ptn and m- csf. total rna was isolated from the cells and the expression of fik-i , tie-2 and vwf, three markers of endothelial cells, as well as gapdh as a control, was determined by rt- pcr (fig. 2). in addition, constitutively expressed gapdh was used to control for the pcr reaction. real-time pcr was performed on samples as follows. treated or untreated monocyte/macrophages were rinsed twice with pbs, and total rna was isolated by using trizol reagent. one μg of total rna was reversibly transcribed to cdna in a reaction condition of 25 mm tris-hcl (ph 8.3), 5 mm mgcl 2 , 50 mm kcl, 2 mm dtt, 1 mm dntp each, 40 μg/ml primer dti 5 and 200 u/ml amv reverse transcriptase in a final volume of 25 μl and incubated for 40 min at 42°c. reverse transcription was terminated by heating at 95°c for 5 min, and 5% of the cdna was used as template for pcr. the reactions were performed in 10 mm tris-hcl (ph 8.3), 1.5 mm mgcl 2 , 50 mm kcl, 0.2 mm each dntp, 0.5 mm each primer, and 1.25 u of taq polymerase in a final reaction volume of 50 μl. cells treated with ptn and m-csf expressed significantly higher levels of the endothelial cell markers than untreated cells (figure 2). gapdh amplification showed that the rt-pcr reactions proceeded efficiently for all tested samples. cd34+ cells isolated from bone marrow were similarly stimulated with ptn and/or m-csf, and expression of the endothelial cell marker genes, flk-i, tie-2, vwf, and the monocytic cell markers, cd68, and c-fms, was determined by real time pcr, as described above. the results shown in figure 3 clearly demonstrate that treatment with ptn + m-csf results in increased expression of endothelial cell markers and reduced expression of monocyte/macrophage markers. these data demonstrate that exposure to ptn induces the expression of endothelial cell markers in monocyte/macrophages, and further establish that exposure to ptn induces monocyte/macrophage trans-differentiation into endothelial-like cells. example 3 ptn transdifferentiates monocytes into vascular endothelial-like cells to examine the role of ptn in macrophage-mediated tumor vascularization and monocytes transdifferentiation into vascular endothelial cells, the expression of several established endothelial cell markers was determined using rt-pcr in ptn-infected cells, as well as a variety of different cell lines. the markers included: vascular endothelial growth factor receptor-2 (fik-i), tie-2, and the von willebrand factor (vwf)(46). the results are presented in figure 8. cell lines examined included the monocytic cells, mouse raw, human thp-i, and human u937, as well as the non-monocytic cells, nih 3t3 cells, human coronary artery smooth muscle cells, and rpmi 8226 mm cell line. human dermal fibroblasts were used as negative controls, and human coronary artery endothelial cells (obtained from cell applications, inc.) were used as a positive control. unless otherwise indicated, cells were obtained from atcc and cultured as recommended. in addition, rna was isolated from thp-i cells infected with a bicistronic retroviral vector harboring ptn sense strand, ptn anti-sense strand, or green fluorescence protein, and either untreated or treated with 25 ng/ml pma to induce differentiation into macrophage-like cells. rna was isolated using rneasy mini kit (qiagen, chatsworth, ca). the rna was subjected to rt-pcr analysis using the qiagen onestep rt-pcr kit with the addition of 10 units rnase inhibitor (gibco/brl) and 40 ng rna with specific primers for endothelial cell-specific markers. to ensure semi-quantitative results of the rt-pcr analysis, the number of pcr cycles for each set of primers was checked to be in the linear range of the amplification. in addition, all rna samples were adjusted to yield equal amplification of glyceraldehyde-3 -phosphate dehydrogenase (gapdh) as an internal standard. the amplified products were separated on 1.2% agarose gels and stained with ethidium bromide. the semi-quantitative rt-pcr analyses are shown in fig. 8. thp-i cells infected with ptn sense strand expressed vascular endothelial growth factor receptor-2 (fik-i), tie-2, and the von willebrand factor (vwf), similar to that of positive control human coronary artery endothelial cells. in contrast, these endothelial cell markers were not detected in thp-i cells infected with the gfp control vector. similarly, the expression of these markers was not detected in uninfected mouse monocytic raw cells, human monocytic thp-i cells, and human promonocytic leukemia u937 cells. furthermore, endothelial cell markers were not expressed in negative control non-monocytic cells, such as nih 3t3 cells, human smooth muscle cells, rpmi 8226 b lymphocyte plasmacytoma cell line, and human skin fibroblasts. the weak expression of fik-i in smooth muscle cells is consistent with the expression of this endothelial cell marker in human smooth muscle cells. the expression pattern of the endothelial cell markers in ptn-infected raw cells was similar to ptn-infected thp-i cells (not shown). rt-pcr analysis of thp-i and endothelial cells was also performed, essentially as described above, using primers specific for the monocytic cell markers, c-fms and cd-68. as shown in figure 8b, these monocytic markers were expressed in thp-i cells either untreated or treated with pma. however, when transduced with ptn sense, the thp-i cells did not express these monocytic markers, even in response to pma treatment. endothelial cells also failed to express these monocytic markers. additional experiments were performed using a co-culture system to induce transdifferentiation. thpl cells were cultured alone or co-cultured with mm cells, and either left untreated or treated with pma, mm or normal serum, anti-ptn antibodies or control igg. the expression of endothelial cell markers, fik-i, tie-2, and vwf, was determined by rt-pcr, as described above. as shown in figure 8c, expression of the endothelial cell markers was induced when thp 1 monocytes were cultured with mm cells or serum from an mm patient or the mm cell lines 8226 or u266. this transdifferentiation was inhibited specifically by a polyclonal ptn antibody. collectively, these data demonstrate that ptn transdifferentiates monocytes into vascular endothelial-like cells. thp-i and raw monocytic cells do not express endothelial cell markers; however, ptn expression led to expression of these markers. similarly, overexpression of ptn in monocytic cells led to down-regulation of monocytic markers. in addition, since the number of pcr cycles for each set of primers was chosen to be in the linear range of the amplification, these data show that the expression levels of endothelial cell markers was similar to those of positive control endothelial cells. example 4 the role of pleiotrophin in multiple myeloma in causing macrophage- mediated tumor vascularization to determine whether high concentrations of ptn in mm patients' serum induce transdifferention of monocyte/macrophages to endothelial-like cells, thpl cells were co-cultured with an mm cell line or with a high level of ptn in a mm patient's serum to compare with normal human serum. results (fig 4.) showed that normal human serum did not stimulate thpl cell expression of the endothelial markers (lane 3, 13, 14). high concentrations of ptn in the mm patient serum (lane 5) and mm cell line (line 6, 7) induced thpl cell expression of endothelial markers. however, this inducing function was abolished by specific anti-ptn antibody (line 11, 12) but antihuman igg had no effect (line 9, 10). example 5 effect of ptn blocking antibody on multiple myeloma-induced endothelial cell gene expression to further explore the role of ptn in the trans-differentiation of monocyte/macrophages into endothelial-like cells, the effect of blocking antibodies specific for ptn was examined in thpl monocyte/macrophage cells. thpl cells treated with pma and co-cultured with u266 myeloma cells or cultured in high level mm serum were additionally exposed to anti-ptn antibody, as indicated in figure 5. in addition, untreated cell and human endothelial cells were examined. rt-pcr was performed on rna isolated from cells undergoing each treatment using primers specific for the endothelial cell markers, tie-2, flk-i and vwf. as shown in figure 5, treatment with pma in the presence of u266 myeloma cells or high level mm serum induced expression of the endothelial cell markers (lanes 3 and 4). however, treatment with pma in the presence of u266 myeloma cells or high level mm serum failed to induce expression of the endothelial cell marker genes in the presence of the anti-ptn antibody. these data indicate that multiple myeloma-induced expression of endothelial cell markers in monocyte/macrophage cells required functional ptn and further establish that ptn mediates the trans-differentiation of monocyte/macrophages into endothelial-like cells associated with multiple myeloma. example 6 expression of ptn in the bone marrow of multiple myeloma patients the expression of ptn in the bone marrow of patients diagnosed with various stages of multiple myeloma was examined by rt-pcr, essentially as described above, using ptn specific primers and gapdh primers as a control. as shown in figure 6a, ptn was overexpressed in the bone marrow of seven of ten multiple myeloma patients. furthermore, ptn mrna levels were elevated in patients with active myeloma relative to patients with indolent disease or in remission, as shown in figure 6b. in situ hybridization analysis of ptn gene expression confirmed that ptn expression is dysregulated in the bone marrow of multiple myeloma patients. in situ hybridization using a ptn antisense probe revealed significant staining in bone marrow sampled from two multiple myeloma patients, but little or no staining in normal bone marrow. in situ hybridization using a ptn sense probe revealed little or no staining in bone marrow from a multiple myeloma patient. these data demonstrate a direct correlation between ptn overexpression and multiple myeloma and establish that expression levels of ptn may be used to diagnose and stage multiple myelomas. example 7 expression of endothelial cell markers induced by ptn in cd 14+ primary monocytes and cd34+ cells the ability of ptn to transdifferentiate monocytic cells into endothelial-like cells was demonstrated in primary human cells by treating isolated mononuclear cells with ptn and measuring endothelial cell marker expression by rt-pcr, essentially as described above. primary cd 14+ cells were isolated from the peripheral blood of normal donors using magnetic beads conjugated to anti-cd 14 antibodies. isolated cd 14+ cells or control human coronary artery endothelial cells were serially diluted, rna was isolated, and rt-pcr was performed using primers specific for the monocytes gene, cd68, and the endothelial markers, fik-i and vwf. the isolated cd 14+ cells expressed cd68 but not the endothelial markers, thereby confirming that there was no endothelial cell contamination of the isolated cd 14+ cell population (data not shown). the isolated cd 14+ monocytes were co-cultured on collagen i with ptn and macrophage colony stimulating factor (mcsf) and/or vascular endothelial growth factor (vegf) to demonstrate that ptn modulates the expression of monocytic genes and induces endothelial genes. following treatment (or no treatment), the cells were serially diluted and assessed for marker gene expression by rt-pcr on total rna. untreated cd14+ cells and cells treated with mcsf alone expressed monocytic but not endothelial markers (data not shown). similarly, untreated cd 14+ cells or cells treated with ptn or vegf alone expressed monocytic but not endothelial markers (data not shown). however, cd14+ cells treated with ptn in combination with mcsf or vegf expressed endothelial cell markers, demonstrating that the combination of ptn and vegf or mcsf induced trans-differentiation of monocytes into endothelial-like cells (figure 1 ia). furthermore, endothelial cell marker gene expression was even higher upon treatment with the triple combination of ptn, mcsf, and vegf, as shown in figure 1 ib. to determine whether ptn' s ability to transdifferentiate cells into endothelial-like cells was specific for monocytes, experiments were performed to assess the effect of treating t cells and b cells with ptn and mcsf. rt-pcr was performed on rna isolated from t cells or b cells treated with ptn and mcsf to measure the expression of the endothelial cell markers, fik-i, tie-2, and vecad, .and the monocytic cell marker, c-fms. treatment with ptn and mcsf did not induce expression of endothelial cell markers in either t cells or b cells (data not shown). the role of ptn in the differentiation of monocyte/macrophages into endothelial-like cells was further examined by immunostaining human bone-marrow derived cd34+ stem cells either untreated or treated with ptn using antibodies specific for the endothelial cell marker fik-i. cells treated with m-csf in combination with ptn expressed significantly higher levels of fik-i than control cells treated with only m-csf (data not shown). these data confirm that ptn induces the expression of endothelial cell- specific polypeptides in monocytic cells and further establishes the role of ptn in multiple myeloma-induced transdifferentation of monocyte/macrophages. a model of the role of ptn in differentiation of stem cells and trans-differentiation of monocytes is provided in figure 12. example 8 ptn antisense inhibits multiple myeloma cell growth to further establish the role of ptn in multiple myeloma, experiments were performed to examine the effect of increasing or reducing ptn expression in multiple myeloma cell lines. a ptn bicistronic retroviral vector expressing green fluorescent protein (gfp) and either ptn sense or antisense polynucleotides under the control of the cmv promoter was constructed and used to infect rpmi 8226 cells. infected cells were isolated by flow cytometry based upon gfp expression. rt-pcr performed using ptn oligonucleotides demonstrated that rpmi 8226 cells expressed increased levels of ptn when transduced with the ptn retroviral vector expressing ptn sense polynucleotides. in contrast, transduction with the ptn retroviral vector expressing ptn antisense polynucleotides nearly abolished ptn transcription. rpmi 8226 cells transduced with either ptn sense or ptn antisense were grown for 48 hours following infection. cell proliferation was determined by mtt assay. as shown in figure 20, rpmi 8226 proliferation was inhibited at 48 hours when transduced with ptn antisense. example 9 ptn antibodies inhibit multiple myeloma proliferation in vitro to further establish the role of ptn in multiple myeloma cell proliferation, experiments were performed using polyclonal anti-ptn blocking antibodies to inhibit ptn activity. rpmi 8226 cells, and rpmi 8226 cells transduced with the bicistronic ptm retrovirus expressing ptn sense polynucleotides, as described above, were grown in low serum conditions of either 0% or 5% serum, in the presence or absence of anti-ptn antibodies. mtt assays were performed at 24 and 48 hours following transduction to measure proliferation. as shown in figure 1oa, the addition of the anti-ptn antibodies slowed growth in low serum conditions. in serum-free culture, transduction with ptn sense enhanced cell growth. similar results were also observed in u266 cells, as shown in figure 1ob. example 10 ptn antibodies inhibit multiple myeloma tumor growth ptn' s role in multiple myeloma tumor growth in vivo was further demonstrated using a scid-hu lagλ-1 mm model to analyze the effect of anti-ptn blocking antibodies. fifteen scid mice were surgically implanted with a 0.4-0.6 cm 3 lagλ-1 tumor fragment into the left hind limb. beginning fourteen days post- implantation, lagλ-1 mice received ptn antibody therapy twice weekly for the duration of the study via intraperitoneal injection. mice were injected with 3.0 or 10.0 mg/kg of anti-ptn antibodies, or were injected with control vehicle lacking antibodies. tumor growth was monitored by measuring human igg levels and tumor volume every seven days. human igg is secreted by the tumor. as shown in figure 1 ia, treatment with anti- ptn antibodies significantly reduced the amount of human igg as compared to control vehicle treatment. in addition, treatment with anti-ptn antibodies also significantly reduced tumor volume as compared to control vehicle treatment, as shown in figure 1 ib. the reduction in tumor growth evidenced by these results was dose-dependent, with tumor growth being inhibited to a greater extent upon treatment with 10 mg/kg anti-ptn antibody, as compared to treatment with 3 mg/kg anti-ptn antibody. example i l ptn induces monocytes to form tube-like arrays the role of ptn in mm-related angiogenesis and neovascularization was demonstrated using purified cd 14+ monocytes, isolated as described above. cd 14+ monocytes were co-cultured on collagen i with ptn and mcsf and/or vegf and their morphological changes observed. in addition, the expression of the vascular endothelial marker, fik-i, was determined by immunostaining using an anti-flk-1 antibody.. treatment with ptn and mcsf and/or vegf induced the cd 14+ monocytes to form ordered tube-like arrays resembling blood vessels, as shown in figure 12. treatment with mcsf alone did not induce the formation of these structures. example 12 increased incidence of tie-2 endothelial cells in the circulation of mm patients to determine if the increased levels of ptn observed in mm patients resulted in an increased amount of endothelial-like cells, the levels of tie-2+ cells was compared in multiple myeloma patients to normal donors. total rna was isolated from peripheral blood mononuclear cells isolated from normal donors and mm patients and analyzed by rt-pcr using tie-2 specific primers. tie-2 was more highly expressed in the peripheral blood of mm patients than normal donors. in addition, immunohistochemistry was performed using a tie-2 specific antibody to analyze peripheral blood samples from mm patients and normal donors. approximately four times as many tie-2+ endothelial cells were found in the peripheral blood of mm patients than in normal donors, indicating that mm patients have more circulating tie-2+ endothelial cells than normal donors. example 13 identification of ptn receptors in mm cells ptn and midkine have been associated with a variety of different cell surface receptors. to identify the most relevant ptn receptors in mm, the presence and level of expression of various receptors in normal and mm cells was compared by flow cytometry and rt-pcr. mm cell lines and pbmcs from myeloma patients (pcl 1016 and 1153) and normal donors (pbmc 1 -4) were stained for the ptn receptors cd 138 and rptpβ/ζ, and analyzed by flow cytometry. the results shown in figure 13 a indicate that mm cells express higher levels of prn receptors as compared to control cells. control cells expressed low amounts of the cdl 38 receptor, but did not express detectable amounts of the rptpβ/ζ receptor. rt-pcr analysis confirmed that the ptn receptor rptpβ/ζ is expressed in mm cells, but not in pbmcs from normal donors (data not shown). the monocytic cell lines, thp-i and u937, were stained for the ptn receptors syndecan 3 and alk, and analyzed by flow cytometry. u937 cells are alk- and did not transdifferentiate when treated with ptn. as shown in figure 13b, thp-i cells express both the syndecan 3 and alk receptors, while u937 cells express only the syndecan 3 receptor, suggesting a role for the alk receptor in ptn-induced transdifferentiation. a schematic diagram comparing a model of ptn signaling is normal monocytes and mm cells provided in figure 14. example 14 pleiotrophin serum levels correlate with multiple myeloma disease progression and treatment response the association of ptn levels with multiple myeloma disease progression was determined by measuring ptn serum protein levels at different stages of disease progression and during remission. since ptn has been shown to be elevated in the serum of some solid tumor patients, it was determined whether ptn may be elevated in the serum of mm patients, and the correlation between these levels and the patients' disease status was examined. by using a highly sensitive and specific enzyme-liked immunosorbent assay (elisa) for ptn, 270 different serum samples were tested (mm (n=194), mgus (n=18) and age-matched healthy control patients (n=58)). serum samples from mm patients were obtained at the time of diagnosis as well as during the course of their disease. serum ptn levels were higher in mm patients than in the control subjects (median = 1.44 ng/ml vs 0.42 ng/ml, p <0.0001), as shown in figure 17. in addition, among patients with mgus and smoldering myeloma, the ptn was also higher than in the controls (median = 1.14 ng/ml vs 0.42 ng/ml, p <0.0001) but lower than among patients with active mm (p <0.0001). patients with untreated mm showed similar ptn levels as those patients who received prior treatment. among previously treated patients, the group with progressive disease at the time of evaluating ptn had higher levels of this protein than patients with responsive or stable disease (median = 1.73 ng/ml vs 1.16 ng/ml, p <0.0001). evaluation of patients who had a change in disease status showed that the serum ptn level increased at the time of progression when compared to their baseline level (median = 1.76 ng/ml vs 1.01 ng/ml, p value=0.009). conversely, patients who responded to anti-myeloma therapy exhibited significant decreases of ptn as compared with their pre-treatment ptn values (median = 0.95 ng/ml v. 1.90 ng/ml, p value=0.007) (figure 17). this increase in ptn serum protein levels in patients with active disease and subsequent decline during remission demonstrate that ptn serum levels may be used to both diagnose multiple myeloma, as well as monitor disease progression and the effectiveness of treatment. in addition, ptn serum protein levels may be used to predict disease prognosis. the change in ptn levels in individual patients throughout the course of multiple myeloma was examined by measuring ptn serum levels in individual patients as their disease progressed or went into remission following treatment. ptn serum protein levels in individual patients rose significantly (p = 0009) with mm disease progression (figure 18a). in contrast, patients that responded to anti-myeloma therapy showed a significant (p = 0.007) decrease in serum ptn (figure 18b). these data establish that serum ptn levels may be used as a clinical marker to measure disease progression and response to treatment. mononuclear cells were isolated from normal or mm bone marrow aspirates (bmmcs) 5 and the cells cultured for 48hrs. ptn levels were measured in the cell supernatants by elisa. mm bmmcs secrete markedly higher levels of ptn than bmmcs of normal donors, as shown in figure 19. these data further demonstrate that increased levels of secreted ptn may be used to diagnose mm. example 15 pleiotrophin-induced trans-differentiation of bone marrow cells into endothelial-like cells in multiple myeloma the ability of ptn to induce differentiation of bone marrow stem cells into endothelial-like cells is examined using both in vitro and in vivo systems. preliminary studies described above showed that ptn mean serum concentrations were much higher in mm patients compared to controls and established that ptn can induce thpl monocytic cells to transdifferentiate into endothelial-like cells. furthermore, ptn serum levels correlated positively with the stage of disease and inversely with response to therapy in lung cancer. this effect appears to be specific to ptn, because no apparent correlation was found between plasma concentrations of other angiogenic factors such as vegf and stage of disease. in vitro studies revealed that ptn mrna was expressed in a vast majority of mm cell lines and patients compared to normal human control. taken together, these data establish a link between ptn expression and mm. this data further demonstrates that ptn can cause bone marrow stem cells of mm to acquire endothelial- like cell phenotypes. in the in vifro system, cd34 cells are infected with a bicistronic retrovirus harboring ptn sense strand or anti-sense strand. these cell lines develop tumor within 21 days at 100% frequency in nude mice inoculated subcutaneously with 10' cells. the exponentially growing cells are infected with the bicistronic retrovirus harboring green fluorescent protein (gfp) with ptn sense strand or anti-sense strand. the infected cells are separated from uninfected cells by using g418 selection media followed by flow cytometric sorting (facs). the expression of ptn in the infected cells is assessed by northern and western blot analyses using endothelial cell specific probes, including those described above. uninfected cd34 cells or cells infected with gfp control vector are used as negative controls. these cells are used to investigate the expression of endothelial cell characteristics, such as expression of endothelial cell markers and formation of tubular structure. the effect of ptn over-expression on cell growth and apoptosis is initially determined using standard assays. also, the impact of ptn over-expression and under- expression on the expression of endothelial cell markers, including the transcription factors gat a-2 and gat a-3, is determined using reverse transcriptive-polymerase chain reaction (rt-pcr), quantitative-polymerase chain reaction (qpcr), flow cytometric staining, and immunostaining, as previously performed and described above. in the in vivo studies, a standard xenograft model is utilized by inoculating 1x10 7 mm cells expressing ptn sense or anti-sense strand into the bone marrow of 6- week-old female severe combined immunodeficient (scid) mice. control cells consist of cancer cells transduced with gfp alone. tumors are removed surgically from euthanized mice every week and growth curves constructed by measuring tumor weight and human igg. in addition, at 5 weeks and at 10 to 13 weeks after bone marrow inoculation, animals are sacrificed and bone marrow is analyzed. tumor tissues are fixed, sections are stained with hematoxylin and eosin (h&e), and immunostained using endothelial cell markers. in addition, the presence of gfp in the inoculated mm cells permits the ready isolation of the injected cells from other cell contaminants (using facs). the impact of an in vivo environment on the ability of cells to transdifferentiate into endothelial-like cells is determined by flow sorting, rt-pcr, and qpcr, as described above. the results of these experiments will demonstrate the role of ptn is inducing trans-differentiation of bone marrow stem cells into endothelial-like cells and, thus, further establish the role of ptn in mm, namely promoting bone marrow vascularization and resulting tumor growth. mm cells induce bone marrow stem cells to express endothelial cell markers. ptn overexpression by mm cells is anticipated to increase the expression of endothelial cell markers in bone marrow stem cells. in constrast, the expression of endothelial cell markers will be down-regulated in cells infected with the ptn anti-sense strand. the level of ptn in mm may be high due to the presence of two sources of ptn - mm cells and macrophages. macrophages are considered a major component of the leukocyte infiltrate of tumors (20). exposure of monocytes/macrophages to interleukin-1 β (il- 1 β) leads to the expression of ptn. il- 1 β is highly expressed by mm in bone marrow. therefore, while mm cells may not normally generate sufficient levels of ptn alone to induce trans-differentiation of bone marrow stem cells into endothelial-like cells, persistent inflammation may lead to over-expression of ptn in tumors, generating a microenvironment that is conducive for trans-differentiation of tumor cells. consistent with this idea, it has been shown that over-expression of ptn in mcf-7 breast cancer cells, a cell line that expresses endogenous ptn, produced tumors that grow significantly faster than uninfected cells or cells transfected with a control dna plasmid (21). furthermore, tumors generated by injection of ptn-transduced mcf-7 cells have a greater vascular density compared to control tumors. similarly, in a corneal angiogenesis assay, it was shown that corneas receiving ptn-transfected mcf-7 cells scored a higher angiogenic response when compared to using non-transfected cells. thus, it is possible that infection of mm cells with ptn generates a more aggressive tumor compared to uninfected mm control cells. accordingly, mm cells infected with a ptn anti-sense strand are anticipated to generate a less vascularized tumor in the nude mice assay. these experiments will confirm that ptn has vasculogenic activity and promotoes mm vascularization. prior studies have shown that tumor cells can assume endothelial-like cell characteristics. for example, expression of vegf, fik-i, and fit-i has been detected in a variety of human tumor cell lines of nonendothelial origin (22). these included melanoma, ovarian, pancreatic and prostate carcinomas, breast cancer, and kaposi's sarcoma. using non-aggressive and aggressive breast cancer cell lines, it was shown that aggressive breast cancer cells expressed tie-2 and cd31 (23). similarly, tie-2 and angiopoietin expression have been detected in tumor cells of kaposi' s sarcoma (24). microarray analysis of highly aggressive and poorly aggressive human cutaneous melanoma cell lines showed that ve-cadherin and tie-2 were exclusively expressed by highly aggressive melanoma cells and undetectable in poorly aggressive tumor cells (25). in addition, these experiments will establish that ptn plays a role in the phenotypic conversion of mm cells into endothelial-like cells (30). example 16 identification of specific domains that mediate pleiotrophin-induced transdifferentiation activity the active domain of ptn that is responsible for its vasculogenic activity is identified by mutational analysis of the ptn polypeptide. past studies demonstrated that expression of a truncated mutant of ptn in breast cancer cells reverted the transformed phenotype of these cells. in addition, ptn deleted of its last 26 amino acids was found to act as a dominant negative effector for its mitogenic, angiogenic, transforming, and tumor- formation activities by heterodimerizing with the wild type protein. mutation or interference of the activity of the vasculogenic domain(s) with dominant negative ptn will block/reduce the transdifferentiation activity of this molecule. since there is no data about the vasculogenic activity of ptn, ptn mutants are constructed with consideration to (i) the c-terminal, n-terminal and domains which contain heparin-binding β-sheet domains and (ii) the middle portion that is a flexible linker between the terminal ends and is associated with transformation activity. using the full- length ptn as a template, these segments are amplified using specific pcr primers, and the veracity of the segments determined by dna sequencing. the pcr products are cloned into the topo pcr-2 vector, essentially as described (31). a tricistronic retroviral vector is generated in order to identify vasculogenic active domain of ptn, by subcloning ires-dominant-negative ptn (dnptn) down- stream of the wild type ptn and upstream of gfp to generate a cmv-ptn-ires- dnptn-ires-gfp construct, using standard molecular biology techniques. the size of the bicistronic construct, cmv-ptn-ires-gfp, is 2.5 kb. the size of the tricistronic construct, cmv-ptn-ires-dnptn-ires-gfp, is 3.7 kb. the maximum size of transgene that can be packaged into retrovirus is 8.0 kb; therefore, the size of the tricistronic transgene is well within the range of the retroviral packaging limit. in the construction of the tricistronic transgene, gfp is placed at the 3' end of the construct, which allows monitoring of the expression of both ptn and its dominant-negative mutant, dnptn. the tricistronic construct is packaged in 293 cells and the retrovirus is used to transduce thp- 1 and raw cells, in order to determine the vasculogenic inhibitory activity of the construct. in addition, mm cells are infected with the tricistronic retrovirus. cells infected with the bicistronic retroviral vector expressing dominant negative ptn and gfp (cmv-dnptn-ires-gfp) serves as a negative control. the infected cells are monitored for the expression of ptn and dnptn using northern and western blot analysis. after demonstrating the expression of tricistronic virus, cell growth, apoptosis, and expression of endothelial cell markers is determined in cultured cells essentially as described above. the in vivo activity of tricistronic-infected cells is examined by a standard xenograft model. cells infected with tricistronic and bicistronic retroviral vectors are implanted subcutaneously into nude mice and those animals with tumors are monitored daily starting at 10 days (10 mice per group). after 6 weeks, selected animals are sacrificed, and tumor size is measured in two perpendicular diameters. tumors are fixed, embedded, sectioned, and stained. the expression of endothelial cell markers is determined as described above. in addition, tumor cells are dispersed by enzymatic digestion and sorted by facs. total rna is extracted and pcr analysis is performed as described above. these experiments will identify the ptn domain responsible for its trans- differentiation activity, which will then be used as a target for therapeutic strategies (gene therapy, peptide therapy, monoclonal antibody, etc.) to control mm cell proliferation. previous studies have shown that different domains of ptn block other ptn activities. for example, the c-terminal (amino acids 111-136) of ptn blocked the mitogenic and transforming activities of ptn (32). in a separate study, the c-terminal- truncated protein inhibited the mitogenic, transforming, and angiogenic activities of ptn (28). similarly, a synthetic peptide corresponding to amino acids 111-136 blocked mitogenic, angiogenic, and tumor formation activities of ptn (28). a different pathway appears to be activated by ptn in nih 3t3 cells. the amino acid residues 41-64 of ptn are required for transformation of nih 3t3 cells; mutant ptn proteins that lacked ptn residues 41-64 did not transform nih 3t3 cells (33), suggesting that residues 41-64 contain a critical domain for signaling. another study reported that in addition to this domain, the n- or c-terminal lysine-rich domain together with amino acid residues 41 -64 were required for transformation of nih 3t3 cells, indicating that these domains support a similar functional role in the transformation by ptn. these studies suggest that various activities of ptn domains are cell dependent. example 17 pleiotrophin overexpression leads to the formation of multiple myeloma past studies have found a positive correlation between ptn serum levels and stages of cancers, and inversely with the response to therapy. an in vitro study has shown that a vast majority of cancer cells express ptn. as stated above, nothing is known about the function of ptn in mm. we hypothesize that ptn is linked to mm. in this study, ptn is over-expressed in murine bone marrow up-regulation of ptn leads to mm tumor formation. transgenic mice over-expressing insulin-like growth factor-i binding protein-4 under the control of the smooth muscle α-actin promoter were previously generated. the transgene was concentrated primarily in sm-rich tissues in the following order: bladder>aorta>stomach=uterus (34). an equivalent approach is used to generate transgenic mice over-expressing ptn under the control of sp-c promoter. briefly, the 3.1 kb ptn-ires-gfp fragment is excised from the retrovirus vector (see fig. 2) and subcloned downstream of the murine sp-c promoter 5 '-flanking region and upstream of the poly a signal (35). in addition, control transgenic mice expressing only gfp under the control of the sp-c promote are also be generated. the expression cassettes are removed from the plasmid backbone by digestion, separated by agarose gel electrophoresis, purified, and verified by dna sequencing. the transgene constructs are sent to the ucla transgenic core facility to be microinjected into c57bl/6 zygotes. the frequency of transgenic integration by this facility is greater than 25%, and over 60 transgenic mouse lines have been produced in 2002. founder animals and their progeny are screened by southern blotting from tail biopsies, using a rabbit β-globin probe. pcr is used for routine genotyping. transgenic mouse lines are identified by southern blot analysis of dna extracted from biopsied mouse tails. restriction dna is separated through agarose gels and transferred to nylon membranes according to standard protocols. hybridization is performed with the randomly labeled transgene. to demonstrate tissue-specific transgene expression, total rna from various tissues is isolated and analyzed by northern blot according to standard protocols. transgenic mouse lines are established from the sp- c/ptn-ires-gfp and sp-c/gfp transgenic founder mice. serum levels of ptn in the transgenic mice is determined by elisa. histopathological analysis is performed as follows. tissues are fixed and processed for immunostaining and in situ hybridization. sections are fixed, dehydrated, and embedded in paraffin. tissue sections are stained with hematoxylin and eosin according to standard protocols. the mouse tumors are classified according to the international agency for research on cancer (iarc)-who (2000). sections are stained with cell-specific markers to determine cellular compositions of transgenic bone marrow. to determine the global impact of ptn expression on the gene expression profile of murine lungs, the gene expression pattern of sp-c/ptn-ires-gfp transgenic mouse lungs is compared to that of sp-c/gfp control mouse lungs. rna is isolated from bone marrow monocytes of transgenic mice (heterozygote and homozygote) and control mice, and microarray analysis is performed on the rna samples. data analysis is performed by clustering genes with respect to their function to better characterize biological activities modulated by ptn expression. these experiments will demonstrate the in vivo role of ptn in the formation of mm. although there is no information about the role of ptn in mm embryogenesis, targeted over-expression of ptn in mouse brain produced transgenic mice with no gross morphological abnormalities (36), suggesting that that the over-expression of ptn is not lethal. furthermore, ptn is most prominently expressed during embryogenesis and perinatal stages of development (37), indicating that it is part of signaling cascade that operates during development. accordingly, mouse embryos will be monitored at various stages of embryonic development. in the development of the transgenic mice, several markers that enable differentiation between endogenous and exogenous expression of ptn are included. in addition to ptn, the bicistronic construct used to generate transgenic mice expresses gfp down-stream of ires. the presence of the ires allows post-transcriptional processing of ptn, a secreted protein, independent of gfp, which is a cellular protein. therefore, cells over-expressing human ptn also express gfp, as previously demonstrated in retrovirally infected thp-i and raw cells. in addition, the presence of gfp allows the ready separation of transgene-containing mm cells from other contaminating cells by facs for in vitro studies. the expression of endothelial cell markers is examined (i) in vivo by immunostaining and confocal microscopy and (ii) in vitro by western blot, rt-pcr, and qpcr, as described earlier. ptn demonstrates considerable species cross-reactivity, due to a high amino acid sequence homology (exceeding 98%) among human, mouse, rat, and bovine. accordingly, human ptn is predicted to interact with its putative receptors in mouse cells, as has been demonstrated in the over-expression of human ptn in the brain of transgenic mice. it is understood that over-expression of ptn under the control of the sp-c promoter will lead to the formation of hyperplasia and vascularization in the bone marrow. persistent elevation of monocyte numbers and their conversion to resident macrophages are hallmarks of chronic inflammation. this accumulation results from either increased recruitment of circulating monocytes or proliferation of residing monocytes/macrophages. it has been reported that ptn stimulates proliferation of peripheral blood-derived monocytes and tissue macrophages. therefore, expression of ptn in bone marrow can lead to the enhancement of macrophage accumulation. there are two potential stimulators that can increase expression of ptn in patients with mm: il-i β and tnf-α, factors shown to up-regulate ptn expression in monocytes/macrophages. it is known that il- 1 β expression is up-regulated in patients with nonmalignant mm and tnf- α expression is increased in patients with mm (51). therefore, ptn is hypothesized to be an important player in the pathogenesis of these diseases. these experiments will establish that over-expression of ptn in transgenic mice leads to mm cell proliferation. all of the above u.s. patents, u.s. patent application publications, u.s. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the application data sheet, are incorporated herein by reference, in their entirety. references cited: i . vacca a. ria r. et al. endothelial cells in the bone marrow of patients with multiple myeloma. blood 2003; 102:3340-3348. 2. kumar s., witzig te, et al. effect of thalidomide therapy on bone marrow angiogenesis in multiple myeloma. leukemia 2004; 18:624-627. 3. carmeliet, p. angiogenesis in health and disease. nat med 2003; 9:653-660. 4. jager, r., list, b., knabbe, c, souttou, b., raulais, d., zeiler, t., wellstein, a., aigner, a., neubauer, a., and zugmaier, g. serum levels of the angiogenic factor pleiotrophin in relation to disease 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r.e., keene, cd., ortiz-gonzalez, x. r., reyes, m., lenvik, t., lund, t., blackstad, m., et al. pluripotency of mesenchymal stem cells derived from adult marrow. nature 2002; 418:41-49. 18. goodell, m.a., jackson, k. a., majka, s.m., mi, t., wang, h., pocius, j., hartley, c.j., majesky, m.w., entman, m.l., michael, l.h., et al. stem cell plasticity in muscle and bone marrow. ann n yacadsci 2001; 938:208-218; discussion 218-220. 19. lagasse, e., connors, h., al-dhalimy, m., reitsma, m., dohse, m., osborne, l., wang, x., finegold, m., weissman, ll. , and grompe, m. purified hematopoietic stem cells can differentiate into hepatocytes in vivo. nat med 2000; 6:1229-1234. 20. balkwill, f., and mantovani, a. inflammation and cancer: back to virchow? lancet 2001 ; 357:539-545. 21 choudhuri, r., zhang, h.t., donnini, s., ziche, m., and bicknell, r. an angiogenic role for the neurokines midkine and pleiotrophin in tumorigenesis. cancer res 1997; 57:1814-1819. 22. masood, r., cai, t., zheng, t., smith, d.l., hinton. d.r., and gill, p.s. vascular endothelial growth factor (vegf) is an autocrine growth factor for vegf receptor-positive human tumors. blood 200l; 98:1904-1913. 23. hendrix, mj., seftor, e.a., kirschmann, d.a., and seftor, r.e. molecular biology of breast cancer metastasis. molecular expression of vascular markers by aggressive breast cancer cells. breast cancer res 2000; 2:417-422. 24. brown, l.f., dezube, b.j., tognazzi, k., dvorak, h.f., and yancopoulos, g.d. expression of tiel, tie2, and angiopoietins 1, 2, and 4 in kaposi's sarcoma and cutaneous angiosarcoma. am j pathol 2000; 156:2179-2183. 25. hendrix, m.j., seftor, e.a., meltzer, p.s., gardner, l.m., hess, a.r., kirschmann, d.a., schatteman, g.c., and seftor, r.e. expression and functional significance of ve-cadherin in aggressive human melanoma cells: role in vasculogenic mimicry. proc natl acad sci usa 2001; 98:8018-8023. 26. vacherot, f., caruelle, d., chopin, d., gil-diez, s., barritault, d., caruelle, j.p., and courty, j. involvement of heparin affin regulatory peptide in human prostate cancer. prostate 1999; 38:126-136. 27. riegel, a.t., and wellstein, a. the potential role of the heparin-binding growth factor pleiotrophin in breast cancer. breast cancer res treat 1994; 31 :309-314. 28. bernard-pierrot, l, delbe, j., rouet, v., vigny, m., kerros, m.e., caruelle, d., raulais, d., barritault, d., courty, j., and milhiet, p.e. dominant negative effectors of heparin affin regulatory peptide (harp) angiogenic and transforming activities. j biol chem 2002; 277:32071-32077. 29. kilpelainen, i., kaksonen, m., avikainen, h., fath, m., linhardt, r.j., raulo, e., and rauvala, h. heparin-binding growth-associated molecule contains two heparin-binding beta -sheet domains that are homologous to the thrombospondin type i repeat. j biol chem 2000; 275:13564-13570. 30. zhang, n., zhong, r., and deuel, t.f. domain structure of pleiotrophin required for transformation. j biol chem 1999; 274:12959-12962. 31. qin, m., zeng, z., zheng, j., shah, p.k., schwartz, s.m., adams, l.d., and sharifi, b. g. suppression subtractive hybridization identifies distinctive expression markers for coronary and internal mammary arteries. arterioscler thromb vase biol 2003; 23:425-433. 32. bernard-pierrot, l, delbe, j., caruelle, d., barritault, d., courty, j., and milhiet, p.e. the lysine-rich c-terminal tail of heparin affin regulatory peptide is required for mitogenic and tumor formation activities. j biol chem 2001; 276:12228-12234. 33. chauhan, a.k., li, y.s., and deuel, t.f. pleiotrophin transforms nih 3t3 cells and induces tumors in nude mice. proc natl acad sci usa 1993; 90:679- 682. 34. wang, j., niu, w., witte, d.p., chernausek, s.d., nikiforov, y.e., clemens, t.l., sharifi, b., strauch, a.r., and fagin, j. a. overexpression of insulin-like growth factor-binding protein-4 (igfbp- 4) in smooth muscle cells of transgenic mice through a smooth muscle alpha-actin-igfbp-4 fusion gene induces smooth muscle hypoplasia. 1998; endocrinology 139:2605-2614. 35. glasser, s.w., korfhagen, t.r., bruno, m.d., dey, c, and whitsett, j.a. structure and expression of the pulmonary surfactant protein sp-c gene in the . ÷, mouse. j biol chem 1990; 265:21986-21991. 36. pavlov, l, voikar, v., kaksonen, m., lauri, s.e., hienola, a., taira, t., and rauvala, h. role of heparin-binding growth-associated molecule (hb-gam) in hippocampal ltp and spatial learning revealed by studies on overexpressing and knockout mice. moi cell neurosci 2002; 20:330-342 37 rauvala, h., vanhala, a., castren, e., noio, r., raulo, e., merenmies, j. 5 and panula, p. expression of hb-gam (heparin-binding growth-associated molecules) in the pathways of developing axonal processes in vivo and neurite outgrowth in vitro induced by hb-gam. brain res dev brain res 1994; 79:157-176. 38. matanic, d., beg-zec, z., stojanovic, d., matakoric, n., flego, v., and milevoj-ribic, f. cytokines in patients with lung cancer. scand j immunol 2003; 57:173-178. 39. lafleur, d.w., fagin, j.a., forrester, j.s., rubin, s.a., and sharifi, b.g. cloning and characterization of alternatively spliced isoforms of rat tenascin. platelet-derived growth factor-bb markedly stimulates expression of spliced variants of tenascin mrna in arterial smooth muscle cells. j biol chem 1994; 269:20757-20763. 40. yang, l., li, s., hatch, h., ahrens, k., cornelius, j.g., petersen, b.e., and peck, a.b. in vitro trans-differentiation of adult hepatic stem cells into pancreatic endocrine hormone-producing cells. proc natl acad sci usa 2002; 99:8078-8083. from the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. accordingly, the invention is not limited except as by the appended claims.
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107-293-373-369-460
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US
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[
"US"
] |
C06B45/14,C06C9/00,C23C14/14,C23C14/34
| 1994-07-15T00:00:00 |
1994
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[
"C06",
"C23"
] |
method for fabricating an ignitable heterogeneous stratified metal structure
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a multilayer structure has a selectable, (i) propagating reaction front velocity v, (ii) reaction initiation temperature attained by application of external energy and (iii) amount of energy delivered by a reaction of alternating unreacted layers of the multilayer structure. because v is selectable and controllable, a variety of different applications for the multilayer structures are possible, including but not limited to their use as ignitors, in joining applications, in fabrication of new materials, as smart materials and in medical applications and devices. the multilayer structure has a period d, and an energy release rate constant k. two or more alternating unreacted layers are made of different materials and separated by reacted zones. the period d is equal to a sum of the widths of each single alternating reaction layer of a particular material, and also includes a sum of reacted zone widths, t.sub.i, in the period d. the multilayer structure has a selectable propagating reaction front velocity v, where v=k(1/d.sup.n).times.[1-(t.sub.i /d)] and n is about 0.8 to 1.2.
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1. an ignitable heterogeneous stratified structure for supporting the propagation of an internal chemical reaction along an expanding wavefront from an ignition starting point, comprising: alternating stratiforms of a first exothermic-constituent material and a second exothermic-constituent material fused together as a whole with a mutual interface of said first exothermic-constituent material reacted with said second exothermic-constituent material, wherein said first exothermic-constituent material independently has a uniform thickness "t.sub.a " in the range of 20-10,000 .ang. (0.002-1.0 .mu.m), said second exothermic-constituent material independently has a uniform thickness "t.sub.b " in the range of 20-10,000 .ang. (0.002-1.0 .mu.m), said interface of reacted first and second exothermic-constituent materials independently has a thickness "t.sub.i " in the range of 3-180 .ang. (0.0003-0.018 .mu.m, wherein a recurring interval "d" that can occur more than once in a single structure is equal to t.sub.a +t.sub.b +2t.sub.i and is in the range of 50-20,000 .ang. (0.005-2.0 .mu.m); wherein said first and second exothermic-constituent materials are limited to materials that can entirely provide between themselves a self-sustained exothermic chemical reaction once started by an externally-sourced ignition; and said stratified structure is capable of creating a predictable velocity "v" in the range of 0.2-100 meters per second that depends on the relative proportions of said thicknesses of said first and second exothermic-constituent materials "t.sub.a " and "t.sub.b ", and said thickness "t.sub.i " of said interface of reacted first and second exothermic-constituent materials, expressed mathematically as, ##equ10## where said recurring interval "d" equals t.sub.a +t.sub.b +2t.sub.i, "k" is an energy release constant having a range of 100-20,000 meters .ang./sec, and the exponent "n" is a constant that ranges from 0.8 to 1.2. 2. the structure of claim 1, wherein the stratified structure is such that a maximum velocity "v" of said expanding internal chemical reaction wavefront is provided by limiting "d" to the range of 6.0 t.sub.i .gtoreq.d.gtoreq.3.0 t.sub.i. 3. the structure of claim 1, wherein the stratified structure is capable of creating said ignition starting point with an ignition temperature "t.sub.a " in the range of 200.degree. c.-1500.degree. c. with total energies .delta.h in the range of 50-5,000 joules per gram, expressed mathematically as, ##equ11## 4. the structure of claim 1, wherein the stratified structure is capable of creating said internal chemical reaction with predictable available heats of formation .delta.h.sub.f in the range of 10k-200k joules per mole that are dependent on particular relative thickness combinations of said first and second exothermic-constituent materials "t.sub.a " and "t.sub.b ", and said interface of reacted first and second exothermic-constituent materials "t.sub.i ", expressed mathematical as, ##equ12## where .delta.h=total energy. 5. the structure of claim 1, further comprising: an isolation stratum interposed and fused between the alternating stratiforms of said first and second exothermic-constituent materials fused together as a whole, and providing for attenuation of said internal chemical reaction. 6. the structure of claim 1, wherein said first and second exothermic-constituent materials comprise thermalizations of their respective elemental atoms and/or molecules providing for a reduction of as-deposited energy. 7. the structure of claim 1, wherein said first exothermic-constituent material and said second exothermic-constituent material are selected to form chemical reactions resulting in at least one of nisi, vb.sub.2 and tib.sub.2 for heats of formation in the range of 70k-120k joules per mole, monel/al 400, nial, pdal, tisn and snv for heats of formation in the range of 45k-70k joules per mole, and zral and tial for heats of formation in the range of 20k-45k joules per mole.
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background of the invention 1. field of the invention this invention relates to multilayer structures, and more particularly to multilayer structures with selectable, rapidly propagating reaction wave fronts, as well as selectable total energies, adiabatic temperatures, ignition temperatures and ignition powers. 2. description of the related art multilayer structures are thin-film materials that are periodic in one dimension in composition or in composition and structure. composition/structure variation is generated during the synthesis of the structure, which is typically accomplished using atom by atom, atom by molecule, or molecule by molecule technologies. individual component layers in a multilayer may vary in thickness from one atomic layer (.about.2 angstroms) to thousands of atomic layers (>10,000 angstroms) of a given material. multilayer structures can be synthesized using elemental, alloy, or compound layers to form both microstructures and combinations of elements/materials that cannot be produced using traditional processing technology. multilayers are made by alternate deposition of two or more different materials. after the first few layers, the structure of all the layers of one material are the same. the structure of each material is clearly of importance for the properties of the multilayer, not only in itself, but also for the influence it can have on the structure of the other material. each material acts as a substrate for the deposition of the other. the simplest multilayer structures are those which consist of a composition modulation imposed on a single structure. in almost all cases of this type, intermixing can lead to a uniform single phase of the starting crystal structure or atomic geometry. while compositionally modulated multilayers may be regarded as a single phase, there are examples of two phase multilayers, in which the two materials have different structures and in which simple homogenization is not possible. if two phase multilayers are annealed, one material may diffuse in the other or react with it to yield a third phase. alternatively, the two materials may be stable in contact with each other. whatever type of multilayer structure, the nature of the interfaces is of great significance. the atomic structure and the volume density of the interfaces between alternate layers in a multilayer can control or strongly affect the physical properties of the materials. in particular with regard to power dissipation of a multilayer structure during exothermic mixing of the alternating unreacted layers, both the number per unit volume and atomic structure of the interfaces control the rate at which the alternating elements mix and produce heat. the interface number per unit volume (density) can be controlled by varying the size of the period. the smaller the period, the closer the interfaces to each other and the higher their density. the atomic structure of the interface can be controlled by varying deposition parameters and/or deposition techniques. although multilayer structures can be found in equilibrium in natural systems, e.g., dichalcogenides, most artificial metallic multilayers have free energies far in excess of equilibrium and are susceptible to some type of transformation if there is sufficient atomic mobility. contributing to the excess free energy are the interfacial free energy, the strain energies and excess chemical energy relative to a mixed composition. stability is clearly important if the special properties of multilayers are to be exploited as deposited. the simplest type of structural change in a multilayer is diffusional mixing at the interfaces. the increased interfacial diffuseness and the reduced amplitude of the composition modulation may affect many properties. the repeat distance of a multilayer period can also change. individual layer materials may show changes in structure. crystalline layers may amorphize and amorphous layers may crystallize. the amorphorization and crystallization temperatures may be raised or lowered by interactions with the surrounding layers. polycrystalline layers and mosaic layers may show grain growth. the grain boundaries running perpendicular to the layers are paths for fast diffusion, and they can enhance diffusional mixing and help destroy a compositional modulation. a further type of structural change is reaction between the materials of the multilayer to give one or more new phases. if the multilayer is composed of elements with a strongly negative enthalpy of mixing, the heat released when the reaction is started with a thermal probe may be sufficient to allow it to proceed unassisted. this has been observed in transition metal/amorphous silicon multilayers. the phase which forms by reaction in a multilayer may itself be metastable. the possible origins of the distinctive properties of multilayers are, (i) thin film effects, due to the limited thickness of one or more of the layers, (ii) interface effects, arising from the interactions between neighboring layers, (iii) coupling effects between layers of the same type, acting through the intervening layers and (iv) periodicity effects from the overall periodicity of the multilayer. multilayer properties can be tailored by controlling the period and structure of the alternate layers. the characteristics of the multilayer which may affect the properties are, (i) layer thickness and its spread (either periodic or non-periodic designs may be desirable), (ii) interfacial structure, including coherency, (iii) the crystal structure and crystallographic orientation (or amorphicity) of the constituent materials, (iii) the grain size in crystalline layers and (iv) the stresses in the layers. the synthesis of multilayer structures can be accomplished by using techniques in which the product is formed by means of atom by atom processes. such techniques include physical vapor deposition, chemical vapor deposition, electrochemical deposition, electrolytic deposition, atomic layer epitaxy and in some cases mechanical processing. multi-vapor-source configurations are used in the synthesis of metal multilayers with thermal sources. these are directly analogous to molecular beam epitaxy systems except that the sources need not be the knudsen cell type. in these systems the sources and samples are stationary, the layering is achieved through interruption of the vapor streams to the substrate by the use of a rotating pin wheel or reciprocating shutters. substrates can be held at temperatures from 4 to about 1300 degrees k. heating mechanisms include electron beam bombardment and resistive and optical heating. sample sizes are usually less than 25 cm.sup.2 and are dictated by specific system geometries and heating requirements. multisource configurations are also used in sputter deposition systems. in these systems the sputter sources are widely separated and the substrates moved past the sources, a single layer being deposited on each pass by a source. sputter sources are solid materials, atoms or atom clusters being ejected from the solid target into the vapor by bombardment of the target surface with energetic particles. the ejected atoms impinge on a substrate and condense to form a film. in most cases, noble gases are used as the sputter gas, their ions being positively charged. the process is called cathodic sputtering. ions are formed by establishing a plasma in much the same manner as a glow discharge is formed in a low pressure gas by an electric field between two electrodes. factors to be considered include sputter source deposition surface coupling, the energy distribution of the sputtered atoms and the geometry of the vapor source substrate configuration. the sputtering process entails establishing a plasma discharge and imposing a potential of the correct polarity so that ionized gas atoms are accelerated to the cathode surface, where, if of sufficient energy, they dislodge other atoms. these secondary atoms travel from the cathode surface to the deposition surface, being adsorbed to form a deposit. there has been a limited understanding on the nature of interfacial interactions and on their relationship to the advance of the reaction front resulting from a chemical reaction between layers in the structure. the use of thin foils to investigate the propagation of such a combustion or reaction wave has been demonstrated for a nickel-aluminum system. initiation of a reaction wave has been found to be triggered by the melting of nickel for a large period structure regardless of the composition of the foil, u. anselmi-tamburini and a. z. munir, j. appl. phys. 66 (10), pp 5039-5045, 1989. additionally, the combustion synthesis of multilayer nickel-aluminum systems has also been reported by t. s. dyer and z. a. munir, scripta metallurgica et materialia, vol. 30, no. 10 pp 1281-1286, 1994. however, these investigators have not produced multilayer structures with selectable wavefronts. accordingly, there is a need for a multilayer structure that has a selectable chemical reaction wavefront, a selectable initiation temperature by an external energy source and a selectable amount of energy delivered by a reaction of the alternating layers of the multilayer structure. it would be an advantage to provide multilayer structures in which one is able to determine the velocity of the chemical reaction wavefront, the total energy release, the rate of energy release, the adiabatic temperature and the ignitition temperature or power for such a wavefront. for a rapid heat source, there is a need to know how fast the wavefront travels which determines the rate at which energy is released by the structure. it would be desirable to provide multilayer structures that can be tailored for different applications depending on their chemical composition and physical structure that control their chemical reaction wavefronts. summary of the invention accordingly, it is an object of the invention to provide a multilayer structure that has a selectable chemical reaction wavefront velocity. another object of the invention is to provide a multilayer structure that has a selectable initiation temperature. still a further object of the invention is to provide a multilayer structure that has a selectable amount of energy delivered by a reaction of the alternating unreacted layers of the multilayer structure. another object of the invention is to provide a multilayer structure that has a selectable chemical reaction wavefront velocity that is initiated at temperatures determined by their physical composition and structure. yet another object of the invention is to provide a multilayer structure that has a selectable chemical reaction wavefront velocity of 0.2 m/sec to about 100 m/sec. another object of the invention is to provide a multilayer structure that has a selectable wavefront velocity that is proportional to an amount of energy that is generated by the chemical reaction wavefront between first and second alternating layers. still another object of the invention is to provide a multilayer structure with an energy release rate constant k, and a selectable chemical reaction wavefront velocity v that is determined by its period d and a sum of reacted zone widths t.sub.i in the period d, where v=k(1/d.sup.n).times.[1-(t.sub.i /d)] and n is about 0.8 to 1.2. another object of the invention is provide a multilayer structure with a selectable chemical reaction wavefront velocity with a period d, a sum of reacted zone widths ti in the period d, where d=(1.5 to 3.0).times.t.sub.i, defining a structure having maximum velocity. another object of the invention is to provided a multilayer structure with a period d, and the period d includes a sum of reacted zone widths t.sub.i, of about 5 to 360 angstrom and the multilayer structure has a selectable chemical reaction wavefront velocity. yet another object of the invention is to provide a multilayer structure with a selectable chemical reaction wavefront with available heats of formation, .delta.h.sub.f, of about 10 k joules/mole to 200 k joules/mole and total energies .delta.h that vary as ##equ1## and range linearly with sample volume for given d and t.sub.i. another object of the invention is to provide a multilayer structure that has a selectable chemical wavefront velocity, and an isolation layer positioned between alternating unreacted layers. the multilayer structure of the invention has a period d for a particular composition of the multilayer structure, and an energy release rate constant k. the multilayer structure includes two or more alternating unreacted layers made of different materials. each layer is separated by a thin reacted zone. period d of the multilayer structure is equal to a sum of widths of each single alternating unreacted layer of given composition and a sum of reacted zone widths t.sub.i. the multilayer structure has a selectable propagating reaction front velocity v, where v=k(1/d.sup.n).times.[1-(t.sub.i /d)] and n is about 0.8 to 1.2. multilayer structures of the invention also have selectable initiation temperatures that are attained by application of external energy, as well as a selectable amount of energy that is delivered by a reaction of the alternating unreacted layers of the multilayer structure. in one embodiment, the multilayer structure has a selectable propagating reaction front velocity v. a first alternating unreacted layer a has a thickness of t.sub.a, a second alternating unreacted layer b has a thickness of t.sub.b. a reacted zone exists between the unreacted layers a and b with a thickness of t.sub.ab. the period d of the multilayer structure is equal to t.sub.a +t.sub.b +2t.sub.ab, and the structure has an energy release rate constant k. the selectable propagating reaction front velocity v can be chosen depending on a number of different parameters, and is highly dependent on the energy available from the chemical reaction between unreacted layers a and b and how fast it can be released. v is expressed as: v=k(1/d.sup.n).times.[1-2t.sub.ab /d]. and n is 0.8 to 1.2. the width of t.sub.ab can be minimized for increased velocities. as the atoms which constitute unreacted layers a and b are deposited on the substrate, the substrate is maintained at a chilled temperature. this chilled temperature should be less than about 100 to 110 degrees c. alternatively, an isolation layer can be positioned between the alternating layers. the isolation layer can suppress up to about 75% of an interfacial reaction between alternating unreacted layers while the alternating unreacted layers are deposited on a substrate, leaving more energy that is available for the chemical reaction between the unreacted layers after the multilayer structure has been formed. another method for minimizing interaction between the alternating unreacted layers during the formation of the multilayer structure is to thermalize the atoms or molecules as they are deposited to form the individual unreacted layers, e.g., a and b. this thermalization reduces the kinetic energy of the atoms or molecules in the vapor and thereby reduces their as-deposited energy which can lead to mixing and interactions. in a specific embodiment of the invention, individual unreacted layers have thicknesses of about 20 to 10,000 angstroms, the period of the structures being about 50 to 20,000 angstroms. the propagating reaction front velocity v is dependent on the size of the reacted zone between the layers and the reactive heat that is generated by the reaction of the unreacted layers. velocity v is proportional to the power generated by the chemical reaction between the alternating unreacted layers. the reaction between alternating unreacted layers produces a selectable amount of energy. in this regard, the velocity v and the total energy are selectable, depending on the application. the chemical reaction between the elemental components in alternating unreacted layers determines the energy available. the rate at which the energy is released is directly proportional to the rate at which these atoms react by thermally activated processes or by structurally enhanced mixing. because these reactions are thermally activated, the higher the sample temperature, the higher the rate of reaction. additionally, a significant parameter is that the number of atoms in close contact near an interface determines the rate of energy release at a given temperature. the higher the number of interfacial atoms, the higher the rate of heat release. therefore, the rate of heat release or reaction delivered power is proportional to the interfacial area per unit volume, which is inversely proportional to the period d. the multilayer structures of the present invention have a selectable reaction front velocity that is controlled by the power delivered to the reaction front by the exothermic chemical reaction to form the compound a.sub.x b.sub.y in a two component structure. other important material properties include but are not limited to thermal property parameters such as, (i) material density, (ii) material specific heat, (iii) thermal conductivity and (iv) any mechanisms for heat loss during reaction-convection/evaporation/melting. because the multilayer structures of the present invention have selectable propagating reaction fronts, they are suitable for a variety of different applications including but not limited to, (i) ignitors, (ii) joining, (iii) new materials, (iv) smart materials and (v) medical devices and treatments. description of the drawings fig. 1 is a schematic of a multilayer cross section showing interfacial reacted zone of thickness t.sub.ab and unreacted layer thicknesses of t.sub.a and t.sub.b. fig. 2 is a graph of reaction velocity as a function of multilayer period d for an al/monel 400 structure. fig. 3 is a graph of exothermic heat of reaction as a function of multilayer period d for the al/monel 400 structure. fig. 4 is a graph of the heat of reaction as a function of 1/d, the inverse of the multilayer period, for an al/monel 400 structure. fig. 5 is a schematic representation of the temperature distribution about the reaction front heat source for a multilayer structure. fig. 6 is a graph of calculated reaction front velocity as a function of the multilayer period for different energy release rate constants k, for a given reacted zone thickness t.sub.ab. fig. 7 is a graph of calculated reaction front velocity as a function of the multilayer period d for different reacted zone thicknesses t.sub.ab, for a given energy release rate constant k of 8400 m.ang./sec. fig. 8 is a graphical comparison of measured reaction front velocity as a function as the multilayer period d for al/monel 400 multilayer structures with calculated reaction front velocities for k values of 8400, 4200 and 2100 m.ang./sec. detailed description of the preferred embodiments multilayer structures of the invention are made of two or more alternating unreacted layers of known composition. each multilayer structure has a period d for a given composition of the multilayer structure equal to the sum of widths of individual alternating unreacted layers and the sum of reacted zone widths of the composition. each multilayer structure has an associated energy release rate constant k. an unreacted layer is only counted once in the period d. however, there may be more than one unreacted layer of the same composition in the period. thus in a multilayer structure that has three different unreacted layers, a, b, and c, the period d is equal to a summation of their three widths, and also includes the widths of reacted zones in the period d. in this example, a reacted zone between unreacted layers a and b is t.sub.ab, a reacted zone between unreacted layers b and c is t.sub.bc and a reacted zone between unreacted layers c and a is t.sub.ac. in this example, the summation of the reacted zone widths in period d, represented as t.sub.i, is the total widths of t.sub.ab +t.sub.bc +t.sub.ac. it will be appreciated that the invention can include only two alternating unreacted layers, or an:/number of different unreacted layers. however, the multilayer structure has a selectable propagating reaction front velocity v, where v=k(1/d.sup.n).times.[1-t.sub.i /d)] equation (1) and n is about 0.8 to 1.2. the reaction between the different alternating unreacted layers requires the attainment of an initiation temperature, represented as t.sub.a. t.sub.a is also selectable and can be in the range of about 200 to 1500 degrees c. in one embodiment the minimum energy to attain t.sub.a is about 1 millijoule in a time period of about 1 millisecond or less. the amount of energy that is delivered by the reaction of the alternating unreacted layers is also selectable. it can be in the range of about 50 joule/g to about 5,000 joule/g. for ease of discussion, a multilayer structure with two alternating unreacted layers a and b will now be presented. however, it will be appreciated that the invention is not limited to this particular structure. a multilayer structure 10 of the invention is illustrated in fig. 1 and is formed of a first alternating unreacted layer 12 of a material a with a thickness of t.sub.a, a second alternating unreacted layer 14 of a material b with a thickness of t.sub.b, that can be deposited on a substrate 16 that can be removed after formation of multilayer structure 10. the unreacted layers can be in the range of 20 to 10,000 angstroms and can be elemental, alloy or compound layers. a reacted zone 18, generally denoted as t.sub.ab is formed between unreacted layers a and b, and has a thickness of t.sub.ab. t.sub.ab can be in the range of about 3 to 180 angstroms and is preferably as small as possible such as less than 30 angstroms for highest velocities. the temperature required to initiate the rapid self propagating reaction between unreacted layers a and b can be selected by control of the reacted zone thickness t.sub.ab and the multilayer period d. the periodicity of multilayer structure 10 is d, and is defined as the summation of t.sub.a, t.sub.b and 2t.sub.ab. period d is about 50 to 20,000 angstroms. multilayer structure 10 has an energy release rate constant k that is dependent on a variety of parameters and varies from structure to structure, as more fully set forth in this specification. multilayer structure 10 is determined during synthesis by control of the individual component layer thicknesses. the layers may vary from 20 to about 10,000 angstroms in thickness. the average composition of the samples is controlled by controlling the relative thicknesses of the individual component layers. multilayer structure 10 has a selectable propagating reaction front velocity v, where v=k(1/d.sup.n).times.[1-(2t.sub.ab /d)] equation (2) and n is 0.8 to about 1.2. k can be about in the range of about 100 to 20,000 m.ang./sec, or 500 to 15,000 m.ang./sec or 1,000 to 10,000 m.ang./sec. in one embodiment of the invention, the period d is about (1.5 to 3.0).times.2t.sub.i for maximum velocity, and t.sub.i is about 5 to 360 angstroms. the chemical reaction between the elemental components in unreacted layers a and b determines the energy available. the rate at which the energy is released is directly proportional to the rate at which these atoms react by thermally activated processes or by structurally enhanced mixing. because these reactions are thermally activated, the higher the sample temperature, the higher the rate of reaction. additionally, a significant parameter of the invention is that the number of atoms in close contact near an interface determines the rate of energy release at a given temperature. the higher the number of interfacial atoms, the higher the rate of heat release. therefore, the rate of heat release or reaction delivered power is proportional to the interfacial area per unit volume, which is inversely proportional to period d. significantly, multilayer structures 10 of the invention can have propagating reaction front velocities v of about 0.2 m/sec to 100 m/sec. the total energies that are available from such reactions scale with the volume of material and the heats of formation that are, by way of example, listed below. propagating reaction front velocity v is selectable in that depending on a variety of different parameters, conditions, and materials, it can be controlled and a desired v obtained. thus, for different applications, v can vary. v is generally in the range of about 0.2 to 100 m/sec. heats of formation are about 10 to 200 k joules/mole. for higher energy multilayer structures, including but not limited to nisi, vb.sub.2 and tib.sub.2, the heats of formation are about 70 to 120 kjoules/mole. mid range heats of formation are about 45 to 70 kjoules/mole. suitable mid range materials include but are not limited to monel/al 400, nial, pdal, tisn and snv. lower range multilayers, such as zral and tial, have heats of formation of about 20 to 45 k joules/mole. heats of formation for various binary alloys and compounds are listed in cohesion in metals: transition metal alloys, f. r. de boer et al., elsevier science publishers b. v., 1988, pages 103 through 634, incorporated herein by reference. the multilayer structures of the present invention have wide spread applications, including use as ignitors, in joining applications, in fabrication of new materials, as smart materials and medical devices and therapies. in the application of ignitors, multilayer structure 14 can be a reaction initiator, wide area heating device or timed explosive initiator. joining applications include composite/metal joining, semiconductors (low temperature), honeycombs, in field repairs and as a low energy replacement for spot or arc welding or joining with the same material. as new materials, multilayer structure 14 can be used to form single crystal foils of reaction intermetallic compounds, metal matrix composites (intermetallic), and near net form structures (intermetallic). smart material applications are in the areas of engineering energy release, controlled distortion, light emission signal and sequence processing. they can also be used as very local heat sources in medical therapies and devices. suitable multilayer ignitors include al/monel 400, nial, zral, nisi, mosi, pdal, and rhal. by way of example, but not intended to limit the invention, an al/monel 400 ignitor can be made having a heat of formation of about 55 kcal/mole, v of about 17 to 20 m/sec. however, its sensitivity may be too high at small periods. another ignitor is zral.sub.3, or zral.sub.2 each with a heat of formation of about 45 kcal/mole, and v of about 2 to 15 m/sec. an advantage of these materials is that they have lower heats of formation, are less sensitive to smaller periods and require less energy to ignite. the ignitor tial has a heat of formation of 33-35 kcal/mole and v of up to 10 m/sec. multilayer structure 10 exhibits compound formation with high heats of formation. it can be ignited and a reaction front propages through the structure to form the compound. these reaction velocities may be quite slow but are observed to increase as the size of multilayer period d decreases. multilayer structure 10 can be made by a variety of methods well known to those skilled in the art, including but not limited to sputtering in a low vacuum environment. sputter deposition can occur in a vacuum chamber of a few millitorr of argon. in one embodiment, multilayer structure 10 is formed from two targets of atoms a and b on a substrate maintained at less than about 100 to 110 degrees c. a voltage is applied and an argon plasma sheath induced. argon atoms are accelerated to the target surface ,and transfer mechanical energy to the target atoms which are ejected out and deposit on the substrate. it is desirable to employ a method of deposition which does not impart a great deal of energy to the atoms as they are deposited because this raises the temperature of the deposited layers which in turn increases their mixing. the goal is to deposit the atoms with low energy and with a minimal reacted zone thickness of t.sub.i. another objective of maintaining a low deposition temperature is to minimize the chance of a complete reaction occurring during deposition of the atoms. multilayer structures 10 of the invention have a controlled reacted zone thickness and a controlled size of period d. these parameters will vary for a particular material system. during formation of multilayer structure 10, the incoming atoms have low energy and are thermalized. additionally, a full or partial isolation layer can be positioned between unreacted layers a and b. this layer permits areas of direct contact between the layers facilitating ignition, and at the same time can suppress up to about 75% of an interfacial reaction between unreacted layers a and b when layers a and b are deposited during synthesis. three types of measurements have been made to characterize multilayer structure 10. these include, (i) reaction front velocity v as a function of multilayer structural parameters, (ii) available heat of reaction stored in multilayer structure 10 as a function of structural parameters by differential scanning calorimetry (dsc) and (iii) structural evaluation by planar and cross-section transmission electron microscopy (tem). the structure of a multilayer material is determined during synthesis by control of individual component layer thicknesses, t.sub.a and t.sub.b. unreacted layers t.sub.a and t.sub.b may be of thicknesses varying from about 20 to 10,000 angstroms. the average composition of such a sample is controlled by controlling the relative thickness of the individual component layers a and b. the period d of multilayer structure 10 is defined as d=t.sub.a +t.sub.b +2t.sub.ab equation (3) the average composition is denoted as a.sub.x b.sub.y, where ##equ2## where: n.sub.a =t.sub.a n.sub.a, and n.sub.b =t.sub.b n.sub.b ; n.sub.a =the number of atoms of a per cm.sup.3 ; n.sub.b =the number of atoms of b per cm.sup.3 ; n.sub.a =the number of atoms of a per cm.sup.2 for a layer of thickness t.sub.a ; n.sub.b =the number of atoms of b per cm.sup.2 for a layer of thickness t.sub.b. it is the average a.sub.x b.sub.y composition that determines the maximum energy available to drive the reaction. by control of relative layer thickness, the average composition of a multilayer material can be defined. the reaction front velocity v dependence on multilayer period d is shown in fig. 2 for an al/monel 400--multilayer designed to form a compound analogous to the equiatomic compound nial. this compound has a heat of formation of about 50 to 55 k joules/mole. it is clear from fig. 2 that the velocity increases rapidly as the multilayer period d decreases below 1000 angstroms. as depicted in fig. 2, the velocity increases with decreasing multilayer period d, reaching a maximum at very small periods, then rapidly falling to a small value or about zero. this velocity dependence of the propagating reaction front on structure is a significant observation. the general qualitative explanation for this dependence of velocity on structure is as follows. first, the chemical reaction between the elemental components in unreacted layers a and b determines the energy available and if the reaction is adiabatic, the maximum temperature attained. second, the rate at which the energy is released is directly proportional to the rate at which these atoms react by thermally activated processes or by structurally enhanced mixing. since these reactions are thermally activated, the higher the sample temperature, the higher the rate of reaction. the number of atoms in close contact between an unreacted layer a to an unreacted layer b at an interface in a multilayer structure determines the rate of energy release at a given temperature. the higher the number of interfacial atoms, the higher the rate of heat release. therefore, the rate of heat release, or reaction delivered power, is directly proportional to the interfacial area per unit volume, or inversely proportional to the period d. higher energy release rates result in higher temperature gradients at the reaction front and higher propagation velocities. at very small periods, d<150 angstroms, chemical reactions that occur at the interfaces between alternating unreacted layers, such as a and b, during synthesis causes the available energy to be decreased. with less heat released over any time period, the temperature gradients at the reaction front and the propagation velocity v are smaller. differential scanning calorimetry was used to measure the heats involved with reactions in multilayers as a function of temperature. in one case the exothermic heat liberated by the chemical reaction was measured between the elements in the monel 400 composition (ni.sub.0.7 cu.sub.0.3) and aluminum layers as a function of multilayer period. this is illustrated in fig. 3. the decrease in the available energy (exothermic heat) as the period d is decreased explains the velocity decrease with multilayer period at periods less than 130 .ang. as shown in fig. 2. again with a multilayer structure with alternating unreacted layers a and b, the available energy, .delta.h, is given as ##equ3## where .delta.h.sub.f is the heat of formation of compound a.sub.x b.sub.y. assuming that t.sub.ab is constant for all multilayer periods, when d=2t.sub.ab equation (6) the driving energy for rapid reaction front propagation goes toward zero and the reaction front velocity is quenched to zero as seen in fig. 2. by plotting .delta.h as determined by dsc at fixed composition as a function of multilayer period 1/d, .delta.h can be extrapolated to zero, and the value of d for 2t.sub.ab /d equal one can be determined. this is shown in fig. 4, where values of 2t.sub.ab are estimated between 60 and 90 angstroms. when 2t.sub.ab equals d it is implied that the reacted layers of thickness 2t.sub.ab comprise the full structure and no exothermic energy remains. it is recognized that there will still be a small amount of exothermic energy available as the chemical mixing proceeds to a more stable state in these reacted zone layers of thickness t.sub.ab. multilayer structure 10 dependence of the reaction front velocity is presented in fig. 2. a qualitative argument that the front velocity is proportional to 1/d is also made. the general form of the data in fig. 2 can be fit by the equation ##equ4## a reasonable fit of data is shown in figs. 2 and 8. in equation 7, the term in brackets is just the fraction of the exothermic energy available for a multilayer of period d. the 1/d dependence defines the time over which the reaction occurs. as d decreases, the higher the rate of reaction at a given temperature and the higher the exothermic power. the constant k describes the magnitude of the exothermic energy that is available per volume and relates itself and the other two parameters to the reaction velocity v. while k is strongly dependent on a multilayer structure's heat of formation, it is also dependent on other parameters such as heat capacity and mass density of the multilayer structure. the reaction front velocity of the multilayer structures of the invention is proportional to the power (energy/unit time) available from the reaction of unreacted layers a and b to form a.sub.x b.sub.y. power delivered, , is assumed constant. the calculated temperature distribution about the reacted front heat source is schematically shown in fig. 5, where .xi.=x-vt where v is reaction front velocity, x is position and t is time. the calculated temperature t is described by the following equation: ##equ5## where ##equ6## where: t.sub.o is the starting temperature; p=density; c.sub.p =specific heat; k=thermal conductivity; h=heat transfer coefficient; c=circumference; a=cross-sectional area. the term hc/ka is a heat loss term. for ease of discussion it is assumed that the process is adiabatic and this term is negligible or zero. equation 9 can be solved for velocity v, giving ##equ7## where ##equ8## the width of a reacted zone in a multilayer can be described by thermally activated atomic diffusion of the two reacting species, a and b, of unreacted layers of thickness t.sub.a and t.sub.b. the time/temperature dependence of the growth of the reacted zone width, termed .omega., is ##equ9## where .omega.=t.sub.ab initially. f is the fractional composition range spanned in the reacted zone of width, .omega., and d is the average interdiffusion coefficient in the compound formed and is given as d=(1-x)d.sub.a +xd.sub.b where d.sub.a, d.sub.b are the interdiffusion coefficient for component atoms a and b in the compound formed. this analysis can be used to show that the rate of mixing has an exponential dependence on temperature. the analysis can also be used to demonstrate that the time required to complete the mixing and reaction of a multilayer structure is proportional to the period d. thus, the rate of heat release, , is proportional to 1/d. equation 12 states that the rate of growth of the reacting layer, d.omega./dt, is inversely proportional to the reacted zone thickness .omega.. therefore the rate of reaction or rate of exothermic heat release at a given temperature is inversely proportional to the initial reacted zone layer thickness. it is therefore possible, by control of the initial reacted layer thickness, to control the temperature which is required to initiate the propagation of a multilayer material reaction front. as shown in fig. 6, for a given reacted zone t.sub.ab with thickness of about 60 angstroms, variations in k produce significant variations in velocity. for a given constant k of 8,400 m.ang./sec, for a particular multilayer structure, t.sub.ab can vary and velocity v changes, as shown in fig. 7 where 2t.sub.ab is in the range of 30 to 180 angstroms. fig. 8 is a graphical comparison of measured velocity as a function as the multilayer period d for al/monel 400 multilayer structures with calculated k values of 8400, 4200 and 2100 m.ang./sec. the engineering of rapidly reacting multilayer structures with controlled propagating reaction front velocities v is dependent on the following parameters: (1) the heat of formation of the compound formed by reaction of the component layers; (2) the reacted zone width formed during synthesis; (3) the specific heats of the components; (4) values of endothermic heats of reactions or melting; (5) thermal conductivity; and (6) interdiffusion kinetics. the foregoing description of preferred embodiments of the present invention has been provided for the purposes of illustration and description. it is not intended to be exhaustive or to limit the invention to the precise forms disclosed. obviously, many modifications and variations will be apparent to practitioners skilled in this art. the embodiments were chosen and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. it is intended that the scope of the invention be defined by the following claims and their equivalents.
|
109-065-143-324-054
|
US
|
[
"US",
"CN",
"DE"
] |
G06T7/20,G06V10/143,G08G1/16,B60W30/12,B60W40/06,B60Q1/08
| 2016-09-14T00:00:00 |
2016
|
[
"G06",
"G08",
"B60"
] |
methods and systems for adaptive on-demand infrared lane detection
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methods and systems for operating a lane sensing system for a vehicle having at least one side-mounted infrared light source are disclosed. one system includes an ambient light sensor configured to detect a light level condition of an environment surrounding the vehicle; an infrared light sensor configured to detect an infrared light reflection from a lane marker; and a controller in communication with the ambient light sensor, the infrared light source, and the infrared light sensor, the controller configured to receive sensor data corresponding to the light level condition, determine if the light level condition is below a threshold, command the infrared light source to illuminate if the light level condition is below the threshold, receive infrared reflection data from the infrared light sensor of infrared light reflected from at least one lane marker, and detect a lane boundary based on the infrared reflection data.
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1 . a method of operating a lane sensing system for a vehicle, the method comprising: providing the vehicle with at least one infrared light sensor, at least one infrared light source, at least one vehicle sensor configured to measure an ambient light level, and a controller in communication with the at least one infrared light source, the at least one infrared light sensor, and the at least one vehicle sensor; receiving sensor data corresponding to the ambient light level of an environment of the vehicle; determining, by the controller, if the ambient light level is below an ambient light threshold; calculating, by the controller, an infrared intensity level based on the ambient light level, if the ambient light level is below the ambient light threshold; commanding, by the controller, the at least one infrared light source to turn on at the calculated infrared intensity level, if the ambient light level is below the ambient light threshold; receiving, by the controller, infrared reflection data from at least one infrared light sensor of infrared light from the at least one infrared light source reflected from at least one lane marker; and detecting, by the controller, a lane boundary based on the infrared reflection data from the infrared light reflected from the at least one lane marker. 2 . the method of claim 1 , further comprising predicting, by the controller, whether the vehicle will pass within a low light area. 3 . the method of claim 2 , wherein predicting whether the vehicle will pass within the low light area comprises receiving, by the controller, map data corresponding to a vehicle location and determining, by the controller, whether the map data indicates that a projected path of the vehicle will pass within the low light area. 4 . the method of claim 3 , further comprising commanding, by the controller, the at least one infrared light source to turn on if the map data indicates that the projected path of the vehicle will pass within the low light area. 5 . the method of claim 1 , wherein the infrared intensity level is a predetermined intensity level. 6 . an automotive vehicle, comprising: a vehicle body; a mirror coupled to a side of the vehicle body, the mirror including a housing, an infrared light source, and an infrared sensor; an ambient light sensor; and a controller in communication with the infrared light source, the infrared sensor, and the ambient light sensor, the controller configured to receive sensor data from the ambient light sensor corresponding to an ambient light level of an environment of the vehicle; determine if the ambient light level is below an ambient light threshold; calculate an infrared intensity level based on the ambient light level, if the ambient light level is below the ambient light threshold; command the at least one infrared light source to turn on at the calculated infrared intensity level, if the ambient light level is below the ambient light threshold; receive infrared reflection data from at least one infrared light sensor of infrared light from the at least one infrared light source reflected from at least one lane marker; and detect a lane boundary based on the infrared reflection data from the infrared light reflected from the at least one lane marker. 7 . the automotive vehicle of claim 6 , wherein the infrared intensity level is a predetermined intensity level. 8 . the automotive vehicle of claim 6 , wherein the ambient light sensor is an optical camera. 9 . the automotive vehicle of claim 6 , wherein the controller is further configured to predict whether the vehicle will pass within a low light area. 10 . the automotive vehicle of claim 9 , wherein predicting whether the vehicle will pass within the low light area comprises receiving map data corresponding to a vehicle location and determining whether the map data indicates that a projected path of the vehicle will pass within the low light area. 11 . the automotive vehicle of claim 10 , wherein the controller is further configured to command the at least one infrared light source to turn on if the map data indicates that the projected path of the vehicle will pass within the low light area. 12 . a system for operating a lane sensing system for a vehicle having at least one side-mounted infrared light source, comprising: an ambient light sensor configured to detect an ambient light level condition of an environment surrounding the vehicle; an infrared light sensor configured to detect an infrared light reflection from a lane marker; and a controller in communication with the ambient light sensor, the infrared light source, and the infrared light sensor, the controller configured to receive sensor data corresponding to the ambient light level condition, determine if the ambient light level condition is below a threshold, command the infrared light source to illuminate if the light level condition is below the threshold, receive infrared reflection data from the infrared light sensor of infrared light reflected from at least one lane marker, and detect a lane boundary based on the infrared reflection data. 13 . the system of claim 12 , wherein the controller is further configured to calculate an infrared intensity level based on the ambient light level condition, if the ambient light level condition is below the threshold. 14 . the system of claim 13 , wherein the infrared intensity level is a predetermined intensity level. 15 . the system of claim 12 , wherein the ambient light sensor is an optical camera. 16 . the system of claim 12 , wherein the controller is further configured to predict whether the vehicle will pass within a low light area. 17 . the system of claim 16 , wherein predicting whether the vehicle will pass within the low light area comprises receiving map data corresponding to a vehicle location and determining whether the map data indicates that a projected path of the vehicle will pass within the low light area.
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introduction the present invention relates generally to the field of vehicles and, more specifically, to methods and systems for adaptive on-demand lane detection using infrared lighting. the operation of modern vehicles is becoming more automated, i.e. able to provide driving control with less and less driver intervention. vehicle automation has been categorized into numerical levels ranging from zero, corresponding to no automation with full human control, to five, corresponding to full automation with no human control. various automated driver-assistance systems, such as cruise control, adaptive cruise control, and parking assistance systems correspond to lower automation levels, while true “driverless” vehicles correspond to higher automation levels. accurate lane sensing in all light conditions is used by autonomous driving systems. additionally, accurate lane sensing can be used to notify a driver of possible drift over a lane marker boundary to prompt the user to take corrective action. however, in some driving conditions, such as when the vehicle passes through a tunnel or under an overpass, detection of lane marker boundaries using visible light may be insufficient to accurately detect the vehicle's position with respect to the lane marker boundaries. summary embodiments according to the present disclosure provide a number of advantages. for example, embodiments according to the present disclosure enable detection of lane boundary markings in low light level conditions, such as when a vehicle passes through a tunnel or under an overpass or during operation at night. embodiments according to the present disclosure may thus provide more robust lane detection and detection accuracy while being non-intrusive to the operator and to other vehicles. in one aspect, a method of operating a lane sensing system for a vehicle is disclosed. the method includes the steps of providing the vehicle with at least one infrared light sensor, at least one infrared light source, at least one vehicle sensor configured to measure an ambient light level, and a controller in communication with the at least one infrared light source, the at least one infrared light sensor, and the at least one vehicle sensor; receiving sensor data corresponding to the ambient light level of an environment of the vehicle; determining, by the controller, if the ambient light level is below an ambient light threshold; calculating, by the controller, an infrared intensity level based on the ambient light level, if the ambient light level is below the ambient light threshold; commanding, by the controller, the at least one infrared light source to turn on at the calculated infrared intensity level, if the ambient light level is below the ambient light threshold; receiving, by the controller, infrared reflection data from at least one infrared light sensor of infrared light from the at least one infrared light source reflected from at least one lane marker; and detecting, by the controller, a lane boundary based on the infrared reflection data from the infrared light reflected from the at least one lane marker. in some aspects, the method further includes predicting, by the controller, whether the vehicle will pass within a low light area. in some aspects, predicting whether the vehicle will pass within the low light area includes receiving, by the controller, map data corresponding to a vehicle location and determining, by the controller, whether the map data indicates that a projected path of the vehicle will pass within the low light area. in some aspects, the method further includes commanding, by the controller, the at least one infrared light source to turn on if the map data indicates that the projected path of the vehicle will pass within the low light area. in some aspects, the infrared intensity level is a predetermined intensity level. in another aspect, an automotive vehicle includes a vehicle body; a mirror coupled to a side of the vehicle body, the mirror including a housing, an infrared light source, and an infrared sensor; an ambient light sensor; and a controller in communication with the infrared light source, the infrared sensor, and the ambient light sensor. the controller is configured to receive sensor data from the ambient light sensor corresponding to an ambient light level of an environment of the vehicle; determine if the ambient light level is below an ambient light threshold; calculate an infrared intensity level based on the ambient light level, if the ambient light level is below the ambient light threshold; command the at least one infrared light source to turn on at the calculated infrared intensity level, if the ambient light level is below the ambient light threshold; receive infrared reflection data from at least one infrared light sensor of infrared light from the at least one infrared light source reflected from at least one lane marker; and detect a lane boundary based on the infrared reflection data from the infrared light reflected from the at least one lane marker. in some aspects, the infrared intensity level is a predetermined intensity level. in some aspects, the ambient light sensor is an optical camera. in some aspects, the controller is further configured to predict whether the vehicle will pass within a low light area. in some aspects, predicting whether the vehicle will pass within the low light area includes receiving map data corresponding to a vehicle location and determining whether the map data indicates that a projected path of the vehicle will pass within the low light area. in some aspects the controller is further configured to command the at least one infrared light source to turn on if the map data indicates that the projected path of the vehicle will pass within the low light area. in yet another aspect, a system for operating a lane sensing system for a vehicle having at least one side-mounted infrared light source is disclosed. the system includes an ambient light sensor configured to detect an ambient light level condition of an environment surrounding the vehicle; an infrared light sensor configured to detect an infrared light reflection from a lane marker; and a controller in communication with the ambient light sensor, the infrared light source, and the infrared light sensor, the controller configured to receive sensor data corresponding to the ambient light level condition, determine if the ambient light level condition is below a threshold, command the infrared light source to illuminate if the light level condition is below the threshold, receive infrared reflection data from the infrared light sensor of infrared light reflected from at least one lane marker, and detect a lane boundary based on the infrared reflection data. in some aspects, the controller is further configured to calculate an infrared intensity level based on the ambient light level condition, if the ambient light level condition is below the threshold. in some aspects, the infrared intensity level is a predetermined intensity level. in some aspects, the ambient light sensor is an optical camera. in some aspects, controller is further configured to predict whether the vehicle will pass within a low light area. in some aspects, predicting whether the vehicle will pass within the low light area includes receiving map data corresponding to a vehicle location and determining whether the map data indicates that a projected path of the vehicle will pass within the low light area. brief description of the drawings the present disclosure will be described in conjunction with the following figures, wherein like numerals denote like elements. fig. 1 is a schematic diagram of a vehicle having at least one infrared light source, according to an embodiment. fig. 2 is a schematic diagram of a side-mounted rear view mirror of a vehicle, such as the vehicle of fig. 1 , illustrating a downward-facing infrared light source mounted to the rear view mirror, according to an embodiment. fig. 3 is a schematic diagram of a vehicle, such as the vehicle of fig. 1 , illustrating an infrared illumination area, according to an embodiment. fig. 4 is a schematic block diagram of a lane sensing system for a vehicle, such as the vehicle of fig. 1 , according to an embodiment. fig. 5 is a flow chart of a method to detect lane boundaries using on-demand, adaptive infrared lighting, according to an embodiment. fig. 6 is a flow chart of a method to detect lane boundaries using on-demand, adaptive infrared lighting, according to another embodiment. the foregoing and other features of the present disclosure will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. understanding that these drawings depict only several embodiments in accordance with the disclosure and are not to be considered limiting of its scope, the disclosure will be described with additional specificity and detail through the use of the accompanying drawings. any dimensions disclosed in the drawings or elsewhere herein are for the purpose of illustration only. detailed description embodiments of the present disclosure are described herein. it is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. the figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention. as those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. the combinations of features illustrated provide representative embodiments for typical applications. various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations. certain terminology may be used in the following description for the purpose of reference only, and thus are not intended to be limiting. for example, terms such as “above” and “below” refer to directions in the drawings to which reference is made. terms such as “front,” “back,” “left,” “right,” “rear,” and “side” describe the orientation and/or location of portions of the components or elements within a consistent but arbitrary frame of reference which is made clear by reference to the text and the associated drawings describing the components or elements under discussion. moreover, terms such as “first,” “second,” “third,” and so on may be used to describe separate components. such terminology may include the words specifically mentioned above, derivatives thereof, and words of similar import. fig. 1 schematically illustrates an automotive vehicle 10 according to the present disclosure. the vehicle 10 generally includes a body 11 and wheels 15 . the body 11 encloses the other components of the vehicle 10 . the wheels 15 are each rotationally coupled to the body 11 near a respective corner of the body 11 . the vehicle 10 further includes side-mounted rear view mirrors 17 coupled to the body 11 . each of the side-mounted rear view mirrors or mirrors 17 includes a housing 18 . the vehicle 10 is depicted in the illustrated embodiment as a passenger car, but it should be appreciated that any other vehicle, including motorcycles, trucks, sport utility vehicles (suvs), or recreational vehicles (rvs), etc., can also be used. the vehicle 10 includes a propulsion system 13 , which may in various embodiments include an internal combustion engine, an electric machine such as a traction motor, and/or a fuel cell propulsion system. the vehicle 10 also includes a transmission 14 configured to transmit power from the propulsion system 13 to the plurality of vehicle wheels 15 according to selectable speed ratios. according to various embodiments, the transmission 14 may include a step-ratio automatic transmission, a continuously-variable transmission, or other appropriate transmission. the vehicle 10 additionally includes wheel brakes (not shown) configured to provide braking torque to the vehicle wheels 15 . the wheel brakes may, in various embodiments, include friction brakes, a regenerative braking system such as an electric machine, and/or other appropriate braking systems. the vehicle 10 additionally includes a steering system 16 . while depicted as including a steering wheel and steering column for illustrative purposes, in some embodiments, the steering system 16 may not include a steering wheel. in various embodiments, the vehicle 10 also includes a navigation system 28 configured to provide location information in the form of gps coordinates (longitude, latitude, and altitude/elevation) to a controller 22 . in some embodiments, the navigation system 28 may be a global navigation satellite system (gnss) configured to communicate with global navigation satellites to provide autonomous geo-spatial positioning of the vehicle 10 . in the illustrated embodiment, the navigation system 28 includes an antenna electrically connected to a receiver. with further reference to fig. 1 , the vehicle 10 also includes a plurality of sensors 26 configured to measure and capture data on one or more vehicle characteristics, including but not limited to vehicle speed, vehicle heading, and ambient light level conditions. in the illustrated embodiment, the sensors 26 include, but are not limited to, an accelerometer, a speed sensor, a heading sensor, gyroscope, steering angle sensor, or other sensors that sense observable conditions of the vehicle or the environment surrounding the vehicle and may include radar, lidar, optical cameras, thermal cameras, ultrasonic sensors, infrared sensors, light level detection sensors, and/or additional sensors as appropriate. in some embodiments, the vehicle 10 also includes a plurality of actuators 30 configured to receive control commands to control steering, shifting, throttle, braking or other aspects of the vehicle 10 . the vehicle 10 includes at least one controller 22 . while depicted as a single unit for illustrative purposes, the controller 22 may additionally include one or more other controllers, collectively referred to as a “controller.” the controller 22 may include a microprocessor or central processing unit (cpu) or graphical processing unit (gpu) in communication with various types of computer readable storage devices or media. computer readable storage devices or media may include volatile and nonvolatile storage in read-only memory (rom), random-access memory (ram), and keep-alive memory (kam), for example. kam is a persistent or non-volatile memory that may be used to store various operating variables while the cpu is powered down. computer-readable storage devices or media may be implemented using any of a number of known memory devices such as proms (programmable read-only memory), eproms (electrically prom), eeproms (electrically erasable prom), flash memory, or any other electric, magnetic, optical, or combination memory devices capable of storing data, some of which represent executable instructions, used by the controller 22 in controlling the vehicle. as illustrated in fig. 2 , the vehicle 10 also includes an infrared light source 20 . in some embodiments, such as the embodiment shown in fig. 2 , the infrared light source 20 may be coupled to the housing 18 of the side-mounted rear view mirror 17 using any type of mechanical connector or fastener. in some embodiments, the infrared light source 20 is coupled to the housing 18 during a molding process. the infrared light source 20 emits infrared light that illuminates a cone-shaped area 102 . in some embodiments, an infrared light sensor or infrared camera 21 , one of the sensors 26 , is mounted near the infrared light source 20 . the infrared light sensor 21 detects infrared light reflected from lane boundary markings and enables detection of the lane boundary markings in low light level conditions. in some embodiments, the infrared light sensor 21 is unitarily formed with the infrared light source 20 . in some embodiments, the infrared light sensor 21 is separate from the infrared light source 20 . fig. 3 schematically illustrates the vehicle 10 traveling along a road in a direction of travel 204 . the road has lane marker boundaries 202 . the vehicle 10 is equipped with a front camera 23 , one of the sensors 26 . as shown, a front camera 23 is positioned on the roof of the vehicle 10 facing the front of the vehicle 10 in the direction of travel 204 . the front camera 23 provides images of an area 104 ahead of the vehicle 10 and also provides information on the lighting condition of the environment surrounding the vehicle 10 . additionally, the front camera 23 provides information on the environment ahead of the vehicle 10 along the predicted path of travel. this information includes, for example and without limitation, an upcoming tunnel or overpass or other low light condition area. furthermore, the front camera 23 provides information on the ambient light condition of the environment of the vehicle 10 . as discussed in greater detail below, as the vehicle 10 approaches and enters the low light area, the front camera 23 captures images illustrating the lighting condition. the images are processed by the controller 22 to detect the lighting condition. the controller 22 processes the lighting condition information, calculates a desired infrared intensity level, and commands illumination from an infrared light source, such as the infrared light source 20 mounted on the mirror 17 . the infrared light from the infrared light source 20 illuminates the area 102 that includes the lane boundary markers 202 indicating a lane of travel on a road, such as lane marker lines. the infrared light is reflected from the lane markers and is received by the infrared light sensor 21 , shown in fig. 2 . the reflected light is processed by the controller 22 to determine if the vehicle 10 is maintaining travel within the lane markers or if the vehicle 10 has drifted to the left or right over the lane markers. if, after processing the reflected light information, the controller 22 determines that the vehicle 10 has departed from the lane of travel by, for example, loss of detection of the lane markers, the controller 22 can trigger notification systems that notify the vehicle operator of the lane departure. these notification methods include, without limitation, visual, audible, tactile, or any other type of warning signal. while the front camera 23 is shown in fig. 3 as mounted on the roof of the vehicle 10 , the front camera 23 could be mounted anywhere on the vehicle 10 that provides a view forward of the vehicle 10 along the predicted path of travel or images that provide information on the ambient light condition. additionally, while the infrared light source 20 is shown as mounted underneath the side-mounted rear view mirror 17 , the infrared light source 20 could be mounted anywhere on the vehicle 10 at a position to illuminate the lane markers. with reference to fig. 4 , the controller 22 includes an infrared-based lane sensing system 24 for illuminating lane markers using infrared light during low light conditions and detecting the lane markers using infrared light reflection from the markers. in an exemplary embodiment, the infrared-based lane sensing system 24 is configured to receive map data corresponding to a vehicle location and/or sensor data corresponding to an ambient light level condition of the environment of the vehicle 10 , determine whether the vehicle 10 is passing through a low light area or whether the projected path of travel of the vehicle 10 will be through a low light area, command illumination from an infrared light source at a predetermined or calculated intensity level, receive infrared reflection data, and detect a lane boundary based on the infrared light reflection data. additionally, the controller 22 can generate an output indicating the lane detection determination that may be used by other vehicle systems, such as an automated driving assistance system (adas), a user notification system, and/or a lane keeping/monitoring system. the lane sensing system 24 includes a sensor fusion module 40 for receiving input on vehicle characteristics, such as a vehicle speed, vehicle heading, an ambient light level condition of the environment of the vehicle 10 , or other characteristics. the sensor fusion module 40 is configured to receive input 27 from the plurality of sensors, such as the sensors 26 illustrated in fig. 1 , including the front camera 23 and the infrared light sensor 21 . in some embodiments, the sensor fusion module 40 contains a video processing module 39 configured to process image data from the sensors 26 , such as the data received from the front camera 23 and the infrared light sensor 21 . additionally, the sensor fusion module 40 is also configured to receive navigation data 29 including longitude, latitude, and elevation information (e.g., gps coordinates) from the navigation system 28 . the sensor fusion module is also configured to receive map data 49 from a map database stored on a storage medium 48 . the map data 49 includes, but is not limited to, road type and road condition data, including tunnels, overpasses, etc. along a predicted path of travel of the vehicle 10 . the sensor fusion module 40 processes and synthesizes the inputs from the variety of sensors 26 , the navigation system 28 , and the map database 48 and generates a sensor fusion output 41 . the sensor fusion output 41 includes various calculated parameters including, but not limited to, an ambient light level condition of the environment through which the vehicle 10 is passing, a projected path of the vehicle 10 , and a current location of the vehicle 10 relative to the projected path. in some embodiments, the sensor fusion output 41 also includes parameters that indicate or predict whether the vehicle 10 will be passing through an area having a low light level, such as a tunnel or under a highway overpass. the lane sensing system 24 also includes an intensity calculation module 42 for calculating a desired intensity of the infrared light source 20 . the intensity of the infrared light source 20 depends on the ambient light level determined by the sensor fusion module 40 based on the input from the sensors 26 , including the front camera 23 . the intensity calculation module 42 processes and synthesizes the sensor fusion output 41 and generates a calculated intensity output 43 . the calculated intensity output 43 includes various calculated parameters including, but not limited to, a calculated intensity level of the infrared light to be emitted by the infrared light source 20 . with continued reference to fig. 4 , the lane sensing system 24 includes a control module 44 for controlling the infrared light source 20 . the control module 44 receives the calculated intensity output 43 and generates a control output 45 that includes various parameters, including but not limited to a control signal to command the infrared light source 20 to emit infrared light at the calculated intensity level. in some embodiments, the intensity level is calculated by the intensity calculation module 42 based on the ambient light level condition detected by the sensors 26 , including the front camera 23 . in some embodiments, the intensity level is a predetermined value. the lane sensing system 24 includes a lane boundary detection module 46 for detecting a lane boundary based on infrared light reflection from the lane boundary markers. the lane boundary detection module 46 processes and synthesizes the sensor fusion output 41 that includes data from the sensors 26 , including the infrared sensor 21 , and generates a detection output 47 . the detection output 47 includes various calculated parameters including, but not limited to, a position of the vehicle 10 with respect to the lane boundary markers (e.g., over the lane boundary to the left, over the lane boundary to the right, or between the lane boundary markers). the position of the vehicle 10 with respect to the lane markers is based on the reflection of infrared light from the lane makers received by the infrared sensor 21 . the detection output 47 is received, in some embodiments, by an automated driving assistance system (adas) 50 , a lane keeping or lane monitoring system 52 , and/or a user notification system 54 . as discussed above, various parameters, including the location of the vehicle 10 with respect to upcoming, known low light areas as indicated by the navigation system 28 , the map data 49 , and the light level condition as detected by the sensors 26 , are used to determine when to use infrared light to illuminate the lane markers. fig. 5 is a flow chart of a method 500 illustrating the determination of when to turn on an infrared light source 20 based on navigation and map data of the projected path of the vehicle. the navigation data is obtained from the navigation system 28 and the map data is obtained from one or more map databases 48 associated with the controller 22 . the method 500 can be utilized in connection with the vehicle 10 , the controller 22 , and the various modules of the lane sensing system 24 , in accordance with exemplary embodiments. the order of operation of the method 500 is not limited to the sequential execution as illustrated in fig. 5 , but may be performed in one or more varying orders as applicable and in accordance with the present disclosure. as shown in fig. 5 , starting at 502 , the method 500 proceeds to step 504 . at 504 , the sensor fusion module 40 of the lane sensing system 24 receives navigation data 29 and map data 49 . together, the navigation data 29 and the map data 49 provide information on the location of the vehicle 10 , the projected path of the vehicle 10 along a roadway, and upcoming low light level areas along the projected path of the vehicle 10 . these low light level areas include tunnels, highway overpasses, bridges, etc. next, at 506 , based on the map data and the navigation data, a determination is made regarding whether the projected path of the vehicle 10 includes a low light level area. a low light level area is defined as an area where visible light is insufficient to illuminate the lane markers to accurately sense the lane markers and monitor the path of the vehicle 10 between the lane markers and the vehicle 10 will be subject to the low light level condition for a predetermined low light level time and/or a low light level distance. in a low light level area, the light level is below a predetermined threshold. in some embodiments, the predetermined light level threshold is between approximately 0.5 and 2 lux. in some embodiments, the predetermined light level threshold is approximately 0.5 lux, approximately 1.0 lux, approximately 1.5 lux, or approximately 2.0 lux. in some embodiments, the predetermined light level threshold is between approximately 0.25 lux and approximately 2.5 lux. in some embodiments, the low light level time is between approximately 0.3 and 0.5 seconds. in some embodiments, the low light level distance is between approximately 10 and 20 meters. if the data indicates that the vehicle 10 is not or will not, within a predetermined time or distance, enter a low light level area, the method 500 proceeds to 508 . if the vehicle 10 includes an adas system, such as the adas 50 , the adas 50 can determine a configurable length of predetermined “look ahead distance” along the path of travel of the vehicle 10 . in some embodiments, the predetermined look ahead distance is between approximately 300 to 3,000 meters. in some embodiments, the predetermined look ahead distance is approximately 500 meters, approximately 1,000 meters, approximately 1,500 meters, approximately 2,000 meters, or approximately 2,500 meters. in some embodiments, the predetermined look ahead distance is independent of vehicle speed. in some embodiments, the predetermined time is approximately 5 seconds. in some embodiments, the predetermined time is between approximately 3 and 10 seconds, between 3 and 8 seconds, or between 4 and 6 seconds. in some embodiments, the predetermined time is approximately 5 seconds, approximately 8 seconds, approximately 10 seconds, or approximately 15 seconds. at 508 , the infrared light 20 is not commanded to illuminate and detection of the lane marker boundaries is sufficient with visible light and visible light sensors. the method 500 returns to 504 and the method proceeds as discussed below. if, at 506 , the navigation and map data indicates that the vehicle 10 is currently traveling through a low light level area or will enter a low light level area within the predetermined time or distance as discussed above, the method 500 proceeds to 510 . at 510 , the control module 44 generates the control signal 45 to turn on the infrared light source 20 . the infrared light source 20 may be turned on at a predetermined intensity level or the intensity level may be determined by the intensity calculation module 42 based on the expected low light level area along the projected path of the vehicle 10 . for example, and without limitation, if the projected path of the vehicle 10 includes a tunnel, the control module 44 generates the control signal 45 to command the infrared light source 20 to turn on at a first intensity level. if the projected path of the vehicle 10 includes an overpass, the control module 44 generates the control signal 45 to command the infrared light source 20 to turn on at a second intensity level that is less than the first intensity level since the ambient light level is expected to be higher when the vehicle passes under an overpass than when the vehicle 10 passes through a tunnel. in some embodiments, the infrared lights source 20 is commanded to emit infrared light with intensity levels equivalent to between approximately 1 to 3 lux for visible light. in some embodiments, the first intensity level is between approximately 0.5 lux and 2 lux. in some embodiments, the second intensity level is between approximately 1 lux and 3 lux. the method 500 proceeds to 512 . at 512 the sensor fusion module 40 receives sensor data from the sensors 26 , including the infrared sensor 21 . the sensor data includes reflection data from the infrared light emitted by the infrared light source 20 , reflected off of the lane markers, and received by the infrared sensor 21 . next, at 514 , the lane boundary detection module 46 detects whether the vehicle 10 has maintained position in the lane by analyzing the sensor data 41 . the analysis includes determining if the reflections of the lane markers are detected on both sides of the vehicle 10 , or if the vehicle 10 has passed over the left or right side lane boundaries. the output from the lane boundary detection module 46 may be transmitted to other vehicle systems, for example and without limitation, the adas 50 , the lane keeping system 52 , and the user notification system 54 shown in fig. 2 . the method 500 returns to 504 and the method 500 continues as discussed above. fig. 6 is a flow chart of a method 600 illustrating the determination of when to turn on an infrared light source 20 based on the detected ambient light level condition. the light level condition is determined from sensor data 27 obtained by the sensors 26 , including the front camera 23 , that is processed and analyzed by the sensor fusion module 40 of the controller 22 . the method 600 can be utilized in connection with the vehicle 10 , the controller 22 , and the various modules of the lane sensing system 24 , in accordance with exemplary embodiments. the order of operation of the method 600 is not limited to the sequential execution as illustrated in fig. 6 , but may be performed in one or more varying orders as applicable and in accordance with the present disclosure. as shown in fig. 6 , starting at 602 , the method 600 proceeds to step 604 . at 604 , the sensor fusion module 40 of the lane sensing system 24 receives sensor data 27 from the sensors 26 , including the front camera 23 . the sensor data 27 is analyzed and processed by the sensor fusion module 40 , including the video processing module 39 , to determine an ambient light level condition. next, at 606 , based on the sensor data 27 , a determination is made regarding whether the vehicle 10 is traveling through a low light area. the determination of whether the vehicle 10 is passing through a low light area is based on a comparison of the ambient light level detected by the sensors 26 , including the front camera 23 , to a predetermined threshold value. as discussed above, the threshold value is between approximately 0.5 and 2.0 lux. in some embodiments, the predetermined light level threshold is approximately 0.5 lux, approximately 1.0 lux, approximately 1.5 lux, or approximately 2.0 lux. in some embodiments, the predetermined light level threshold is between approximately 0.25 lux and approximately 2.5 lux. if the detected light level is below the predetermined threshold, the sensor data indicates that the vehicle 10 is traveling through a low light area. if the data indicates that the vehicle 10 is not passing through a low light level area, that is, the detected light level is above the predetermined threshold light level, the method 600 proceeds to 608 . at 608 , the infrared light 20 is not commanded to illuminate and detection of the lane markers is sufficient with visible light and visible light sensors. the method 600 returns to 604 and the method proceeds as discussed below. if, at 606 , the data indicates that the vehicle 10 is currently traveling through a low light level area, the method 600 proceeds to 610 . at 610 , the intensity calculation module 42 calculates a desired infrared lighting or intensity level based on the detected ambient light level. for example, and without limitation, when the vehicle 10 travels through a tunnel, the ambient light level will be lower than when the vehicle 10 passes under an overpass. thus, the desired intensity level of the infrared light source 20 is calculated to be a higher value when the vehicle 10 travels through a tunnel than when the vehicle 10 passes under an overpass. in some embodiments, the desired intensity level is equivalent to approximately 1 to 3 lux for visible light. next, at 612 , the control module 44 generates the control signal 45 to turn on the infrared light source 20 at the calculated intensity level. the method 600 proceeds to 614 . at 614 , the sensor fusion module 40 receives sensor data from the sensors 26 , including the infrared sensor 21 . the sensor data includes reflection data from the infrared light emitted by the infrared light source 20 reflected off of the lane boundary markers and received by the infrared sensor 21 . next, at 616 , the lane boundary detection module 46 detects whether the vehicle 10 has maintained its position in the lane. the analysis includes determining if the reflections of the lane markers are detected on both sides of the vehicle 10 , or if the vehicle 10 has passed over the left or right side lane boundaries. the output from the lane boundary detection module 46 may be transmitted to other vehicle systems, for example and without limitation, the adas 50 , the lane keeping system 52 , and the user notification system 54 shown in fig. 2 . the method 600 returns to 604 and the method 600 continues as discussed above. the methods 500 and 600 are discussed separately, however, in some embodiments, for vehicles equipped with navigation systems and optical sensors, the methods 500 and 600 could operate concurrently. when the methods 500 and 600 operate concurrently, the information on upcoming low light level areas determined at 504 in method 500 and the results of the ambient light level detection made at 604 in method 600 are compared and either the information analyzed at 504 or the results determined at 604 or the information obtained at both 504 and 604 are used to determine whether to illuminate the infrared light source 20 . for example and without limitation, if the information on upcoming low light level areas analyzed at 504 indicates an upcoming low light level area but the results of the ambient light level detection made at 604 do not indicate a low light level condition, the infrared light source 20 the infrared light source is commanded to illuminate as discussed above with respect to method 500 . conversely, if the results of the ambient light level detection made at 604 indicate the vehicle is in or approaching a low light level are but the information on upcoming low light level areas determined at 504 does not indicate an upcoming low light level area, the infrared light source 20 is commanded to illuminate as discussed above with respect to method 600 . it should be emphasized that many variations and modifications may be made to the herein-described embodiments, the elements of which are to be understood as being among other acceptable examples. all such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims. moreover, any of the steps described herein can be performed simultaneously or in an order different from the steps as ordered herein. moreover, as should be apparent, the features and attributes of the specific embodiments disclosed herein may be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. conditional language used herein, such as, among others, “can,” “could,” “might,” “may,” “e.g.,” and the like, unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or states. thus, such conditional language is not generally intended to imply that features, elements and/or states are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without author input or prompting, whether these features, elements and/or states are included or are to be performed in any particular embodiment. moreover, the following terminology may have been used herein. the singular forms “a.” “an,” and “the” include plural referents unless the context clearly dictates otherwise. thus, for example, reference to an item includes reference to one or more items. the term “ones” refers to one, two, or more, and generally applies to the selection of some or all of a quantity. the term “plurality” refers to two or more of an item. the term “about” or “approximately” means that quantities, dimensions, sizes, formulations, parameters, shapes and other characteristics need not be exact, but may be approximated and/or larger or smaller, as desired, reflecting acceptable tolerances, conversion factors, rounding off, measurement error and the like and other factors known to those of skill in the art. the term “substantially” means that the recited characteristic, parameter, or value need not be achieved exactly, but that deviations or variations, including for example, tolerances, measurement error, measurement accuracy limitations and other factors known to those of skill in the art, may occur in amounts that do not preclude the effect the characteristic was intended to provide. numerical data may be expressed or presented herein in a range format. it is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also interpreted to include all of the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. as an illustration, a numerical range of “about 1 to 5” should be interpreted to include not only the explicitly recited values of about 1 to about 5, but should also be interpreted to also include individual values and sub-ranges within the indicated range. thus, included in this numerical range are individual values such as 2, 3 and 4 and sub-ranges such as “about 1 to about 3.” “about 2 to about 4” and “about 3 to about 5,” “1 to 3.” “2 to 4,” “3 to 5,” etc. this same principle applies to ranges reciting only one numerical value (e.g., “greater than about 1”) and should apply regardless of the breadth of the range or the characteristics being described. a plurality of items may be presented in a common list for convenience. however, these lists should be construed as though each member of the list is individually identified as a separate and unique member thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary. furthermore, where the terms “and” and “or” are used in conjunction with a list of items, they are to be interpreted broadly, in that any one or more of the listed items may be used alone or in combination with other listed items. the term “alternatively” refers to selection of one of two or more alternatives, and is not intended to limit the selection to only those listed alternatives or to only one of the listed alternatives at a time, unless the context clearly indicates otherwise. the processes, methods, or algorithms disclosed herein can be deliverable to/implemented by a processing device, controller, or computer, which can include any existing programmable electronic control unit or dedicated electronic control unit. similarly, the processes, methods, or algorithms can be stored as data and instructions executable by a controller or computer in many forms including, but not limited to, information permanently stored on non-writable storage media such as rom devices and information alterably stored on writeable storage media such as floppy disks, magnetic tapes, cds, ram devices, and other magnetic and optical media. the processes, methods, or algorithms can also be implemented in a software executable object. alternatively, the processes, methods, or algorithms can be embodied in whole or in part using suitable hardware components, such as application specific integrated circuits (asics), field-programmable gate arrays (fpgas), state machines, controllers or other hardware components or devices, or a combination of hardware, software and firmware components. such example devices may be on-board as part of a vehicle computing system or be located off-board and conduct remote communication with devices on one or more vehicles. while exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. the words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. as previously described, the features of various embodiments can be combined to form further exemplary aspects of the present disclosure that may not be explicitly described or illustrated. while various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. these attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. as such, embodiments described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics are not outside the scope of the disclosure and can be desirable for particular applications.
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109-355-835-994-45X
|
US
|
[
"EP",
"US",
"KR",
"JP",
"WO",
"CN"
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H01L29/78,H01L29/66,H01L29/792,H01L21/336,H01L21/8247,H01L27/115,H01L21/28,H01L29/788,H01L27/10,H01L27/11568,H01L29/51,H01L21/3105,H01L21/321
| 2010-12-20T00:00:00 |
2010
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[
"H01"
] |
edge rounded field effect transistors and methods of manufacturing
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embodiments of the present technology are directed toward gate sidewall engineering of field effect transistors. the techniques include formation of a blocking dielectric region and nitridation of a surface thereof. after nitridation of the blocking dielectric region, a gate region is formed thereon and the sidewalls of the gate region are oxidized to round off gate sharp corners and reduce the electrical field at the gate corners.
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1 . a method comprising: forming a tunneling dielectric region on a substrate; forming a charge trapping region on the tunneling dielectric region; forming a blocking dielectric region on the charge trapping region; nitridating a surface of the blocking dielectric region; forming a gate region on the nitridated blocking dielectric region; and oxidizing the gate region wherein edge encroachment of the gate region is suppressed by the nitridated blocking dielectric region. 2 . the method according to claim 1 , further comprising oxidizing the charge trapping region along with the gate region. 3 . the method according to claim 1 , wherein forming the charge trapping region comprises depositing a silicon rich nitride layer. 4 . the method according to claim 3 , wherein forming the charge trapping region comprises forming a silicon oxynitride layer from a portion of the silicon rich nitride layer. 5 . a method comprising: forming a blocking dielectric region on a charge trapping region; nitridating a surface of the blocking dielectric region; form a gate region on the nitridated blocking dielectric region; and oxidizing sidewalls of the gate region and charge trapping region. 6 . the method according to claim 5 , wherein forming the charge trapping region comprises depositing a silicon rich nitride layer. 7 . the method according to claim 6 , wherein forming the blocking dielectric region comprises forming a silicon oxynitride layer from a portion of the silicon rich nitride layer. 8 . the method according to claim 7 , wherein nitridating the surface of the blocking dielectric region comprises exposing the surface of the blocking dielectric region to nitrogen in a furnace anneal. 9 . the method according to claim 5 , wherein edge encroachment of the gate region is suppressed by nitridation of the blocking dielectric region. 10 . the method according to claim 5 , wherein edge encroachment of the gate region is suppressed by oxide implanting the sidewalls of the gate region. 11 . an integrated circuit memory cell comprising: a drain region; a source region; a channel region disposed between the source and drain regions; a tunneling dielectric region disposed between the channel region and a charge trapping region; a blocking dielectric region disposed between the charge trapping region and a gate region, wherein a surface of the blocking dielectric region adjacent the gate region is nitridated; an oxide disposed on sidewalls of the charge trapping region and the gate region, wherein edge encroachment into the gate region from the oxide is suppressed by the nitridated surface of the blocking dielectric region. 12 . the integrated circuit memory cell of claim 11 , wherein: the drain region comprises silicon heavily doped with a first type of dopant; the source region comprises silicon heavily doped with the first type of dopant; and the channel region comprises silicon moderately doped with a second type of dopant. 13 . the integrated circuit memory cell of claim 12 , wherein: the first type of dopant comprises phosphorous or arsenic; and the second type of dopant comprises boron. 14 . the integrated circuit memory cell of claim 11 , wherein the tunnel dielectric region comprises silicon oxide. 15 . the integrated circuit memory cell of claim 14 , wherein the charge trapping region comprises a silicon rich nitride. 16 . the integrated circuit memory cell of claim 15 , wherein the blocking dielectric region comprises a silicon oxynitride. 17 . the integrated circuit memory cell of claim 16 , wherein the gate region comprises a polysilicon. 18 . the integrated circuit memory cell of claim 11 , wherein an equivalent dielectric thickness between the gate region and the channel region is substantially the same at the center and the edge of the gate region. 19 . the integrated circuit memory cell of claim 18 , wherein program-erase speed of the integrated circuit memory cell is increased by the suppressed edge encroachment of the gate region and substantially the same equivalent dielectric thickness between the gate region and the channel region at the center and the edge of the gate region. 20 . the integrated circuit memory cell of claim 18 , wherein endurance of the integrated circuit memory cell is increased by the suppressed edge encroachment of the gate region and substantially the same equivalent dielectric thickness between the gate region and the channel region at the center and the edge of the gate region.
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background of the invention data storage devices are an important part of numerous electronic devices such as computers, smart phones, digital content players (e.g., mp3 players), game consoles, control systems, and the like. many electronic devices include non-volatile solid state memory devices, such as flash memory. one common type of flash memory device is the charge trapping (ct) nand integrated circuit (ic). fig. 1 shows an exemplary ct-nand based flash memory ic. the flash memory ic 100 includes a ct-nand memory cell array 110 , control circuits 120 , column decoders 130 , row decoders 140 , input/output (i/o) buffers 150 , and the like fabricated on a monolithic semiconductor substrate. the control circuits 120 , column decoders 130 , row decoders 140 , i/o buffers 150 , and the like operate to read and write data 160 at an address 170 , 175 in the memory cell array 110 in accordance with various control signals 180 received by, internal to, and/or output from the flash memory ic 100 . the circuits of the flash memory ic 100 are well known in the art and therefore those aspects of the flash memory ic 100 not particular to embodiments of the present technology will not be discussed further. referring now to fig. 2 , an exemplary memory cell array is shown. the ct-nand memory cell array 110 includes a plurality of ct field effect transistors (fet) 210 , a plurality of drain select gates 220 , a plurality of source select gates 230 , a plurality of bit lines 240 , a plurality of word lines 250 , a plurality of drain select signal lines 260 , and a plurality of source select signal lines 270 . each column of the array 110 includes a drain select gate 220 , a plurality of ct-fets 210 , and a source select gate 230 serially connected source to drain between a corresponding bit line 240 and a ground potential 280 . the gates of each of a plurality of ct-fets 210 in each row of the array 110 are coupled to a corresponding word line 250 . the gate of each drain select gate 220 is connected to a corresponding drain select signal line 260 . the gate of each source select gate 230 is connected to a corresponding drain select signal line 270 . in one implementation, the ct-fets may be silicon-oxide-nitride-oxide-silicon (sonos) fets or the like. the ct-nand memory cell array 110 is well known in the art and therefore those aspects of the ct-nand memory cell array 110 not particular to embodiments of the present technology will not be discussed further. in a ct-nand memory cell array 110 a given memory cell is programmed by injecting charge into a charge trapping layer across a tunneling dielectric layer of the ct-fet 210 . the given memory cell is erased by removing the charge from the charge trapping layer across the tunneling dielectric layer. in one implementation, the ct-fet 210 is programmed and erased using fowler-nordheim (f-n) tunneling. the process of programming and erasing the ct-fet memory cell 210 damages the tunneling dielectric layer resulting in a finite number of program-erase cycles that can be performed on the flash memory ic 100 . accordingly, there is a continued need for improved ct-fet memory cells 210 and the like. summary of the invention the present technology may best be understood by referring to the following description and accompanying drawings that are used to illustrate embodiments of the present technology directed toward field effect transistor gate engineering. in one embodiment, a fabrication method includes forming a tunneling dielectric region on a substrate. a charge trapping region is formed on the tunneling dielectric region. a blocking dielectric region is formed on the charge trapping region. the surface of the blocking dielectric region is nitridated and then a gate region is formed on the nitridated surface of the blocking dielectric region. the gate region is then oxidized, wherein edges of the gate region are rounded and encroachment of the block dielectric region into the gate region is suppressed by the nitridated blocking dielectric region. brief description of the drawings embodiments of the present technology are illustrated by way of example and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which: fig. 1 shows a block diagram of an exemplary ct-nand based flash memory ic according to the conventional art. fig. 2 shows a block diagram of an exemplary memory cell array according to the conventional art. fig. 3 shows a block diagram of a memory cell array structure, in accordance with one embodiment of the present technology. fig. 4 shows a block diagram of an enlarged cross-sectional view of a ct-fet, in accordance with embodiments of the present technology. figs. 5a and 5b show block diagrams of ct-fets according to the conventional art. figs. 6a and 6b show a flow diagram of a method of fabricating a memory cell array, in accordance with one embodiment of the present technology. figs. 7a-7e show block diagrams illustrating fabrication of a memory cell array, in accordance with one embodiment of the present technology. detailed description of the invention reference will now be made in detail to the embodiments of the present technology, examples of which are illustrated in the accompanying drawings. while the present technology will be described in conjunction with these embodiments, it will be understood that they are not intended to limit the invention to these embodiments. on the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. furthermore, in the following detailed description of the present technology, numerous specific details are set forth in order to provide a thorough understanding of the present technology. however, it is understood that the present technology may be practiced without these specific details. in other instances, well-known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the present technology. in this application, the use of the disjunctive is intended to include the conjunctive. the use of definite or indefinite articles is not intended to indicate cardinality. in particular, a reference to “the” object or “a” object is intended to denote also one of a possible plurality of such objects. referring to fig. 3 , a memory cell array structure, in accordance with one embodiment of the present technology, is shown. in one implementation, the memory cell array may be a ct-nand memory cell array 110 . however, it is appreciated that embodiments of the present technology may be applied to any field effect transistor device. in one implementation, each column of ct-fets may be separated by a shallow trench isolation (sti) region 305 . each ct-fet may include a drain region 310 , a source region 315 , a channel region 320 , a tunneling dielectric region 325 (also commonly referred to as a bottom dielectric region), a charge trapping region 330 , a blocking dielectric region 335 (also commonly referred to as a top dielectric region), and a gate region 340 . the source and drain regions 310 , 315 may be semiconductor regions of the substrate 345 having a heavy doping concentration of a first type of impurity. in one implementation, the source and drain regions 310 , 315 may be silicon heavily doped with phosphorous or arsenic. the channel region 320 may be a semiconductor region of the substrate 345 having moderate doping concentration of a second type of impurity, disposed laterally between the source and drain regions 310 , 315 . in one implementation, the channel region 320 may be silicon moderately doped with boron. the tunneling dielectric region 325 may be a dielectric layer disposed over the channel region 320 and adjacent portions of the source and drain regions 310 , 315 . in one implementation, the tunneling dielectric region 325 may be silicon oxide, oxynitride, silicon oxynitride, or the like layer. the charge trapping region 330 may be a dielectric, semiconductor or the like layer disposed between the tunneling dielectric region 325 and the blocking dielectric region 335 . in one implementation, the charge trapping region 330 may be a nitride, silicon-rich-nitride, or the like layer. the blocking dielectric region 335 may be a dielectric layer disposed between the charge trapping region 330 and the gate region 340 . in one implementation, the blocking dielectric region 335 may be a silicon oxide, oxynitride, silicon oxynitride, or the like layer. the gate region 340 may be a semiconductor or a conductor layer disposed on the blocking dielectric region 335 opposite the charge trapping region 330 . in one implementation, the gate region 340 may be a polysilicon layer having a heavy doping concentration of the first type of impurity. the surface of the blocking dielectric region 335 is nitrided before the gate region 340 is formed. the nitridation of the surface of the blocking dielectric region 335 suppresses oxidation encroachment into the gate region 340 at the interface with the blocking dielectric region 335 . therefore, the thickness of blocking dielectric 335 is substantially the same at the center and edges of the gate region 340 as the gate edge is rounded in the following oxidation step. referring now to fig. 4 , an enlarged cross-sectional view of a ct-fet, in accordance with embodiments of the present technology, is shown. the nitridation 410 of the blocking dielectric region 335 reduces oxidation encroachment into the gate region 340 . the reduced encroachment results in a blocking dielectric thickness at the edges 420 that is substantially the same as the effective dielectric thickness at the center 425 of the gate region 340 , which increases program-erase endurance. in comparison, a ct-fet having no appreciable gate region 340 edge rounding 510 according to the conventional art is illustrated in fig. 5a . if the gate region 340 of a ct-fet does not have any appreciable edge rounding 510 , the electric field during erasing is substantially higher at the edges of the gate region 340 . the substantially higher electric field at the edges decreases the program-erase endurance of the ct-fet due to electron injection from the gate edge. in fig. 5b , a ct-fet having gate region edge rounding 520 produced by oxidation according to the conventional art is illustrated. the gate sidewall oxidation to round gate corners 520 produces encroachment which makes the block dielectric at the gate edges thicker 530 than at the gate center 540 . the encroachment of the blocking dielectric region 335 into the gate region 340 , resulting from oxidation, reduces the effective electric field across the blocking dielectric region 335 . the increase in the effective thickness of blocking dielectric 335 due to encroachment of the block dielectric region 335 into the gate region 340 decreases the program-erase speed of the flash memory ic. accordingly, the gate side-wall engineering utilizing blocking dielectric nitridation to suppress oxidation encroachment at the edges of the gate region improves the performance of the ct-fets in flash memory ics over the conventional art. it is also appreciated that gate side-wall engineering utilizing blocking dielectric nitridation to suppress oxidation encroachment at the edges of gate regions may be applied to improve the performance of other integrated circuits including fets. referring now to figs. 6a-6b , a method of fabricating a memory cell array, in accordance with one embodiment of the present technology, is shown. the method of fabricating the memory cell array will be further explained with reference to figs. 7a-7e , which illustrates fabrication of the memory cell array, in accordance with one embodiment of the present technology. as depicted in figs. 6a and 7a , the process begins, at 605 , with various initial processes upon a semiconductor wafer substrate 702 , such as cleaning, depositing, doping, etching and/or the like. the substrate 702 may be a semiconductor doped at a first concentration with a first dopant type. in one implementation, the substrate 702 may be silicon moderately doped with boron (p). at 610 , a tunneling dielectric region 706 is formed on the substrate 702 . in one implementation, the tunneling dielectric region 706 may be formed by oxidizing the exposed surface of the substrate 702 in the memory cell array region by any well known thermal dry oxidation process. in another implementation, the tunneling dielectric region 706 may be formed by depositing a silicon oxynitride film by any well known chemical vapor deposition process. in one implementation, the tunneling dielectric region 706 may be formed to a thickness of about 3 to 8 nanometers. referring now to fig. 7b , charge trapping region 708 is formed on the tunneling dielectric region 706 , at 615 . at 620 , a blocking dielectric region 710 is formed on the charge trapping region 708 . in one implementation, the charge trapping region and blocking dielectric region may be formed by first depositing a nitride layer 708 , by any well know process such a chemical vapor deposition (cvd) or atomic layer deposition (ald), on the tunneling dielectric region 706 . the nitride layer may include silicon rich nitride having an atomic ratio of silicon to nitrogen that is about 3:4 or greater. the charge trapping region may be formed by depositing multiple layers, such as a nitride layer on a silicon rich nitride layer. in addition, one or more of the layers may have substantially constant and/or graded concentration profiles. a sacrificial oxide may then be formed on the silicon nitride layer by any well known process. the sacrificial oxide and a portion of the nitride layer may then be etched back, before a portion of the remaining nitride layer is oxidized to form an oxynitride or silicon oxynitride layer 710 . in one implementation, the resulting charge trapping region 708 may be formed to a thickness of about 4 to 15 nanometers and the resulting blocking dielectric region 710 may be formed to a thickness of about 3 to 8 nanometers. at 625 , the exposed surface of the blocking dielectric region 710 is nitridated 712 . in one implementation, the exposed surface of the oxynitride or silicon oxynitride layer 710 is exposed to nitrogen in a furnace anneal or the like process. referring now to fig. 7c , a gate region 714 is formed on the blocking dielectric region 710 , at 630 . in one implementation, a polysilicon layer 714 is deposited, by any well known process such as chemical vapor deposition, on the nitridated oxynitride layer 712 , 710 . a photo resist is deposited on the polysilicon layer 714 and patterned by any well know photolithography process to form a gate/charge trapping mask 716 . referring now to fig. 7d , the polysilicon layer 714 , nitridated oxynitride layer 712 , 710 , and nitride layer 708 exposed by the gate/charge trapping mask 716 are then selectively etched by any well known anisotropic etching process. the gate/charge trapping mask 716 may then be removed by any well known process such as resist striping or resist ashing. referring now to figs. 6b and 7e , the gate region 714 , and optionally the charge trapping region 708 , is oxidized, wherein gate corner edge rounding 718 of the gate region 714 is done while encroachment is suppressed by the nitridated blocking dielectric region 712 , 710 , at 635 . in one implementation, the sidewalls of the gate region 714 , and optionally the charge trapping region 708 , are oxidized to form gate region 712 , and optionally charge trapping region 708 , having suppressed edge rounding 718 with suppressed encroachment, and a sidewall dielectric layer 720 . at 640 , the process continues with various subsequent processes, such as implanting, doping, etching, cleaning and/or the like, to form one or more additional regions, such as source, drain and channel regions, gate, source and drain contacts, peripheral circuits, interconnects, vias, passivation layer and/or the like. the source/drain region 704 may be portions of the substrate 702 doped at a second concentration with a second dopant type. in one implementation, the source/drain regions 704 may be silicon heavily doped with phosphorous or arsenic (n+). it is appreciated that the above described method of fabricating a memory cell array may also include other additional processes and that the order of the processes may vary from the order described above. embodiments of the present technology advantageously suppress encroachment by the block dielectric region into the gate region while rounding off the sharp edges and corners of the gate region. the encroachment is advantageously suppressed by nitridation of the blocking dielectric region. the electrical oxide thickness (eot) between the gate region and the channel region is substantially the same at the center and the edge of the gate region as a result of the suppressed edge encroachment during oxidation rounding of gate edges and corners. furthermore, program-erase speed and endurance is advantageously increased by the suppressed edge encroachment of the gate region and/or substantially the same eot between the gate region and the channel region at the center and the edge of the gate region. the foregoing descriptions of specific embodiments of the present technology have been presented for purposes of illustration and description. they are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. the embodiments were chosen and described in order to best explain the principles of the present technology and its practical application, to thereby enable others skilled in the art to best utilize the present technology and various embodiments with various modifications as are suited to the particular use contemplated. it is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
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109-492-990-601-848
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US
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B42D25/00,B42D25/328,B42D25/36,B42D25/30,B42D25/29,B42D25/373,B42D25/405,B42D25/40
| 2013-03-15T00:00:00 |
2013
|
[
"B42"
] |
optical security device
|
an improved form of optical security device for use in the protection of documents and articles of value from counterfeit and to verify authenticity is provided. the inventive device, which is made up of an optionally embedded array of icon focusing elements, at least one grayscale in-plane image, and a plurality of coextensive control patterns of icons contained on or within the in-plane image, each control pattern being mapped to areas of the grayscale in-plane image having a range of grayscale levels, provides enhanced design capability, improved visual impact, and greater resistance to manufacturing variations.
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claims 1. an optical security device, which comprises: an optionally embedded array of icon focusing elements; at least one grayscale in-plane image that visually lies substantially in a plane of a substrate on which the in-plane image is carried; and a plurality of coextensive control patterns of icons contained on or within the at least one in-plane image forming an icon layer, each control pattern being mapped to areas of the in-plane image having a range of grayscale levels, wherein placement of the control patterns of icons within the in-plane image is determined using one or more control pattern probability distributions associated with each grayscale level within all or part of the in-plane image, wherein the array of icon focusing elements is positioned to form at least one synthetically magnified image of at least a portion of the icons in each coextensive control pattern of icons, the at least one synthetically magnified image having one or more dynamic effects, wherein the one or more dynamic effects of the at least one synthetically magnified image are controlled and choreographed by the control patterns of icons. 2. the optical security device of claim 1 , wherein the array of icon focusing elements is an embedded array of icon focusing elements. 3. the optical security device of claim 1 or 2, wherein the at least one synthetically magnified image is viewable over a range of viewing angles, and wherein a silhouette of the in- plane image is also viewable over this range of viewing angles. 4. the optical security device of claim 1 , wherein one or more layers of metallization cover an outer surface of the icon layer. 5. the optical security device of claim 1 , which comprises a grayscale in-plane image, a plurality of control patterns of icons contained within the in-plane image thereby forming an icon layer, and an array of icon focusing elements positioned to form at least one synthetically magnified image of the control patterns of icons. 6. the optical security device of claim 1 , which comprises a sequence of grayscale in-plane images, a set of control patterns of icons for each in-plane image, wherein each set of control patterns of icons is contained within its respective in-plane image, which together form an icon layer, and an array of icon focusing elements positioned to form an animation of the synthetically magnified images of the control patterns of icons. 7. a method for making the optical security device of claim 1 , the method comprising: (a) providing at least one grayscale in-plane image that visually lies substantially in a plane of a substrate on which the in-plane image is carried; (b) providing a plurality of coextensive control patterns of icons contained on or within the at least one in-plane image forming an icon layer, each control pattern being mapped to areas of the in-plane image having a range of grayscale levels, wherein placement of the control patterns of icons within the in-plane image is determined using one or more control pattern probability distributions associated with each grayscale level within all or part of the in-plane image; (c) providing an optionally embedded array of icon focusing elements; and (d) providing the optionally embedded array of icon focusing elements relative to the icon layer so as to form at least one synthetically magnified image of at least a portion of the icons in each coextensive control pattern of icons, the at least one synthetically magnified image, which intersects with the at least one in-plane image, having one or more dynamic effects, wherein the one or more dynamic effects of the at least one synthetically magnified image are controlled and choreographed by the control patterns of icons. 8. a method for forming an icon layer of an optical security device that includes a grayscale in-plane image, a plurality of control patterns of icons contained within the in-plane image thereby forming an icon layer, and an array of icon focusing elements positioned to form at least one synthetically magnified image of the control patterns of icons, the method comprising: selecting a grayscale in-plane image; and using the grayscale in-plane image to drive placement of the control patterns of icons within the in-plane image to together form the icon layer. 9. the method of claim 8, which comprises: (a) selecting a grayscale in-plane image and scaling the grayscale image to a size suitable for use in the icon layer; (b) superimposing a tiling onto the scaled grayscale in-plane image, the tiling comprising cells that will contain the control patterns of icons, wherein each cell has a preferred size similar to one or several focusing elements; (c) selecting a numerical range to represent the colors black and white and the various levels of gray in between black and white; (d) determining the level of grayscale of the scaled grayscale in-plane image in each cell of the superimposed tiling; (e) assigning to each cell a number which represents the determined level of grayscale and which falls within the selected numerical range, wherein the assigned number is the cell's grayscale value; (f) selecting a number of control patterns of icons for use in a control pattern palette, and for each control pattern of icons, assigning a range of grayscale levels which fall within the selected numerical range; (g) specifying a control pattern probability distribution within the in-plane image and for each possible grayscale value, using the control pattern probability distribution to assign a range of random numbers to each control pattern; (h) providing each cell in the tiling with a random number that falls with the selected numerical range using a random number generator; (i) determining which control pattern will be used to fill each cell using the cell's grayscale value and the cell's random number in conjunction with a mathematical construct which corresponds to the control pattern probability distribution; and (j) filling each cell with its determined control pattern of icons. 10. a method for forming an icon layer of an optical security device that includes a sequence of grayscale in-plane images, a set of control patterns of icons for each in-plane image where each set of control patterns of icons is contained within its respective in-plane image together forming an icon layer, and an array of icon focusing elements positioned to form an animation of synthetically magnified images of the control patterns of icons, the method comprising: selecting a sequence of grayscale in-plane images, selecting a set of control patterns of icons for each grayscale in-plane image; and using the grayscale in-plane images to drive placement of its respective control patterns of icons within the in-plane image to form the icon layer. 1 1 . the method of claim 10, which comprises: (a) selecting a sequence of grayscale in-plane images that form an animation and scaling the grayscale images to a size suitable for use in the icon layer {e.g., several square millimeters to several square centimeters); (b) superimposing a tiling onto each scaled grayscale in-plane image, the tiling comprising cells that will contain the control patterns of icons, wherein each cell has a preferred size similar to one or several focusing elements {e.g., several microns to tens of microns); (c) selecting a numerical range to represent the colors black and white and the various levels of gray in between black and white {e.g., 0 for black, 1 for white, and the continuum of real numbers in between as representing the various levels of gray); (d) determining the level of grayscale of the scaled grayscale in-plane image in each cell of the superimposed tiling; (e) assigning to each cell a number which represents the determined level of grayscale and which falls within the selected numerical range, wherein the assigned number is the cell's grayscale value; (f) for each grayscale in-plane image that forms the animation, selecting a number of control patterns of icons for use in a control pattern palette, and for each control pattern of icons, assigning a range of grayscale levels which fall within the selected numerical range, wherein the selected number of control patterns of icons constitutes a set of control patterns for the grayscale in-plane image, with each grayscale in-plane image having one set of control patterns of icons; (g) specifying, for each set of control patterns of icons, a control pattern probability distribution within the respective in-plane image and for each possible grayscale value, using the control pattern probability distribution to assign a range of random numbers to each control pattern; (h) providing each cell in the tiling with a random number that falls with the selected numerical range using a random number generator; (i) determining, for each set of control patterns, each set being assigned to a specific and different grayscale image, which control pattern will be used to fill each cell using the cell's grayscale value and the cell's random number in conjunction with a mathematical construct which corresponds to the control pattern probability distribution; and (j) filling each cell with its determined control pattern of icons, each cell receiving a determined control pattern from each set of control patterns of icons. 12. a method for increasing design space, reducing sensitivity to manufacturing variations, and reducing blurriness of images formed by an optical security device, the optical security device including at least one grayscale in-plane image, a plurality of control patterns of icons contained within the in-plane image forming an icon layer, and an array of icon focusing elements positioned to form at least one synthetically magnified image of the control patterns of icons, the method comprising: using at least one grayscale in-plane image; and using coordinated control patterns of icons on or within each in-plane image to control and choreograph one or more dynamic effects of the synthetically magnified images. 13. a sheet material that is made from or employs the optical security device of claim 1. 14. a base platform that is made from or employs the optical security device of claim 1. 15. a document made from the sheet material of claim 13, or the base platform of claim 14.
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optical security device related application [0001] this application claims priority to u.s. provisional patent application serial no. 61/791 ,695, filed march 15, 2013, which is incorporated herein in its entirety by reference. technical field [0002] this invention relates to an improved form of optical security device for use in the protection of documents and articles of value from counterfeit and to verify authenticity. more specifically, this invention relates to an optical security device that provides enhanced design capability, improved visual impact, and greater resistance to manufacturing variations. background and summary of the invention [0003] micro-optic film materials projecting synthetic images generally comprise: an arrangement of micro-sized image icons; an arrangement of focusing elements {e.g., microlenses, microreflectors); and optionally, a light-transmitting polymeric substrate. the image icon and focusing element arrangements are configured such that when the arrangement of image icons is viewed using the arrangement of focusing elements, one or more synthetic images are projected. these projected images may show a number of different optical effects. [0004] such film materials may be used as security devices for authentication of banknotes, secure documents and products. for banknotes and secure documents, these materials are typically used in the form of a strip, patch, or thread and can be either partially or completely embedded within the banknote or document, or applied to a surface thereof. for passports or other identification (id) documents, these materials could be used as a full laminate or inlayed in a surface thereof. for product packaging, these materials are typically used in the form of a label, seal, or tape and are applied to a surface thereof. [0005] one example of a micro-optic security device is known from u.s. patent no. 7,738,175, which reveals a micro-optic system that embodies (a) an in-plane image having a boundary and an image area within the boundary that is carried on and visually lies in the plane of a substrate, (b) a control pattern of icons contained within the boundary of the in-plane image, and (c) an array of icon focusing elements. the icon focusing element array is positioned to form at least one synthetically magnified image of the control pattern of icons, the synthetically magnified image providing a limited field of view for viewing the in-plane image operating to modulate the appearance of the in-plane image. in other words, the appearance of the in-plane image visually appears and disappears, or turns on and off, depending upon the viewing angle of the system. [0006] several drawbacks in this micro-optic system become evident when used in a sealed lens format {i.e., a system utilizing an embedded lens array). first, when the synthetic image is in its "off" state a slight ghost image of the synthetic image may remain visible because of light scattered through or around the focusing optics. these ghost images are especially pronounced in the sealed lens format. second, the sealed lens format has a relatively high f-number, typically around 2. as will be readily appreciated by one skilled in the field of micro- optics, a higher f-number leads to more rapid movement of synthetic images, but also increases blurriness and the system's sensitivity to manufacturing variations. these drawbacks effectively render this system unsuitable for use in a sealed lens format. [0007] the present invention addresses these drawbacks by providing an optical security device, which comprises: an optionally embedded array of icon focusing elements; at least one grayscale in-plane image that visually lies substantially in a plane of a substrate on which the in-plane image is carried; and a plurality of coextensive (intermingled) control patterns of icons contained on or within the at least one in-plane image forming an icon layer, each control pattern being mapped to areas of the in-plane image having a range of grayscale levels, wherein placement of the control patterns of icons within the in-plane image is determined using one or more control pattern probability distributions associated with each grayscale level within all or part of the in-plane image, wherein the array of icon focusing elements is positioned to form at least one synthetically magnified image of at least a portion of the icons in each coextensive control pattern of icons, the at least one synthetically magnified image (which intersects with the at least one in-plane image) having one or more dynamic effects, wherein the one or more dynamic effects of the at least one synthetically magnified image are controlled and choreographed by the control patterns of icons. [0008] as the optical security device is tilted the synthetically magnified images demonstrate dynamic optical effects in the form of, for example, dynamic bands of rolling color running through the in-plane image, growing concentric circles, rotating highlights, strobe-like effects, pulsing text, pulsing images, rolling parallel or non-parallel lines, rolling lines that move in opposite directions but at the same rate, rolling lines that move in opposition directions but at different or spatially varying rates, bars of color that spin around a central point like a fan, bars of color that radiate inward or outward from a fixed profile, embossed surfaces, engraved surfaces, as well as animation types of effects such as animated figures, moving text, moving symbols, animated abstract designs that are mathematical or organic in nature, etc. dynamic optical effects also include those optical effects described in u.s. patent no. 7,333,268 to steenblik et al., u.s. patent no. 7,468,842 to steenblik et al., and u.s. patent no. 7,738,175 to steenblik et a/., all of which, as noted above, are fully incorporated by reference as if fully set forth herein. [0009] in an exemplary embodiment, one or more layers of metallization cover an outer surface of the icon layer. [0010] by way of the inventive optical security device, the synthetically magnified image(s) of the in-plane image(s) is always on'. in one exemplary embodiment, as the device is tilted synthetically magnified images in the form of bands of color sweep over the surface of the in-plane image, revealing tremendous detail {i.e., improved visual impact). the bands of color are 'choreographed' using the multiple control patterns of icons. the 'ghost image', which is troublesome for the micro-optic system of u.s. patent no. 7,738,175, helps the optical effects of the present invention to be more convincing by providing a silhouette of the in-plane image at every tilt angle that can always be seen. also, because the image never turns 'off', and is visually defined by the choreographed optical effects {e.g., bands of rolling color), the in-plane image may be made much larger thereby providing enhanced design capability. in addition, the inventive device is less sensitive to manufacturing variations. while any such manufacturing variation may serve to change the angle and shape of the synthetic images, the relative choreography will remain the same, and thus the effect will not be disturbed to the same extent as the prior art system. [0011] the present invention also provides a method for making the optical security device described above, the method comprising: (a) providing at least one grayscale in-plane image that visually lies substantially in a plane of a substrate on which the in-plane image is carried; (b) providing a plurality of coextensive (intermingled) control patterns of icons contained on or within the at least one in-plane image forming an icon layer, each control pattern being mapped to areas of the in-plane image having a range of grayscale levels, wherein placement of the control patterns of icons within the in-plane image is determined using one or more control pattern probability distributions associated with each grayscale level within all or part of the in-plane image; (c) providing an optionally embedded array of icon focusing elements; and (d) positioning the optionally embedded array of icon focusing elements relative to the icon layer so as to form at least one synthetically magnified image of at least a portion of the icons in each coextensive control pattern of icons, the at least one synthetically magnified image (which intersects with the at least one in-plane image) having one or more dynamic effects, wherein the one or more dynamic effects of the at least one synthetically magnified image are controlled and choreographed by the control patterns of icons. [0012] in an exemplary embodiment of the inventive optical security device, the device includes a grayscale in-plane image, a plurality of control patterns of icons contained within the in-plane image thereby forming an icon layer, and an array of icon focusing elements positioned to form at least one synthetically magnified image of the control patterns of icons. the method for forming the icon layer in this exemplary embodiment comprises: selecting a grayscale in- plane image; and using the grayscale in-plane image to drive placement of the control patterns of icons within the in-plane image to form the icon layer. [0013] in an exemplary embodiment, the inventive method comprises: (a) selecting a grayscale in-plane image and scaling the grayscale image to a size suitable for use in the icon layer {e.g., several square millimeters to several square centimeters); (b) superimposing a tiling onto the scaled grayscale in-plane image, the tiling comprising cells that will contain the control patterns of icons, wherein each cell has a preferred size similar to one or several focusing elements {e.g., several microns to tens of microns); (c) selecting a numerical range to represent the colors black and white and the various levels of gray in between black and white {e.g., 0 for black, 1 for white, and the continuum of real numbers in between as representing the various levels of gray); (d) determining the level of grayscale of the scaled grayscale in-plane image in each cell of the superimposed tiling; (e) assigning to each cell a number which represents the determined level of grayscale and which falls within the selected numerical range {e.g., 0-1 ), wherein the assigned number is the cell's grayscale value; (f) selecting a number of control patterns of icons for use in a control pattern palette, and for each control pattern of icons, assigning a range of grayscale levels which fall within the selected numerical range; (g) specifying a control pattern probability distribution within the in-plane image and for each possible grayscale value, using the control pattern probability distribution to assign a range of random numbers to each control pattern; (h) providing each cell in the tiling with a random number that falls with the selected numerical range {e.g., 0-1 ) using a random number generator (rng); (i) determining which control pattern will be used to fill each cell using the cell's grayscale value and the cell's random number in conjunction with a mathematical construct which corresponds to the control pattern probability distribution; and (j) filling each cell with its determined control pattern of icons. [0014] in another exemplary embodiment of the inventive optical security device, the device includes a sequence of grayscale in-plane images, a set of control patterns of icons for each in-plane image, wherein each set of control patterns of icons is contained within its respective in-plane image, which together form an icon layer, and an array of icon focusing elements positioned to form an animation of the synthetically magnified images of the control patterns of icons. the method for forming the icon layer in this exemplary embodiment comprises: selecting a sequence of grayscale in-plane images, selecting a set of control patterns of icons for each grayscale in-plane image; and using the grayscale in-plane images to drive placement of its respective control patterns of icons within the in-plane image to together form the icon layer. [0015] in an exemplary embodiment, the inventive method comprises: (a) selecting a sequence of grayscale in-plane images that form an animation and scaling the grayscale images to a size suitable for use in the icon layer {e.g., several square millimeters to several square centimeters); (b) superimposing a tiling onto each scaled grayscale in-plane image, the tiling comprising cells that will contain the control patterns of icons, wherein each cell has a preferred size similar to one or several focusing elements {e.g., several microns to tens of microns); (c) selecting a numerical range to represent the colors black and white and the various levels of gray in between black and white {e.g., 0 for black, 1 for white, and the continuum of real numbers in between as representing the various levels of gray); (d) determining the level of grayscale of the scaled grayscale in-plane image in each cell of the superimposed tiling; (e) assigning to each cell a number which represents the determined level of grayscale and which falls within the selected numerical range {e.g., 0-1 ), wherein the assigned number is the cell's grayscale value; (f) for each grayscale in-plane image that forms the animation, selecting a number of control patterns of icons for use in a control pattern palette, and for each control pattern of icons, assigning a range of grayscale levels which fall within the selected numerical range, wherein the selected number of control patterns of icons constitutes a set of control patterns for the grayscale in-plane image, with each grayscale in-plane image having one set of control patterns of icons; (g) specifying, for each set of control patterns of icons, a control pattern probability distribution within the respective in-plane image and for each possible grayscale value, using the control pattern probability distribution to assign a range of random numbers to each control pattern; (h) providing each cell in the tiling with a random number that falls with the selected numerical range {e.g., 0-1 ) using an rng; (i) determining, for each set of control patterns, each set being assigned to a specific and different grayscale image, which control pattern will be used to fill each cell using the cell's grayscale value and the cell's random number in conjunction with a mathematical construct which corresponds to the control pattern probability distribution; and (j) filling each cell with its determined control pattern of icons, each cell receiving a determined control pattern from each set of control patterns of icons. [0016] the present invention further provides a method for increasing design space, reducing sensitivity to manufacturing variations, and reducing blurriness of images formed by an optical security device, the optical security device including at least one in-plane image, a plurality of control patterns of icons contained within the in-plane image forming an icon layer, and an array of icon focusing elements positioned to form at least one synthetically magnified image of the control patterns of icons, the method comprising: using at least one grayscale in- plane image; and using coordinated control patterns of icons on or within the in-plane image to control and choreograph one or more dynamic effects of the synthetically magnified images. [0017] the present invention further provides sheet materials and base platforms that are made from or employ the inventive optical security device, as well as documents made from these materials. [0018] in an exemplary embodiment, the inventive optical security device is a micro- optic film material such as an ultra-thin (e.g., a thickness ranging from about 1 to about 10 microns), sealed lens structure for use in banknotes. [0019] in another exemplary embodiment, the inventive optical security device is a sealed lens polycarbonate inlay for base platforms used in the manufacture of plastic passports. [0020] other features and advantages of the invention will be apparent to one of ordinary skill from the following detailed description and accompanying drawings. [0021] unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. all publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. in case of conflict, the present specification, including definitions, will control. in addition, the materials, methods/processes, and examples are illustrative only and not intended to be limiting. brief description of the drawings [0022] the present disclosure may be better understood with reference to the following drawings. components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. while exemplary embodiments are disclosed in connection with the drawings, there is no intent to limit the present disclosure to the embodiment or embodiments disclosed herein. on the contrary, the intent is to cover all alternatives, modifications and equivalents. [0023] particular features of the disclosed invention are illustrated by reference to the accompanying drawings in which: fig. 1a illustrates an exemplary embodiment of a grayscale in-plane image used in the practice of the present invention, while fig. 1 b illustrates a tiling superimposed onto the grayscale in-plane image of fig. 1a; fig. 2 illustrates an enlarged portion of the tiled grayscale in-plane image of fig. 1a, showing grayscale levels of the in-plane image measured at the lower-left corner of four rectangular tiles or cells; fig. 3 illustrates an example of a control pattern probability distribution with vertical overlap between the control patterns in the distribution in which the random numbers are chosen between 0 and 1 and the grayscale values range from 0.0 to 1.0; fig. 4 illustrates an example of a control pattern probability distribution with no vertical overlap between the control patterns in the distribution in which the random numbers are again chosen between 0 and 1 and the grayscale values again range from 0.0 to 1.0; fig. 5 illustrates a collection of six control patterns of grayscale icons that are each contained in separate contiguous rectangular tiles, while in fig. 7, these six control patterns are shown overlaid onto the same tile; fig. 6 illustrates a tessellated collection of six coextensive (intermingled) control patterns of icons; figs. 8 and 9 both illustrate the intersection of a grayscale in-plane image with synthetically magnified images generated by the control patterns of icons; figs. 10 and 11 illustrate different control pattern distributions (figs. 10a and 11 a), and the resulting images that a viewer would see (figs. 10b and 11 b); fig. 12 illustrates the grayscale in-plane image shown in fig. 1a 'filled' with the control patterns of icons shown in fig. 6; fig. 13 illustrates one of the images (without dynamic optical effects) viewable from a surface of an exemplary embodiment of the inventive optical security device that employs the 'filled' in-plane image shown in fig. 12; fig. 14 illustrates a collection of six grayscale images that form an animation; and fig. 15 illustrates a stage in the formation of an icon layer used to produce the animation shown in fig. 14, which has six sets of control patterns of icons (as columns), each containing six control patterns of icons (as rows). detailed description of the invention [0024] by way of the optical security device of the present invention, a new platform for giving very detailed images is provided. as mentioned above, the inventive device provides enhanced design capability, improved visual impact, and greater resistance to manufacturing variations. [0025] the two exemplary embodiments of the inventive optical security device described above will now be depicted in more detail below in conjunction with the drawings. in-plane image [0026] the in-plane image of the inventive optical security device is an image that has some visual boundary, pattern, or structure that visually lies substantially in the plane of the substrate on which or in which the in-plane image is carried. [0027] in fig. 1a, an exemplary embodiment of a grayscale in-plane image in the form of a monkey's face is marked with reference numeral 10. grayscale in-plane image 10, which is simply an image in which the only colors are shades of gray {i.e., shades from black to white), has a boundary 12 and an image area 14 within the boundary that, as noted above, visually lies substantially in a plane of a substrate on which the in-plane image 10 is carried. in this exemplary embodiment, the grayscale image was made so that the parts that seem 'closest' to the viewer (the eyes and nose) are whitest, while the parts that seem 'farthest away' from the viewer are darkest. [0028] when forming the icon layer of the inventive optical security device, a single grayscale image (such as that shown in fig. 1a) is chosen and scaled to the 'actual size' that it should be in physical form. in one exemplary embodiment, the image is scaled to a size ranging from about several square millimeters to about several square centimeters. this is typically much larger than the focusing elements, which in terms of microlenses typically having a size on the order of microns or tens of microns. [0029] next, as best shown in fig. 1 b, a tiling 16 is superimposed onto the grayscale image 10. this tiling 16 represents cells that will contain the control patterns of icons. the size of each cell is not limited, but in an exemplary embodiment, is on the order of the size of one or several focusing elements {e.g., from several microns to tens of microns). while rectangular- shaped cells are shown in fig. 1 b, any variety of shapes that form a tessellation can be used {e.g., parallelograms, triangles, regular or non-regular hexagons, or squares). [0030] a numerical range is then selected to represent the colors black and white and the various levels of gray in between black and white. some methods map black to 0 and white to 255, and the levels of gray to the integers in between {e.g., in 8-bit grayscale images), while some methods use larger ranges of numbers {e.g., in 16 or 32 bit grayscale images). in the present exemplary embodiment, however, for simplicity, 0 is used for black and 1 is used for white and the continuum of real numbers in between 0 and 1 is used to represent the various levels of gray. [0031] the level of grayscale at the location of each cell in the grayscale image 10 is then determined. for example, and as best shown in fig. 2, for each cell, a common point is chosen {e.g., the lower-left corner of each rectangular tile or cell) and the level of grayscale of the in-plane image 10 corresponding to that point is measured at the common point and assigned to the cell. this can be achieved through direct measurement of the grayscale image at that point (as illustrated in fig. 2), or the value can be interpolated from the pixels of the grayscale image using various image sampling techniques. [0032] in fig. 2, the pixels of the grayscale in-plane image 10 are smaller than the cells of the tiling 16. the pixels of the grayscale in-plane image, however, can be larger than the cells. as will be readily appreciated by those skilled in the art, in the latter case, it may be advantageous to use an interpolation method or technique for sub-sampling the pixels. [0033] each cell is then assigned a number which represents the determined level of grayscale and which falls within the selected numerical range {e.g., 0-1 ). this assigned number is referred to as the cell's grayscale value. control patterns of icons [0034] as previously noted, the coextensive control patterns of icons are contained on or within the in-plane image(s) forming an icon layer, with each control pattern containing icons mapped to areas of the in-plane image that fall within a range of grayscale levels {e.g., a grayscale level between 0 (black) and 0.1667). [0035] once each cell in the tiling 16 has been assigned a grayscale value (and accordingly each possible grayscale value has been determined), a control pattern probability distribution is specified, which serves to assign a range of random numbers to each control pattern. each cell is then provided with a random number that falls with the selected numerical range {e.g., 0-1 ) using a rng. [0036] once a cell's random number is selected and the grayscale value of that cell is known, a particular control pattern for that particular cell can be assigned. the control pattern probability distribution effectively sets the probability that a particular control pattern in the control pattern palette will be used to fill a particular cell. [0037] an example of a control pattern distribution is shown in fig. 3. in this example, three different control patterns are in the control pattern palette (control pattern a (cp a), control pattern b (cp b), control pattern c (cp c)), with each control pattern occupying its own triangular region in the control pattern distribution. each possible grayscale value is mapped to a vertical cross section of this distribution. the vertical cross section showing which random numbers correspond to which control pattern. [0038] by way of example, for a cell whose grayscale value is 1 .0, this would correspond to a point along the distribution where the probability that control pattern a should be chosen is 100%, the probability that control pattern b should be chosen is 0%, and the probability that control pattern c should be chosen is 0%. this is because all of the random numbers between 0 and 1 will correspond to control pattern a. [0039] by way of further example, for a cell whose grayscale value is 0.7, a random number chosen between 0 and 0.4 will correspond to that particular cell being filled with control pattern a, while a random number chosen between 0.4 and 1.0 will correspond to that particular cell being filled with control pattern b. there is no possibility for this cell to be filled with control pattern c. [0040] by way of yet a further example, for a cell whose grayscale value is 0.25, a random number between 0 and 0.5 will correspond to that particular cell being filled with control pattern c, while a random number chosen between 0.5 and 1.0 will correspond to that particular cell being filled with control pattern b. in other words, there is a 50% probability that the cell will be filled with control pattern c and a 50% probability that the cell will be filled with control pattern b. [0041] there is no practical limit on the definition of the control pattern probability distribution, which is simply a mathematical construct that connects a random number to the choice of control pattern. the control pattern distribution can adjust many different aspects of the dynamic optical effects of the subject invention, such as, for example, more rapid or slower transition between control patterns, and multiple control patterns visible simultaneously. in addition, and as alluded to above, different portions of the in-plane image may have different control pattern distributions and different collections or palettes of control patterns. this would allow some portions of the in-plane image to be activated with left-right tilting, while other portions are activated with towards-away tilting, and yet other portions to be activated regardless of the direction of tilt. in the present exemplary embodiment, the primary purpose of the control pattern distribution is to automatically 'dither' or smooth the boundaries between the parts of the grayscale image that would be filled with different control patterns of icons. because the control pattern distribution provides a probabilistic means by which the control patterns of icons are chosen, the areas of the in-plane image that are assigned to a given control pattern need not be sharply defined. instead, there can be smooth transition from one control pattern's area to the next. [0042] sharp boundaries can, however, be made to exist through proper definition of the control pattern probability distribution. a control pattern distribution that would provide sharp transition from one control pattern to the next is shown in fig. 4. because there is no vertical overlap between the control pattern regions in this distribution, the random numbers essentially play no role in the selection of the control patterns. that being said, any grayscale value from 0.0 to 0.25 would result in that cell being filled with control pattern c, any grayscale value from 0.25 to 0.7 would result in that cell being filled with control pattern b, and any grayscale value from 0.7 to 1.0 would result in that cell being filled with control pattern a. [0043] the next step in the inventive method for forming an icon layer of an optical security device is filling each cell with its determined control pattern of icons. [0044] as previously indicated, the dynamic effects of the synthetically magnified images generated by the inventive optical security device are controlled and choreographed by the control patterns of icons. more specifically, the choreography of these images is prescribed by the relative phasing of the control patterns and by the control pattern distribution, in addition to the nature of the grayscale in-plane image. [0045] referring now to fig. 5, a collection of six (6) control patterns, each made up of different gray-toned icons in the form of horizontal lines 18, is shown for illustrative purposes. the bold black outlines 20 represent the tile which would be used to repeat (tessellate) the control patterns of icons on a plane. the tiles for these six control patterns, which define the manner in which the control patterns are tessellated onto a plane, happen to be the same rectangular shape. the tiles, however, as noted above, can adopt any shape that forms a tessellation. the tiles shown in fig. 5 also have the same dimensions. the tiles are 'in phase' in the sense that they meet up along the same grid. this ensures that, when the control patterns are distributed on or within the in-plane image, the relative timing of when the control patterns are 'activated' remains constant. [0046] as shown in fig. 5 and also in fig. 6 (where six control patterns 22a-f are shown tessellated onto a plane), the icons in each control pattern are shifted relative to the icons in other control patterns. the icons may be very slightly shifted up by a few hundred nanometers or slightly more dramatically shifted by a few microns. for control patterns of icons in the form of vertical lines, the icons in each control pattern could be shifted left-right or right- left, while for control patterns of icons in the form of diagonal lines, the icons in each control pattern could be shifted along the diagonal. [0047] it is noted here that there are numerous other ways of coordinating the control patterns to each other. for example, the control patterns could have an intentionally coordinated 'starting point' and fall along different grids. [0048] while six (6) control patterns are shown in figs. 5 and 6, the number of control patterns used in the present invention is not so limited. in fact, the number of control patterns of icons could be of infinite number and variety if they are generated mathematically. [0049] referring now to fig. 7, the six control patterns in fig. 5 are shown overlaid onto the same tile 24. here, the control patterns a-f are shown 'doubled' in the rectangular tile 24 because this tile is sized to several focusing elements. in one contemplated embodiment, each tile is sized to two focusing elements with hexagonal base diameters. in other words, each tile is in the shape of a rectangular box that represents two hexagons. there is no loss of generality to consider a tile to be a group of control patterns of icons, and the use of rectangular tilings as opposed to hexagonal tilings may make tessellation and algorithms easier to work with. [0050] the collective group of all of the control patterns shown in fig. 7 completely and evenly covers the tile 24. the idea that the control patterns 'completely and evenly' cover the tile, however, is not meant to be limiting. for example, depending on the desired effect, the collective group of all of the control patterns may only partially cover the tile, or may cover the tile multiple times {i.e., several control patterns occupy the same space on the tile). [0051] in figs. 8 and 9, the intersection of the grayscale in-plane image 10 with a synthetically magnified image generated by a control pattern of icons is shown. in the illustrations shown in these figures, the synthetic images are depicted as small rectangles floating above the surface of this exemplary embodiment of the inventive optical security device. the surface of the inventive device carries the grayscale in-plane image 10. where the synthetic images generated by the control patterns of icons can be thought of as being projected onto the surface of the inventive device, they are also shown in these figures as lying on the surface of the device. the intersection of the in-plane image 10 and the synthetic image, along with the control pattern distribution, determines what a viewer 26 will actually see. in both of these exemplary embodiments, as the inventive optical security device is tilted towards-away from the viewer, the collective focal points of the focusing elements will effectively shift upward and downward. this means that the intersection of a synthetic image with the in-plane image 10 will shift accordingly so that the synthetic image from a new contributing control pattern will highlight the in-plane image. for example, in fig. 8, the viewer 26 sees the intersection of the synthetic image 28 formed by control pattern f with the middle of the in-plane image 10, while in fig. 9, the viewer 26, now looking from a different angle, sees the intersection of the synthetic image 30 formed by control pattern d with the middle of the in-plane image 10. [0052] because the synthetic images shown in figs. 8 and 9, completely cover the in- plane image 10, there will always be portions of the in-plane image 10 that are visible or 'turned on', no matter what viewing angle. additionally, the slight ghost images of the synthetic images that remain visible because of light scattered through or around the focusing optics (as mentioned above) will help outline the in-plane image as a whole so that the coherent in-plane image is always visible. [0053] in figs. 10 and 11 , examples of control pattern distributions, and the resulting images that a viewer would see, are shown. [0054] the control pattern distribution 32 shown in fig. 10a is a "hard transition" control pattern distribution, which as alluded to above, results in sharp transitions between the synthetic images generated by the control patterns of icons. in fig. 10b, the grayscale image 10 is shown for reference purposes along with a collection of views 34 of the intersection between the control patterns' synthetic images and the in-plane image. [0055] the control pattern distribution 36 shown in fig. 11a is a "soft transition" control pattern distribution, which as also alluded to above, results in smooth transitions between the synthetic images generated by the control patterns of icons. in fig. 11 b, the grayscale in-plane image 10 is shown for reference purposes along with a collection of views 38 of the intersection between the control patterns' synthetic images and the in-plane image. [0056] in figs. 10 and 11 , the synthetic images formed by control pattern f, when intersected with the grayscale in-plane image 10, will yield a version of the monkey face with highlighted ears. this is because the ears represent the darkest parts of this grayscale in-plane image and the control pattern distribution has its darkest grayscale values associated with control pattern f. [0057] referring to the 'frames' of the animation offered by these exemplary embodiments of the inventive optical security device, which are shown in figs. 10b and 11 b, it will be seen that the use of a 'hard transition' control pattern distribution results in a 'hard boundary' between the different control pattern contributions to the in-plane image as a whole, while the use of a 'soft transition' control pattern distribution results in 'soft boundary' contributions to the in-plane image as a whole. in both embodiments, the viewer will see sweeping elevations rolling over a surface shaped like the in-plane image (i.e., a monkey's face). [0058] as is evident from the above discussion, the dynamic optical effects demonstrated by the present invention are determined by the relative phasing of the control patterns and by the control pattern distribution, in addition to the nature of the grayscale in-plane image. [0059] in fig. 12, the in-plane image 10 is shown 'filled' with the six (6) control patterns of icons shown in fig. 6. in fig. 13, one of the images (without dynamic optical effects) 40 viewable from a surface of the inventive optical security device employing the 'filled' in-plane image shown in fig. 12, is illustrated. [0060] in another exemplary embodiment of the inventive optical security device, more than one grayscale image is used, which allows for the animation of the synthetically magnified images. in this embodiment, each grayscale image is assigned a column, or "set" of control patterns of icons. the method for forming the icon layer in this exemplary embodiment is described above, with the selection of control patterns of icons being carried out for each grayscale image simultaneously, forming an overlay of the results of a plurality of grayscale images. [0061] in the example shown in figs. 14 and 15, a collection of six grayscale images form an animation. as best shown in fig. 15, the control patterns within the same "set" have variation in the vertical direction. that means that, for a given set (or, similarly, for a given grayscale image), tilting in the vertical direction will have the effect of rolling the color through the image in a choreography described by that set's control pattern probability distribution. corresponding control patterns in adjacent sets have variation in the horizontal direction. that means that tilting in the horizontal direction will have the effect of changing the grayscale image and can produce the effect of an animation. [0062] in this example, the sets of control patterns of icons can be coordinated such that there is one effect when the device is tilted towards-away (due to the variation within a set of control patterns of icons) and a different effect when the device is tilted right-left or left-right (due to the variation among the sets of control patterns of icons). [0063] generally speaking, there is no limit to the number of sets of control patterns of icons (equivalently the number grayscale in-plane images), or the number of control patterns within the set. this is due to the fact that the variation within either the horizontal or vertical direction can be continuous and can be based off of the continuum of time (for "frames" of animation), or the continuum of grayscale (equivalently, the real numbers on a range {e.g., [0,1])). [0064] although not a required feature, the icons shown and described herein are rather simple in design, adopting the shape of simple geometric shapes (e.g., circles, dots, squares, rectangles, stripes, bars, etc.) and lines {e.g., horizontal, vertical, or diagonal lines). [0065] the icons may adopt any physical form and in one exemplary embodiment are microstructured icons {i.e., icons having a physical relief). in a preferred embodiment the microstructured icons are in the form of: (a) optionally coated and/or filled voids or recesses formed on or within a substrate. the voids or recesses each measure from about 0.01 to about 50 microns in total depth; and/or (b) shaped posts formed on a surface of a substrate, each measuring from about 0.01 to about 50 microns in total height. [0066] in one such embodiment, the microstructured icons are in the form of voids or recesses in a polymeric substrate, or their inverse shaped posts, with the voids (or recesses) or regions surrounding the shaped posts optionally filled with a contrasting substance such as dyes, coloring agents, pigments, powdered materials, inks, powdered minerals, metal materials and particles, magnetic materials and particles, magnetized materials and particles, magnetically reactive materials and particles, phosphors, liquid crystals, liquid crystal polymers, carbon black or other light absorbing materials, titanium dioxide or other light scattering materials, photonic crystals, non-linear crystals, nanoparticles, nanotubes, buckeyballs, buckeytubes, organic materials, pearlescent materials, powdered pearls, multilayer interference materials, opalescent materials, iridescent materials, low refractive index materials or powders, high refractive index materials or powders, diamond powder, structural color materials, polarizing materials, polarization rotating materials, fluorescent materials, phosphorescent materials, thermochromic materials, piezochromic materials, photochromic materials, tribolumenscent materials, electroluminescent materials, electrochromic materials, magnetochromic materials and particles, radioactive materials, radioactivatable materials, electret charge separation materials, and combinations thereof. examples of suitable icons are also disclosed in u.s. patent no. 7,333,268 to steenblik et al., u.s. patent no. 7,468,842 to steenblik et al., and u.s. patent no. 7,738,175 to steenblik et al., all of which, as noted above, are fully incorporated by reference as if fully set forth herein. [0067] the icon layer of the inventive optical security device may have one or more layers of metallization applied to an outer surface thereof. the resulting effect is like an anisotropic lighting effect on metal, which may be useful for select applications. icon focusing elements [0068] the optionally embedded array of icon focusing elements is positioned to form at least one synthetically magnified image of at least a portion of the icons in each coextensive control pattern of icons. as the optical security device is tilted the synthetically magnified image of the in-plane image appears to have one or more dynamic optical effects {e.g., dynamic bands of rolling color running through it, growing concentric circles, rotating highlights, strobe-like effects). upon proper placement of an icon focusing element array over the 'filled' in-plane image, one or more synthetically magnified images are projected, the dynamic optical effects of which are controlled and choreographed by the control patterns of icons. [0069] the icon focusing elements used in the practice of the present invention are not limited and include, but are not limited to, cylindrical and non-cylindrical refractive, reflective, and hybrid refractive/reflective focusing elements. [0070] in an exemplary embodiment, the focusing elements are non-cylindrical convex or concave refractive microlenses having a spheric or aspheric surface. aspheric surfaces include conical, elliptical, parabolic, and other profiles. these lenses may have circular, oval, or polygonal {e.g., hexagonal, substantially hexagonal, square, substantially square) base geometries, and may be arranged in regular, irregular, or random, one- or two-dimensional arrays. in a preferred embodiment, the microlenses are aspheric concave or convex lenses having polygonal {e.g., hexagonal) base geometries that are arranged in a regular, two- dimensional array on a substrate or light-transmitting polymer film. [0071] the focusing elements, in one such exemplary embodiment, have preferred widths (in the case of cylindrical lenses) and base diameters (in the case of non-cylindrical lenses) of less than or equal to 1 millimeter including (but not limited to) widths/base diameters: ranging from about 200 to about 500 microns; and ranging from about 50 to about 199 microns, preferred focal lengths of less than or equal to 1 millimeter including (but not limited to) the sub- ranges noted above, and preferred f-numbers of less than or equal to 10 (more preferably, less than or equal to 6. in another contemplated embodiment, the focusing elements have preferred widths/base diameters of less than about 50 microns (more preferably, less than about 45 microns, and most preferably, from about 10 to about 40 microns), preferred focal lengths of less than about 50 microns (more preferably, less than about 45 microns, and most preferably, from about 10 to about 30 microns), and preferred f-numbers of less than or equal to 10 (more preferably, less than or equal to 6). in yet another contemplated embodiment, the focusing elements are cylindrical or lenticular lenses that are much larger than the lenses described above with no upper limit on lens width. [0072] as alluded to above, the array of icon focusing elements used in the inventive optical security device may constitute an array of exposed icon focusing elements {e.g., exposed refractive microlenses), or may constitute an array of embedded icon focusing elements {e.g., embedded microlenses), the embedding layer constituting an outermost layer of the optical security device. optical separation [0073] although not required by the present invention, optical separation between the array of focusing elements and the control patterns of icons may be achieved using one or more optical spacers. in one such embodiment, an optical spacer is bonded to the focusing element layer. in another embodiment, an optical spacer may be formed as a part of the focusing element layer, an optical spacer may be formed during manufacture independently from the other layers, or the thickness of the focusing element layer increased to allow the layer to be free standing. in yet another embodiment, the optical spacer is bonded to another optical spacer. [0074] the optical spacer may be formed using one or more essentially colorless materials including, but not limited to, polymers such as polycarbonate, polyester, polyethylene, polyethylene napthalate, polyethylene terephthalate, polypropylene, polyvinylidene chloride, and the like. [0075] in other contemplated embodiments of the present invention, the optical security device does not employ an optical spacer. in one such embodiment, the optical security device is an optionally transferable security device with a reduced thickness ("thin construction"), which basically comprises an icon layer substantially in contact with an array of optionally embedded icon focusing elements. method of manufacture [0076] the inventive optical security device may be prepared (to the extent not inconsistent with the teachings of the present invention) in accordance with the materials, methods and techniques disclosed in u.s. patent no. 7,333,268 to steenblik et al., u.s. patent no. 7,468,842 to steenblik et al., u.s. patent no. 7,738,175 to steenblik et al., and u.s. patent application publication no. 2010/0308571 a1 to steenblik et al., all of which are fully incorporated herein by reference as if fully set forth herein. as described in these references, arrays of focusing elements and image icons can be formed from a variety of materials such as substantially transparent or clear, colored or colorless polymers such as acrylics, acrylated polyesters, acrylated urethanes, epoxies, polycarbonates, polypropylenes, polyesters, urethanes, and the like, using a multiplicity of methods that are known in the art of micro-optic and microstructure replication, including extrusion {e.g., extrusion embossing, soft embossing), radiation cured casting, and injection molding, reaction injection molding, and reaction casting. high refractive index, colored or colorless materials having refractive indices (at 589 nm, 20°c) of more than 1.5, 1 .6, 1.7, or higher, such as those described in u.s. patent application publication no. us 2010/0109317 a1 to hoffmuller et al., may also be used. as also described, embedding layers can be prepared using adhesives, gels, glues, lacquers, liquids, molded or coated polymers, polymers or other materials containing organic or metallic dispersions, etc. [0077] as noted above, the optical security device of the present invention may be used in the form of sheet materials and base platforms that are made from or employ the inventive optical security device, as well as documents made from these materials. for example, the inventive device may take the form of a security strip, thread, patch, overlay, or inlay that is mounted to a surface of, or at least partially embedded within a fibrous or non-fibrous sheet material {e.g., banknote, passport, id card, credit card, label), or commercial product {e.g., optical disks, cds, dvds, packages of medical drugs). the inventive device may also be used in the form of a standalone product, or in the form of a non-fibrous sheet material for use in making, for example, banknotes, passports, and the like, or it may adopt a thicker, more robust form for use as, for example, a base platform for an id card, high value or other security document. [0078] in one such exemplary embodiment, the inventive device is a micro-optic film material such as an ultra-thin, sealed lens structure for use in banknotes, while in another such exemplary embodiment; the inventive device is a sealed lens polycarbonate inlay for base platforms used in the manufacture of plastic passports. [0079] while various embodiments of the present invention have been described above it should be understood that they have been presented by way of example only, and not limitation. thus, the breadth and scope of the present invention should not be limited by any of the exemplary embodiments. [0080] what is claimed is:
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112-504-717-866-275
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US
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H01L21/68,G01B11/27,G01B11/30,G03F7/20,H01L23/544,G01N21/47,G01B11/00,G03F9/00
| 2012-07-05T00:00:00 |
2012
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metrology method and apparatus, lithographic system, device manufacturing method and substrate
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a lithographic process is used to form a plurality of target structures distributed at a plurality of locations across a substrate and having overlaid periodic structures with a number of different overlay bias values distributed across the target structures. at least some of the target structures comprising a number of overlaid periodic structures (e.g., gratings) that is fewer than said number of different overlay bias values. asymmetry measurements are obtained for the target structures. the detected asymmetries are used to determine parameters of a lithographic process. overlay model parameters including translation, magnification and rotation, can be calculated while correcting the effect of bottom grating asymmetry, and using a multi-parameter model of overlay error across the substrate.
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1. a substrate comprising: a plurality of target structures distributed at a plurality of locations across the substrate, wherein three or more of the target structures comprise: overlaid periodic structures having different overlay biases, wherein a number of the overlaid periodic structures is greater than a number of the different overlay biases; and bottom grating asymmetry; wherein the three or more target structures have three different respective overlay biases and are disposed at different locations across the substrate, wherein the three or more target structures each comprise pairs of x and y gratings that are diagonal to each other, and wherein the three different respective overlay biases are configured to be used by a metrology apparatus to correct for feature asymmetries associated with the overlaid periodic structures, including the bottom grating asymmetry, by determining the feature asymmetries from a measurement by the metrology apparatus. 2. the substrate of claim 1 , wherein the different overlay biases span a range greater than 4%, 10%, 15%, or 20% of a respective pitch of the overlaid periodic structures. 3. the substrate of claim 1 , wherein the different overlay biases correspond to a location bias along an x axis, y axis, or both x and y axes. 4. the substrate of claim 1 , wherein at least one of the three or more target structures is distributed outside a device within the substrate and a remaining number of the three or more target structures are distributed inside the device. 5. the substrate of claim 4 , wherein the at least one target structure distributed outside the device has an overlay bias that does not correspond to an overlay bias of any of the target structures distributed inside the device. 6. the substrate of claim 4 , wherein one of the three or more target structures, different than the at least one target structure, are distributed along a predetermined density at different locations inside the device corresponding to device features. 7. the substrate of claim 4 , wherein the three different respective overlay biases are associated with at least first and second orders of diffraction and are further configured to be used by the metrology apparatus to correct for the feature asymmetries using the first and second orders. 8. the substrate of claim 7 , wherein: the number of overlaid periodic structures are configured to allow a number of propagating diffraction orders based on grating pitch of the overlaid periodic structures, and the number of propagating diffraction orders consists of the first and second diffraction orders.
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this application incorporates by reference in their entireties u.s. patent application ser. no. 14/412,771, 371(c) date jan. 5, 2015, int'l application no. pct/ep2013/062516, filed jun. 17, 2103 and u.s. provisional application 61/668,277, filed jul. 5, 2012. background field of the invention the present invention relates to methods and apparatus for metrology usable, for example, in the manufacture of devices by lithographic techniques and to methods of manufacturing devices using lithographic techniques. background art a lithographic apparatus is a machine that applies a desired pattern onto a substrate, usually onto a target portion of the substrate. a lithographic apparatus can be used, for example, in the manufacture of integrated circuits (ics). in that instance, a patterning device, which is alternatively referred to as a mask or a reticle, may be used to generate a circuit pattern to be formed on an individual layer of the ic. this pattern can be transferred onto a target portion (e.g., including part of, one, or several dies) on a substrate (e.g., a silicon wafer). transfer of the pattern is typically via imaging onto a layer of radiation-sensitive material (resist) provided on the substrate. in general, a single substrate will contain a network of adjacent target portions that are successively patterned. known lithographic apparatus include so-called steppers, in which each target portion is irradiated by exposing an entire pattern onto the target portion at one time, and so-called scanners, in which each target portion is irradiated by scanning the pattern through a radiation beam in a given direction (the “scanning”-direction) while synchronously scanning the substrate parallel or anti parallel to this direction. it is also possible to transfer the pattern from the patterning device to the substrate by imprinting the pattern onto the substrate. in lithographic processes, it is desirable frequently to make measurements of the structures created, e.g., for process control and verification. various tools for making such measurements are known, including scanning electron microscopes, which are often used to measure critical dimension (cd), and specialized tools to measure overlay, the accuracy of alignment of two layers in a device. recently, various forms of scatterometers have been developed for use in the lithographic field. these devices direct a beam of radiation onto a target and measure one or more properties of the scattered radiation—e.g., intensity at a single angle of reflection as a function of wavelength; intensity at one or more wavelengths as a function of reflected angle; or polarization as a function of reflected angle—to obtain a “spectrum” from which a property of interest of the target can be determined. determination of the property of interest may be performed by various techniques: e.g., reconstruction of the target structure by iterative approaches such as rigorous coupled wave analysis or finite element methods; library searches; and principal component analysis. the targets used by some conventional scatterometers are relatively large, e.g., 40 μm by 40 μm, gratings and the measurement beam generates a spot that is smaller than the grating (i.e., the grating is underfilled). this simplifies mathematical reconstruction of the target as it can be regarded as infinite. however, in order to reduce the size of the targets, e.g., to 10 μm by 10 μm or less, e.g., so they can be positioned in amongst product features, rather than in the scribe lane, metrology has been proposed in which the grating is made smaller than the measurement spot (i.e., the grating is overfilled). typically such targets are measured using dark field scatterometry in which the zeroth order of diffraction (corresponding to a specular reflection) is blocked, and only higher orders processed. diffraction-based overlay using dark-field detection of the diffraction orders enables overlay measurements on smaller targets. these targets can be smaller than the illumination spot and may be surrounded by product structures on a wafer. multiple targets can be measured in one image. in the known metrology technique, overlay measurement results are obtained by measuring the target twice under certain conditions, while either rotating the target or changing the illumination mode or imaging mode to obtain separately the −1 st and the +1 st diffraction order intensities. comparing these intensities for a given grating provides a measurement of asymmetry in the grating, and asymmetry in an overlay grating can be used as an indicator of overlay error. although the known dark-field image-based overlay measurements are fast and computationally very simple (once calibrated), they rely on an assumption that overlay is the only cause of asymmetry in the target structure. any other asymmetry in the stack, such as asymmetry of features within one or both of the overlaid gratings, also causes an asymmetry in the 1 st orders. this asymmetry which is not related to the overlay clearly perturbs the overlay measurement, giving an inaccurate overlay result. asymmetry in the bottom grating of the overlay grating is a common form of feature asymmetry. it may originate for example in wafer processing steps such as chemical-mechanical polishing (cmp), performed after the bottom grating was originally formed. accordingly at this time the skilled person has to choose between, on the one hand, a simple and fast measurement process that gives overlay measurements but is subject to inaccuracies when other causes of asymmetry are present, and on the other hand more traditional techniques that are computationally intensive and typically require several measurements of large, underfilled gratings to avoid the pupil image is polluted with signal from the environment of the overlay grating, which hampers the reconstruction on this. therefore, it is desired to distinguish the contributions to target structure asymmetry that are caused by overlay and other effects in a more direct and simple way, while minimizing the area of the substrate required for target structures. summary it is desirable to provide a method and apparatus for overlay metrology using target structures, in which throughput and accuracy can be improved over prior published techniques. furthermore, although the invention is not limited to this, it would be of great advantage, if this could be applied to small target structures that can be read out with the dark-field image-based technique. according to a first aspect of the present invention, there is provided a method of measuring parameters of a lithographic process, the method comprising using the lithographic process to form a plurality of target structures distributed at a plurality of locations across the substrate and having overlaid periodic structures with a number of different overlay bias values distributed across said target structures, at least some of the target structures comprising a number of overlaid periodic structures that is fewer than said number of different overlay bias values, illuminating the target structures and detecting asymmetries in the radiation scattered by said target structures, using the detected asymmetries to determine said parameters. according to a second aspect of the present invention, there is provided an inspection apparatus for measuring parameters of a lithographic process, the apparatus comprising a support for a substrate having a plurality of target structures distributed at a plurality of locations across the substrate and having overlaid periodic structures with a number of different overlay bias values distributed across said target structures, at least some of the target structures comprising a number of overlaid periodic structures that is fewer than said number of different overlay bias values, an optical system for illuminating the target structures and detecting asymmetries in the radiation scattered by said target structures, and a processor arranged to use the detected asymmetries to determine said parameters. according to a third aspect of the present invention, there is provided a computer program product comprising machine-readable instructions for causing a processor to perform the processing of a method according to the first aspect. according to a fourth aspect of the present invention, there is provided a lithographic system comprising a lithographic apparatus comprising, an illumination optical system arranged to illuminate a pattern, a projection optical system arranged to project an image of the pattern onto a substrate, and an inspection apparatus according to the second aspect. the lithographic apparatus is arranged to use the measurement results from the inspection apparatus in applying the pattern to further substrates. according to a fifth aspect of the present invention, there is provided a method of manufacturing devices wherein a device pattern is applied to a series of substrates using a lithographic process, the method including inspecting at least one periodic structure formed as part of or beside said device pattern on at least one of said substrates using a method according to the first aspect and controlling the lithographic process for later substrates in accordance with the result of the method. according to a sixth aspect of the present invention, there is provided a substrate comprising a plurality of target structures distributed at a plurality of locations across the substrate and having overlaid periodic structures with a number of different overlay bias values distributed across said target structures, at least some of the target structures comprising a number of overlaid periodic structures that is fewer than said number of different overlay bias values. further features and advantages of the invention, as well as the structure and operation of various embodiments of the invention, are described in detail below with reference to the accompanying drawings. it is noted that the invention is not limited to the specific embodiments described herein. such embodiments are presented herein for illustrative purposes only. additional embodiments will be apparent to persons skilled in the relevant art(s) based on the teachings contained herein. brief description of the drawings/figures the accompanying drawings, which are incorporated herein and form part of the specification, illustrate the present invention and, together with the description, further serve to explain the principles of the invention and to enable a person skilled in the relevant art(s) to make and use the invention. fig. 1 depicts a lithographic apparatus, according to an embodiment of the invention. fig. 2 depicts a lithographic cell or cluster, according to an embodiment of the invention. figs. 3a to 3d show (a) a schematic diagram of a dark field scatterometer for use in measuring targets according to embodiments of the invention using a first pair of illumination apertures, (b) a detail of diffraction spectrum of a target grating for a given direction of illumination (c) a second pair of illumination apertures providing further illumination modes in using the scatterometer for diffraction based overlay measurements and (d) a third pair of illumination apertures combining the first and second pair of apertures. fig. 4 depicts a known form of multiple grating target and an outline of a measurement spot on a substrate. fig. 5 depicts an image of the target of fig. 4 obtained in the scatterometer of fig. 3 . fig. 6 is a flowchart showing an overlay measurement method, according to embodiments of the present invention. fig. 7 illustrates principles of overlay measurement in an ideal target structure, not subject to feature asymmetry. fig. 8 illustrates principles of overlay measurement in a non-ideal target structure, with correction of feature asymmetry using an embodiment of the present invention. fig. 9 illustrates a patterning device having product areas, scribe lane areas and metrology targets in both the scribe lane and product areas. fig. 10 illustrates an embodiment of a patterning device for use with embodiments of the present invention. fig. 11 illustrates three composite grating structures distributed across a substrate and having a bias scheme that can be used in embodiments of the present invention, combining component gratings for two orthogonal directions of overlay measurement. and fig. 12 illustrates five composite grating structures distributed across a substrate and having a bias scheme that can be used in embodiments of the present invention. the features and advantages of the present invention will become more apparent from the detailed description set forth below when taken in conjunction with the drawings, in which like reference characters identify corresponding elements throughout. in the drawings, like reference numbers generally indicate identical, functionally similar, and/or structurally similar elements. the drawing in which an element first appears is indicated by the leftmost digit(s) in the corresponding reference number. detailed description this specification discloses one or more embodiments that incorporate the features of this invention. the disclosed embodiment(s) merely exemplify the invention. the scope of the invention is not limited to the disclosed embodiment(s). the invention is defined by the claims appended hereto. the embodiment(s) described, and references in the specification to “one embodiment”, “an embodiment”, “an example embodiment”, etc., indicate that the embodiment(s) described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. moreover, such phrases are not necessarily referring to the same embodiment. further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is understood that it is within the knowledge of one skilled in the art to effect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described. embodiments of the invention may be implemented in hardware, firmware, software, or any combination thereof. embodiments of the invention may also be implemented as instructions stored on a machine-readable medium, which may be read and executed by one or more processors. a machine-readable medium may include any mechanism for storing or transmitting information in a form readable by a machine (e.g., a computing device). for example, a machine-readable medium may include read only memory (rom); random access memory (ram); magnetic disk storage media; optical storage media; flash memory devices; electrical, optical, acoustical or other forms of propagated signals (e.g., carrier waves, infrared signals, digital signals, etc.), and others. further, firmware, software, routines, instructions may be described herein as performing certain actions. however, it should be appreciated that such descriptions are merely for convenience and that such actions in fact result from computing devices, processors, controllers, or other devices executing the firmware, software, routines, instructions, etc. before describing embodiments of the invention in detail, it is instructive to present an example environment in which embodiments of the present invention may be implemented. fig. 1 schematically depicts a lithographic apparatus la. the apparatus includes an illumination system (illuminator) il configured to condition a radiation beam b (e.g., uv radiation or duv radiation), a patterning device support or support structure (e.g., a mask table) mt constructed to support a patterning device (e.g., a mask) ma and connected to a first positioner pm configured to accurately position the patterning device in accordance with certain parameters; a substrate table (e.g., a wafer table) wt constructed to hold a substrate (e.g., a resist coated wafer) w and connected to a second positioner pw configured to accurately position the substrate in accordance with certain parameters; and a projection system (e.g., a refractive projection lens system) ps configured to project a pattern imparted to the radiation beam b by patterning device ma onto a target portion c (e.g., including one or more dies) of the substrate w. the illumination system may include various types of optical components, such as refractive, reflective, magnetic, electromagnetic, electrostatic or other types of optical components, or any combination thereof, for directing, shaping, or controlling radiation. the patterning device support holds the patterning device in a manner that depends on the orientation of the patterning device, the design of the lithographic apparatus, and other conditions, such as for example whether or not the patterning device is held in a vacuum environment. the patterning device support can use mechanical, vacuum, electrostatic or other clamping techniques to hold the patterning device. the patterning device support may be a frame or a table, for example, which may be fixed or movable as required. the patterning device support may ensure that the patterning device is at a desired position, for example with respect to the projection system. any use of the terms “reticle” or “mask” herein may be considered synonymous with the more general term “patterning device.” the term “patterning device” used herein should be broadly interpreted as referring to any device that can be used to impart a radiation beam with a pattern in its cross-section such as to create a pattern in a target portion of the substrate. it should be noted that the pattern imparted to the radiation beam may not exactly correspond to the desired pattern in the target portion of the substrate, for example if the pattern includes phase-shifting features or so called assist features. generally, the pattern imparted to the radiation beam will correspond to a particular functional layer in a device being created in the target portion, such as an integrated circuit. the patterning device may be transmissive or reflective. examples of patterning devices include masks, programmable mirror arrays, and programmable lcd panels. masks are well known in lithography, and include mask types such as binary, alternating phase-shift, and attenuated phase-shift, as well as various hybrid mask types. an example of a programmable mirror array employs a matrix arrangement of small mirrors, each of which can be individually tilted so as to reflect an incoming radiation beam in different directions. the tilted mirrors impart a pattern in a radiation beam, which is reflected by the mirror matrix. the term “projection system” used herein should be broadly interpreted as encompassing any type of projection system, including refractive, reflective, catadioptric, magnetic, electromagnetic and electrostatic optical systems, or any combination thereof, as appropriate for the exposure radiation being used, or for other factors such as the use of an immersion liquid or the use of a vacuum. any use of the term “projection lens” herein may be considered as synonymous with the more general term “projection system”. as here depicted, the apparatus is of a transmissive type (e.g., employing a transmissive mask). alternatively, the apparatus may be of a reflective type (e.g., employing a programmable mirror array of a type as referred to above, or employing a reflective mask). the lithographic apparatus may be of a type having two (dual stage) or more substrate tables (and/or two or more mask tables). in such “multiple stage” machines the additional tables may be used in parallel, or preparatory steps may be carried out on one or more tables while one or more other tables are being used for exposure. the lithographic apparatus may also be of a type wherein at least a portion of the substrate may be covered by a liquid having a relatively high refractive index, e.g., water, so as to fill a space between the projection system and the substrate. an immersion liquid may also be applied to other spaces in the lithographic apparatus, for example, between the mask and the projection system. immersion techniques are well known in the art for increasing the numerical aperture of projection systems. the term “immersion” as used herein does not mean that a structure, such as a substrate, must be submerged in liquid, but rather only means that liquid is located between the projection system and the substrate during exposure. referring to fig. 1 , the illuminator il receives a radiation beam from a radiation source so. the source and the lithographic apparatus may be separate entities, for example when the source is an excimer laser. in such cases, the source is not considered to form part of the lithographic apparatus and the radiation beam is passed from the source so to the illuminator il with the aid of a beam delivery system bd including, for example, suitable directing mirrors and/or a beam expander. in other cases the source may be an integral part of the lithographic apparatus, for example when the source is a mercury lamp. the source so and the illuminator il, together with the beam delivery system bd if required, may be referred to as a radiation system. the illuminator il may include an adjuster ad for adjusting the angular intensity distribution of the radiation beam. generally, at least the outer and/or inner radial extent (commonly referred to as σ-outer and σ-inner, respectively) of the intensity distribution in a pupil plane of the illuminator can be adjusted. in addition, the illuminator il may include various other components, such as an integrator in and a condenser co. the illuminator may be used to condition the radiation beam, to have a desired uniformity and intensity distribution in its cross section. the radiation beam b is incident on the patterning device (e.g., mask) ma, which is held on the patterning device support (e.g., mask table mt), and is patterned by the patterning device. having traversed the patterning device (e.g., mask) ma, the radiation beam b passes through the projection system ps, which focuses the beam onto a target portion c of the substrate w. with the aid of the second positioner pw and position sensor if (e.g., an interferometric device, linear encoder, 2-d encoder or capacitive sensor), the substrate table wt can be moved accurately, e.g., so as to position different target portions c in the path of the radiation beam b. similarly, the first positioner pm and another position sensor (which is not explicitly depicted in fig. 1 ) can be used to accurately position the patterning device (e.g., mask) ma with respect to the path of the radiation beam b, e.g., after mechanical retrieval from a mask library, or during a scan. in general, movement of the patterning device support (e.g., mask table) mt may be realized with the aid of a long-stroke module (coarse positioning) and a short-stroke module (fine positioning), which form part of the first positioner pm. similarly, movement of the substrate table wt may be realized using a long-stroke module and a short-stroke module, which form part of the second positioner pw. in the case of a stepper (as opposed to a scanner) the patterning device support (e.g., mask table) mt may be connected to a short-stroke actuator only, or may be fixed. patterning device (e.g., mask) ma and substrate w may be aligned using mask alignment marks m 1 , m 2 and substrate alignment marks p 1 , p 2 . although the substrate alignment marks as illustrated occupy dedicated target portions, they may be located in spaces between target portions (these are known as scribe-lane alignment marks). similarly, in situations in which more than one die is provided on the patterning device (e.g., mask) ma, the mask alignment marks may be located between the dies. small alignment markers may also be included within dies, in amongst the device features, in which case it is desirable that the markers be as small as possible and not require any different imaging or process conditions than adjacent features. the alignment system, which detects the alignment markers is described further below. the depicted apparatus could be used in at least one of the following modes: 1. in step mode, the patterning device support (e.g., mask table) mt and the substrate table wt are kept essentially stationary, while an entire pattern imparted to the radiation beam is projected onto a target portion c at one time (i.e., a single static exposure). the substrate table wt is then shifted in the x and/or y direction so that a different target portion c can be exposed. in step mode, the maximum size of the exposure field limits the size of the target portion c imaged in a single static exposure. 2. in scan mode, the patterning device support (e.g., mask table) mt and the substrate table wt are scanned synchronously while a pattern imparted to the radiation beam is projected onto a target portion c (i.e., a single dynamic exposure). the velocity and direction of the substrate table wt relative to the patterning device support (e.g., mask table) mt may be determined by the (de-)magnification and image reversal characteristics of the projection system ps. in scan mode, the maximum size of the exposure field limits the width (in the non-scanning direction) of the target portion in a single dynamic exposure, whereas the length of the scanning motion determines the height (in the scanning direction) of the target portion. 3. in another mode, the patterning device support (e.g., mask table) mt is kept essentially stationary holding a programmable patterning device, and the substrate table wt is moved or scanned while a pattern imparted to the radiation beam is projected onto a target portion c. in this mode, generally a pulsed radiation source is employed and the programmable patterning device is updated as required after each movement of the substrate table wt or in between successive radiation pulses during a scan. this mode of operation can be readily applied to maskless lithography that utilizes programmable patterning device, such as a programmable mirror array of a type as referred to above. combinations and/or variations on the above described modes of use or entirely different modes of use may also be employed. lithographic apparatus la is of a so-called dual stage type which has two substrate tables wta, wtb and two stations—an exposure station and a measurement station—between which the substrate tables can be exchanged. while one substrate on one substrate table is being exposed at the exposure station, another substrate can be loaded onto the other substrate table at the measurement station and various preparatory steps carried out. the preparatory steps may include mapping the surface control of the substrate using a level sensor ls and measuring the position of alignment markers on the substrate using an alignment sensor as. this enables a substantial increase in the throughput of the apparatus. if the position sensor if is not capable of measuring the position of the substrate table while it is at the measurement station as well as at the exposure station, a second position sensor may be provided to enable the positions of the substrate table to be tracked at both stations. as shown in fig. 2 , the lithographic apparatus la forms part of a lithographic cell lc, also sometimes referred to a lithocell or cluster, which also includes apparatus to perform pre- and post-exposure processes on a substrate. conventionally these include spin coaters sc to deposit resist layers, developers de to develop exposed resist, chill plates ch and bake plates bk. a substrate handler, or robot, ro picks up substrates from input/output ports i/o 1 , i/o 2 , moves them between the different process apparatus and delivers then to the loading bay lb of the lithographic apparatus. these devices, which are often collectively referred to as the track, are under the control of a track control unit tcu which is itself controlled by the supervisory control system scs, which also controls the lithographic apparatus via lithography control unit lacu. thus, the different apparatus can be operated to maximize throughput and processing efficiency. examples of dark field metrology can be found in international patent applications wo 2009/078708 and wo 2009/106279 which documents are hereby incorporated by reference in their entirety. further developments of the technique have been described in patent publications us20110027704a and us20110043791a and in published us patent application us 20120123581. the contents of all these applications are also incorporated herein by reference in their entireties. a dark field metrology apparatus suitable for use in embodiments of the invention is shown in fig. 3(a) . a target grating t and diffracted rays are illustrated in more detail in fig. 3(b) . the dark field metrology apparatus may be a stand-alone device or incorporated in either the lithographic apparatus la, e.g., at the measurement station, or the lithographic cell lc. an optical axis, which has several branches throughout the apparatus, is represented by a dotted line o. in this apparatus, light emitted by source 11 (e.g., a xenon lamp) is directed onto substrate w via a beam splitter 15 by an optical system comprising lenses 12 , 14 and objective lens 16 . these lenses are arranged in a double sequence of a 4f arrangement. a different lens arrangement can be used, provided that it still provides a substrate image onto a detector, and simultaneously allows for access of an intermediate pupil-plane for spatial-frequency filtering. therefore, the angular range at which the radiation is incident on the substrate can be selected by defining a spatial intensity distribution in a plane that presents the spatial spectrum of the substrate plane, here referred to as a (conjugate) pupil plane. in particular, this can be done by inserting an aperture plate 13 of suitable form between lenses 12 and 14 , in a plane which is a back-projected image of the objective lens pupil plane. in the example illustrated, aperture plate 13 has different forms, labeled 13 n and 13 s, allowing different illumination modes to be selected. the illumination system in the present examples forms an off-axis illumination mode. in the first illumination mode, aperture plate 13 n provides off-axis from a direction designated, for the sake of description only, as ‘north’. in a second illumination mode, aperture plate 13 s is used to provide similar illumination, but from an opposite direction, labeled ‘south’. other modes of illumination are possible by using different apertures. the rest of the pupil plane is desirably dark as any unnecessary light outside the desired illumination mode will interfere with the desired measurement signals. as shown in fig. 3(b) , target grating t is placed with substrate w normal to the optical axis o of objective lens 16 . a ray of illumination i impinging on grating t from an angle off the axis o gives rise to a zeroth order ray (solid line 0) and two first order rays (dot-chain line +1 and double dot-chain line −1). it should be remembered that with an overfilled small target grating, these rays are just one of many parallel rays covering the area of the substrate including metrology target grating t and other features. since the aperture in plate 13 has a finite width (necessary to admit a useful quantity of light, the incident rays i will in fact occupy a range of angles, and the diffracted rays 0 and +1/−1 will be spread out somewhat. according to the point spread function of a small target, each order +1 and −1 will be further spread over a range of angles, not a single ideal ray as shown. note that the grating pitches and illumination angles can be designed or adjusted so that the first order rays entering the objective lens are closely aligned with the central optical axis. the rays illustrated in figs. 3(a) and 3(b) are shown somewhat off axis, purely to enable them to be more easily distinguished in the diagram. at least the 0 and +1 orders diffracted by the target on substrate w are collected by objective lens 16 and directed back through beam splitter 15 . returning to fig. 3(a) , both the first and second illumination modes are illustrated, by designating diametrically opposite apertures labeled as north (n) and south (s). when the incident ray i is from the north side of the optical axis, that is when the first illumination mode is applied using aperture plate 13 n, the +1 diffracted rays, which are labeled +1(n), enter the objective lens 16 . in contrast, when the second illumination mode is applied using aperture plate 13 s the −1 diffracted rays (labeled −1(s)) are the ones which enter the lens 16 . a second beam splitter 17 divides the diffracted beams into two measurement branches. in a first measurement branch, optical system 18 forms a diffraction spectrum (pupil plane image) of the target on first sensor 19 (e.g., a ccd or cmos sensor) using the zeroth and first order diffractive beams. each diffraction order hits a different point on the sensor, so that image processing can compare and contrast orders. the pupil plane image captured by sensor 19 can be used for focusing the metrology apparatus and/or normalizing intensity measurements of the first order beam. the pupil plane image can also be used for many measurement purposes such as reconstruction, which are not the subject of the present disclosure. in the second measurement branch, optical system 20 , 22 forms an image of the target on the substrate w on sensor 23 (e.g., a ccd or cmos sensor). in the second measurement branch, an aperture stop 21 is provided in a plane that is conjugate to the pupil-plane. aperture stop 21 functions to block the zeroth order diffracted beam so that the image of the target formed on sensor 23 is formed only from the −1 or +1 first order beam. the images captured by sensors 19 and 23 are output to image processor and controller pu, the function of which will depend on the particular type of measurements being performed. note that the term ‘image’ is used here in a broad sense. an image of the grating lines as such will not be formed, if only one of the −1 and +1 orders is present. the particular forms of aperture plate 13 and field stop 21 shown in fig. 3 are purely examples. in another embodiment of the invention, on-axis illumination of the targets is used and an aperture stop with an off-axis aperture is used to pass substantially only one first order of diffracted light to the sensor. in yet other embodiments, 2nd, 3rd and higher order beams (not shown in fig. 3 ) can be used in measurements, instead of or in addition to the first order beams. in order to make the illumination adaptable to these different types of measurement, the aperture plate 13 may comprise a number of aperture patterns formed around a disc, which rotates to bring a desired pattern into place. alternatively or in addition, a set of plates 13 could be provided and swapped, to achieve the same effect. a programmable illumination device such as a deformable mirror array or transmissive spatial sight modulator can be used also. moving mirrors or prisms can be used as another way to adjust the illumination mode. as just explained in relation to aperture plate 13 , the selection of diffraction orders for imaging can alternatively be achieved by altering the pupil-stop 21 , or by substituting a pupil-stop having a different pattern, or by replacing the fixed field stop with a programmable spatial light modulator. in that case the illumination side of the measurement optical system can remain constant, while it is the imaging side that has first and second modes. in the present disclosure, therefore, there are effectively three types of measurement method, each with its own advantages and disadvantages. in one method, the illumination mode is changed to measure the different orders. in another method, the imaging mode is changed. in a third method, the illumination and imaging modes remain unchanged, but the target is rotated through 180 degrees. in each case the desired effect is the same, namely to select first and second portions of the non-zero order diffracted radiation which are symmetrically opposite one another in the diffraction spectrum of the target. in principle, the desired selection of orders could be obtained by a combination of changing the illumination modes and the imaging modes simultaneously, but that is likely to bring disadvantages for no advantage, so it will not be discussed further. while the optical system used for imaging in the present examples has a wide entrance pupil which is restricted by the field stop 21 , in other embodiments or applications the entrance pupil size of the imaging system itself may be small enough to restrict to the desired order, and thus serve also as the field stop. different aperture plates are shown in figs. 3(c) and (d) which can be used as described further below. typically, a target grating will be aligned with its grating lines running either north-south or east-west. that is to say, a grating will be aligned in the x direction or the y direction of the substrate w. note that aperture plate 13 n or 13 s can only be used to measure gratings oriented in one direction (x or y depending on the set-up). for measurement of an orthogonal grating, rotation of the target through 90° and 270° might be implemented. more conveniently, however, illumination from east or west is provided in the illumination optics, using the aperture plate 13 e or 13 w, shown in fig. 3(c) . the aperture plates 13 n to 13 w can be separately formed and inter changed, or they may be a single aperture plate which can be rotated by 90, 180 or 270 degrees. as mentioned already, the off-axis apertures illustrated in fig. 3(c) could be provided in field stop 21 instead of in illumination aperture plate 13 . in that case, the illumination would be on axis. fig. 3(d) shows a third pair of aperture plates that can be used to combine the illumination modes of the first and second pairs. aperture plate 13 nw has apertures at north and east, while aperture plate 13 se has apertures at south and west. provided that cross-talk between these different diffraction signals is not too great, measurements of both x and y gratings can be performed without changing the illumination mode. fig. 4 depicts a composite target formed on a substrate according to known practice. the composite target comprises four gratings 32 to 35 positioned closely together so that they will all be within a measurement spot 31 formed by the illumination beam of the metrology apparatus. the four targets thus are all simultaneously illuminated and simultaneously imaged on sensors 19 and 23 . in an example dedicated to overlay measurement, gratings 32 to 35 are themselves composite gratings formed by overlying gratings that are patterned in different layers of the semi-conductor device formed on substrate w. gratings 32 to 35 may have differently biased overlay offsets in order to facilitate measurement of overlay between the layers in which the different parts of the composite gratings are formed. gratings 32 to 35 may also differ in their orientation, as shown, so as to diffract incoming radiation in x and y directions. in one example, gratings 32 and 34 are x-direction gratings with biases of the +d, −d, respectively. this means that grating 32 has its overlying components arranged so that if they were both printed exactly at their nominal locations one of the components would be offset relative to the other by a distance d. grating 34 has its components arranged so that if perfectly printed there would be an offset of d but in the opposite direction to the first grating and so on. gratings 33 and 35 are y-direction gratings with offsets +d and −d respectively. while four gratings are illustrated, another embodiment might require a larger matrix to obtain the desired accuracy. for example, a 3×3 array of nine composite gratings may have biases −4d, −3d, −2d, −d, 0, +d, +2d, +3d, +4d. separate images of these gratings can be identified in the image captured by sensor 23 . fig. 5 shows an example of an image that may be formed on and detected by the sensor 23 , using the target of fig. 4 in the apparatus of fig. 3 , using the aperture plates 13 nw or 13 se from fig. 3(d) . while the pupil plane image sensor 19 cannot resolve the different individual gratings 32 to 35 , the image sensor 23 can do so. the dark rectangle represents the field of the image on the sensor, within which the illuminated spot 31 on the substrate is imaged into a corresponding circular area 41 . within this, rectangular areas 42 - 45 represent the images of the small target gratings 32 to 35 . if the gratings are located in product areas, product features may also be visible in the periphery of this image field. image processor and controller pu processes these images using pattern recognition to identify the separate images 42 to 45 of gratings 32 to 35 . in this way, the images do not have to be aligned very precisely at a specific location within the sensor frame, which greatly improves throughput of the measuring apparatus as a whole. however the need for accurate alignment remains if the imaging process is subject to non-uniformities across the image field. in one embodiment of the invention, four positions p 1 to p 4 are identified and the gratings are aligned as much as possible with these known positions. once the separate images of the gratings have been identified, the intensities of those individual images can be measured, e.g., by averaging or summing selected pixel intensity values within the identified areas. intensities and/or other properties of the images can be compared with one another. these results can be combined to measure different parameters of the lithographic process. overlay performance is an important example of such a parameter. fig. 6 illustrates how, using for example the method described in application wo 2011/012624, which is incorporated by reference herein in its entirety, overlay error between the two layers containing the component gratings 32 to 35 is measured through asymmetry of the gratings, as revealed by comparing their intensities in the +1 order and −1 order dark field images. at step s 1 , the substrate, for example a semiconductor wafer, is processed through the lithographic cell of fig. 2 one or more times, to create a structure including the overlay targets 32 - 35 . at s 2 , using the metrology apparatus of fig. 3 , an image of the gratings 32 to 35 is obtained using only one of the first order diffracted beams (say −1). then, whether by changing the illumination mode, or changing the imaging mode, or by rotating substrate w by 180° in the field of view of the metrology apparatus, a second image of the gratings using the other first order diffracted beam (+1) can be obtained (step s 3 ). consequently the +1 diffracted radiation is captured in the second image. note that, by including only half of the first order diffracted radiation in each image, the ‘images’ referred to here are not conventional dark field microscopy images. the individual grating lines will not be resolved. each grating will be represented simply by an area of a certain intensity level. in step s 4 , a region of interest (roi) is carefully identified within the image of each component grating, from which intensity levels will be measured. this is done because, particularly around the edges of the individual grating images, intensity values can be highly dependent on process variables such as resist thickness, composition, line shape, as well as edge effects generally. having identified the roi for each individual grating and measured its intensity, the asymmetry of the grating structure, and hence overlay error, can then be determined. this is done by the image processor and controller pu in step s 5 comparing the intensity values obtained for +1 and −1 orders for each grating 32 - 35 to identify any difference in their intensity, and (s 6 ) from knowledge of the overlay biases of the gratings to determine overlay error in the vicinity of the target t. in the prior applications, mentioned above, various techniques are disclosed for improving the quality of overlay measurements using the basic method mentioned above. for example, the intensity differences between images may be attributable to differences in the optical paths used for the different measurements, and not purely asymmetry in the target. the illumination source 11 may be such that the intensity and/or phase of illumination spot 31 is not uniform. corrections can the determined and applied to minimize such errors, by reference for example to the position of the target image in the image field of sensor 23 . these techniques are explained in the prior applications, and will not be explained here in further detail. they may be used in combination with the techniques newly disclosed in the present application, which will now be described. in the present application, we propose the use of gratings with three or more biases distributed at locations across the substrate to measure overlay by the method of fig. 6 . by measuring asymmetries for gratings with at least three different biases, the calculations in step s 6 can be modified so as to correct for feature asymmetry in the target gratings, such as is caused by bottom grating asymmetry (bga) in a practical lithographic process. using a multi-parameter model of overlay error across the substrate enables the distribution of the overlay-biased gratings at locations across the substrate, saving real-estate as it not necessary to have compound targets with all the overlay-biased gratings located together. in fig. 7 a curve 702 illustrates the relationship between overlay error ov and measured asymmetry a for an ‘ideal’ target having zero offset and no feature asymmetry within the individual gratings forming the overlay grating. these graphs are to illustrate the principles of the invention only, and in each graph, the units of measured asymmetry a and overlay error ov are arbitrary. examples of actual dimensions will be given further below. in the ‘ideal’ situation of fig. 7 , the curve 702 indicates that the measured asymmetry a has a sinusoidal relationship with the overlay. the period p of the sinusoidal variation corresponds to the period of the gratings. the sinusoidal form is pure in this example, but could include harmonics in other circumstances. for the sake of simplicity, it is assumed in this example (a) that only first order diffracted radiation from the targets reaches the image sensor 23 (or its equivalent in a given embodiment), and (b) that the experimental target design is such that within these first orders a pure sine-relation between intensity and overlay between top and bottom grating results. whether this is true in practice is a function of the optical system design, the wavelength of the illuminating radiation and the pitch p of the grating, and the design and stack of the target. in an embodiment where 2 nd , 3 rd or higher orders also contribute to the intensities measured by sensor 23 , or where the target design introduces harmonics in the first order, the skilled reader can readily adapt the teaching of the present application to allow for higher orders being present. as mentioned above, biased gratings can be used to measure overlay, rather than relying on a single measurement. this bias has a known value defined in the patterning device (e.g., a reticle) from which it was made, that serves as an on-wafer calibration of the overlay corresponding to the measured signal. in the drawing, the calculation is illustrated graphically. in steps s 1 -s 5 , asymmetry measurements a(+d) and a(−d) are obtained for component gratings having biases +d an −d respectively. fitting these measurements to the sinusoidal curve gives points 704 and 706 as shown. knowing the biases, the true overlay error ov can be calculated. the pitch p of the sinusoidal curve is known from the design of the target. the vertical scale of the curve 702 is not known to start with, but is an unknown factor which we can call a 1 st harmonic proportionality constant, k 1 . using two measurements with of gratings with different, known biases one can solve two equations to calculate the unknowns k 1 and overlay ov. fig. 8 shows the effect of introducing feature asymmetry, for example by the effect of processing steps on the bottom grating layer. the ‘ideal’ sinusoidal curve 702 no longer applies. however, the inventors have recognized that, at least approximately, bottom grating asymmetry or other feature asymmetry has the effect of adding an offset to the asymmetry value a, which is relatively constant across all overlay values. the resulting curve is shown as 712 in the diagram, with label a bga indicating the offset due to feature asymmetry. by providing multiple gratings with a biasing scheme having three or more different bias values, accurate overlay measurements can still be obtained by fitting the measurements to the off-set sine curve 712 and eliminating the constant. for a simple example to illustrate the principle of the modified measurement and calculations, fig. 8 shows three measurement points 714 , 716 and 718 fitted to the curve 712 . the points 714 and 716 are measured from gratings having bias +d and −d, the same as for the points 704 and 706 in fig. 7 . a third asymmetry measurement from a grating with zero bias (in this example) is plotted at 718 . fitting the curve to three points allows the constant asymmetry value a bga that is due to feature asymmetry to be separated from the sinusoidal contribution a ov that is due to overlay error, so that the overlay error can be calculated more accurately. as noted already, the overlay calculations of modified step s 6 rely on certain assumptions. firstly, it is assumed that 1 st order intensity asymmetry due to the feature asymmetry (for example bga) is independent of the overlay for the overlay range of interest, and as a result it can be described by a constant offset k 0 . the validity of this assumption has been tested in model-based simulations. another assumption is that intensity asymmetry behaves as a sine function of the overlay, with the period p corresponding to the grating pitch. the number of harmonics can be designed to be small for diffraction-based overlay, by using a small pitch-wavelength ratio that only allows for a small number of propagating diffraction orders from the grating. therefore, in some embodiments, the overlay contribution to the intensity-asymmetry may be assumed to be only sinusoidal with a 1 st harmonic, and if necessary a 2 nd harmonic. also, in the target design, line-widths and spacings can be used for optimization, tuning for the presence of mainly a first harmonic, or first two or three harmonics. fig. 9 shows schematically the overall layout of a patterning device m. the metrology targets 92 may be included in a scribe lane portion of the applied pattern, between functional device pattern areas 90 . as is well known, patterning device m may contain a single device pattern, or an array of device patterns if the field of the lithographic apparatus is large enough to accommodate them. the example in fig. 9 shows four device areas labeled d 1 to d 4 . scribe lane targets 92 are placed adjacent these device pattern areas and between them. on the finished substrate, such as a semiconductor device, the substrate w will be diced into individual devices by cutting along these scribe lanes, so that the presence of the targets does not reduce the area available for functional device patterns. where targets are small in comparison with conventional metrology targets, they may also be deployed within the device area, to allow closer monitoring of lithography and process performance across the substrate. some targets 94 of this type are shown in device area d 1 . while fig. 9 shows the patterning device m, the same pattern is reproduced on the substrate w after the lithographic process, and consequently this description applies to the substrate w as well as the patterning device. fig. 10 shows in more detail one of the product areas 90 on the patterning device m, showing the targets 92 and 94 in more detail. the same pattern is produced and repeated at each field on the substrate. product areas are labeled d and scribe-line areas are labeled sl. in the device areas 90 , targets 94 are spread with a desired density at different locations among the product features. in the scribe-lane areas sl, targets 92 are provided. the targets 92 and 94 have, for example, the form illustrated in fig. 4 , and can be measured using the dark-field imaging sensor 23 of the scatterometer of fig. 3 . fig. 11 illustrates three composite grating structures distributed across a substrate and having a bias scheme that can be used in embodiments of the present invention, combining component gratings for two orthogonal directions of overlay measurement. fig. 11 shows three example targets 111 , 112 and 113 , which can be used to implement overlay model parameter measurement with bga correction. to solve for the overlay, at least three biases are required, because of the at least three unknowns: k 0 , k 1 , and overlay. embodiments of the present invention may have single biased gratings distributed over the area to be measured: the field, die or smaller. other embodiments, such as illustrated in fig. 11 are compatible with 2×2 target designs. with the notations: bias=+d. bias=−d or bias=0, for example 10×10 μm 2 targets can be produced with gratings using the following bias-scheme with three layouts in this example: target 111 : +d,x; +d,y, −d,y, −d,xtarget 112 : +d,x; +d,y, 0,y, 0,xtarget 113 : 0,x; 0,y, −d,y, −d,x all these three targets can also be used to calculate local values of overlay using pupil-detection diffraction based overlay (provided that the scatterometer spot size is small enough) or dark-field diffraction based overlay methods, using symmetric and asymmetric first harmonic methods. simultaneously, local results can be compared with the outcome of the model-parameterized model, for example the described six-parameter model, recalculated to the local values, but including all bga and higher harmonics corrections. it will be appreciated that embodiments of the present invention are not limited to only two higher harmonics. the common property of these targets is that they can all be read out for overlay also with the dark-field image-based technique known from the previous patent applications mentioned above. this enables bga-corrected overlay at small targets without stack-reconstruction. fig. 11 shows composite grating targets having three different biases, in which both x- and y-direction gratings are provided across the target areas. the bias schemes for each direction are shown, but of course other schemes can be envisaged, provided that at least two, and preferably at least three different biases are included distributed across the substrate in the individual target structures. the x and y gratings with each bias value are side-by-side, though that is not essential. the x and y gratings are interspersed with one another in an alternating pattern, so that different x gratings are diagonally spaced, not side-by-side with one another, and y gratings are diagonally spaced, not side-by-side with one another. this arrangement may help to reduce cross-talk between diffraction signals of the different biased gratings. the whole arrangement thus allows a compact target design, without good performance. while the component gratings in fig. 11 are square, composite grating targets with x and y component gratings can also be made with elongate gratings. examples are described for example in published patent application us20120044470, which is incorporated by reference herein in its entirety. with reference to fig. 12 , one biased grating per target (per direction) may also be used. for example, in order to take into account k 0 and k 1 there are five unknown parameters for the x-direction (t x , m x , r x , k 0x , k 1x ) and five unknown parameters for the y-direction (t y , m y , r y , k 0y , k 1y ). one can then solve at least five equations per direction, therefore one needs five asymmetry measurements per direction. in this example, this means that five targets are sufficient in each direction (in the example of fig. 12 there are five targets and each target has one biased grating per direction) in the ideal case with negligible noise. in practice, it is useful toe have redundancy, for example to average noise and possible model errors out. in order to take into account three parameters k 0 , k 1 and overlay, three different biases are required (e.g., +d, 0, −d). in this example case the number of targets (five) is higher than the number of biases (three). with reference to fig. 12 , five targets are depicted and there are three different biases (+d, 0, −d) although not all the targets are different. the configuration depicted in fig. 12 is nevertheless sufficient to determine all the unknown parameters in this example, as mentioned above in the ideal case with negligible noise. with more redundancy than indicated in fig. 12 noise may be averaged out and a better answer in terms of t, r, and m for x and y may be achieved. more redundancy is also useful if the experimental reality is more complex than this 6-parameter model. overlay error may be determined by a direct comparison of the asymmetry in two biased gratings. the overlay may be modeled to have the following single-harmonic relation with asymmetry: where a is the asymmetry between detected + 1 st and −1 st diffraction order intensities, ov is overlay, p is the pitch of the target grating and k 1 is the first harmonic proportionality constant. two gratings are used in the x-direction and two gratings in y-direction. a typical dark-field diffraction-based overlay target has a real estate of 10×10 μm 2 . the issue with the single-harmonic method of equation 1 is, that no bottom-grating asymmetry or higher orders than the 1st harmonic due to non-linearity can be taken into account. using only two gratings per overlay error measurement only allows for the determination of two unknowns, k 1 and ov. any higher order term or asymmetric term will need for more gratings and thus more space. in reality the relation above is a truncation of an infinite sum of pitch-periodic functions, for the asymmetry property: a sine-series, due to the pitch-periodicity in overlay of the signal from the grating structure, and the complete expression (including a constant term describing the asymmetry contribution which can be considered as the first cosine term) is: the higher order k terms k 2 , k 3 , etc. are especially important for targets where the overlay targets have a relative small distance between the upper and lower overlaid gratings, thus having strong coupling. the k 0 term is important for all process steps introducing asymmetries. it is possible to add gratings to a target in one location on the substrate, in order to measure more harmonics in the equation (2). however, this has the drawback of an increased real estate per target. it can be acceptable in some cases to add to gratings to the conventional four grating target to give to a total of six for bga correction. however, for many on-product applications not only k 0 but also k 2 and possibly k 3 or higher are important. this would mean further increasing the real-estate for metrology targets, which is undesirable. embodiments of the present invention solve the overlay model parameters (i.e. not directly determining the overlay per target location but rather using a six-parameter model), combined with a bottom grating asymmetry term k 0 and higher order k-terms for non-linearity correction. this is achieved by virtue of combining a distribution of targets over the die, or over the area to be measured and modeled for overlay. an advantage is that the real estate per target is not increased. furthermore, the method directly solves only for the model parameters, e.g., translation, magnification, and rotation, in which the semiconductor manufacturer is interested. this is because it is those parameters which can be controlled in the lithographic apparatus. afterwards, if desired, or for verification purposes, the overlay can be retrieved locally by recalculating from the model parameters. embodiments of the present invention can be implemented by measuring only targets and, in the end, a distribution of biased gratings over the die. this is followed by solving the intensity-difference measurements for overlay and the required harmonics. the gratings have a distribution of biases across the substrate. this can be two, three or more biases. the number of biases used depends on how many harmonics are taken into account. in the single target case: if only k 1 and overlay are the unknowns then two biases are sufficient; if k 0- , k 1 , and overlay are the unknowns then three biases are sufficient; if k 0 , k 1 , k 2 , and overlay are the unknowns then four biases, etc. in the case of a distribution over the field/die, as is the case in this embodiment, that is solved in one block (see equation below). note that such a distribution over the die and decoupling of x- and y-direction metrology is experimentally very difficult for the bar-in-bar (bib) targets in the image-based overlay (ibo) metrology. the set of equations in an embodiment of the present invention are as follows, for k 0 , k 1 and k 2 and using a six-parameter intra-field model: here, n is the number of x- and the number of y-gratings (though they do not need necessarily be the same). this is different from other notation in which n refers to the harmonic number in the sine-expansion (here m is used as the harmonic number). thus n is not the number of different biases, but is the number of different gratings, which all may have a different bias. however, a number of different gratings can also have the same bias (but different substrate position and different local overlay), as long as there is a sufficient number of different biases for the model to be solved over the substrate where the model is applied. the gratings can both be in the scribe-lane and in the die. the scribe-lane gratings possibly have k m -values (where the m here stands for the k 0 , k 1 , k 2 , etc in the harmonic sine series) that are different from the in-die gratings, because processing and layers maybe slightly different. separation into k m(scribe) and k m(in-die) in the model can take that into account when both fitting in the same modeling step. embodiments of the present invention use fast read-out of a large number of (ultra) small targets and then solve the measured information for the model-parameters over the field rather than locally at each measurement site (substrate location at which targets are placed). the large number of gratings or targets allows for the extraction of more than one overlay and more than one k-value. furthermore, noise averaging occurs by solving at once for the model parameters. in the discussion of fig. 7 , a first assumption was that the k m -values (m=0, 1, 2, . . . ) are constant over the substrate locations for which the model parameters are solved. solvers exist to solve for such a multi-parameter system. these may be models such as least-squares non-linear, trust-region, levenberg-marquardt, etc. such as may be used in the scanners and steppers to correct for overlay and grid deformations, so that one can directly feedback the scatterometer measured model parameters into the scanners. however, this assumption will in the general case not always be correct, due to local stack and etch variations from processing. in an embodiment, this is solved by floating the k m coefficients, for example as function of radius on the wafer substrate, which although possibly increasing the confidence interval, leads to improved accuracy of determined overlay. in a different embodiment, the coefficients can be considered constant over part of a die or field on the wafer, therefore not floated over such a part, however varying somewhat between neighboring die or field parts. some potential advantages of one or more embodiments of the present invention include: overlay is determined more accurately with bga correction and higher harmonics non-linearity included. intrinsic target asymmetry contributions to the overlay are reduced. higher-order terms are taken into account in the asymmetry versus overlay relation, which improves linearity of dark-field diffraction-based metrology. by averaging over many small targets or gratings, and calculating the model parameters as a “single” step per field, the noise on the measurement is averaged out. also, printing errors (e.g., line edge roughness) and wafer errors are averaged out. while the target structures described above are metrology targets specifically designed and formed for the purposes of measurement, in other embodiments, properties may be measured on targets which are functional parts of devices formed on the substrate. many devices have regular, grating-like structures. the terms ‘target grating’ and ‘target structure’ as used herein do not require that the structure has been provided specifically for the measurement being performed. in association with the physical grating structures of the targets as realized on substrates and patterning devices, an embodiment may include a computer program containing one or more sequences of machine-readable instructions describing a methods of producing targets on a substrate, measuring targets on a substrate and/or analyzing measurements to obtain information about a lithographic process. this computer program may be executed for example within unit pu in the apparatus of fig. 3 and/or the control unit lacu of fig. 2 . there may also be provided a data storage medium (e.g., semiconductor memory, magnetic or optical disk) having such a computer program stored therein. where an existing metrology apparatus, for example of the type shown in fig. 3 , is already in production and/or in use, the invention can be implemented by the provision of updated computer program products for causing a processor to perform the modified step s 6 and so calculate overlay error with reduced sensitivity to feature asymmetry. the program may optionally be arranged to control the optical system, substrate support and the like to perform the steps s 2 -s 5 for measurement of asymmetry on a suitable plurality of target structures. although specific reference may have been made above to the use of embodiments of the invention in the context of optical lithography, it will be appreciated that the invention may be used in other applications, for example imprint lithography, and where the context allows, is not limited to optical lithography. in imprint lithography a topography in a patterning device defines the pattern created on a substrate. the topography of the patterning device may be pressed into a layer of resist supplied to the substrate whereupon the resist is cured by applying electromagnetic radiation, heat, pressure or a combination thereof. the patterning device is moved out of the resist leaving a pattern in it after the resist is cured. the terms “radiation” and “beam” used herein encompass all types of electromagnetic radiation, including ultraviolet (uv) radiation (e.g., having a wavelength of or about 365, 355, 248, 193, 157 or 126 nm) and extreme ultra-violet (euv) radiation (e.g., having a wavelength in the range of 5-20 nm), as well as particle beams, such as ion beams or electron beams. the term “lens”, where the context allows, may refer to any one or combination of various types of optical components, including refractive, reflective, magnetic, electromagnetic and electrostatic optical components. the foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying knowledge within the skill of the art, readily modify and/or adapt for various applications such specific embodiments, without undue experimentation, without departing from the general concept of the present invention. therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. it is to be understood that the phraseology or terminology herein is for the purpose of description by example, and not of limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guidance. the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. it is to be appreciated that the detailed description section, and not the summary and abstract sections, is intended to be used to interpret the claims. the summary and abstract sections may set forth one or more but not all exemplary embodiments of the present invention as contemplated by the inventor(s), and thus, are not intended to limit the present invention and the appended claims in any way. the present invention has been described above with the aid of functional building blocks illustrating the implementation of specified functions and relationships thereof. the boundaries of these functional building blocks have been arbitrarily defined herein for the convenience of the description. alternate boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed. the foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying knowledge within the skill of the art, readily modify and/or adapt for various applications such specific embodiments, without undue experimentation, without departing from the general concept of the present invention. therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. it is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guidance. the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
|
115-681-714-775-585
|
US
|
[
"WO"
] |
G01N21/65,G01K11/32,G01J5/60,G01J3/12,G01J3/44,G01J5/0802,G01J5/0806,G01J5/10
| 2022-02-14T00:00:00 |
2022
|
[
"G01"
] |
system and method for temperature profiling with raman scattering
|
the invention is directed to a system and method for temperature profiling based on using raman scattering spectral shape changes that occur with temperature and the concentration of one or more components. in the case of water, as an example, raman scattering spectral shape changes that occur with temperature and salinity are used. raman scattering from liquid or solid water can be used to provide a temperature profile as a function of water depth/range without requiring contacting the water or air containing the water. a raman spectrum can be analyzed to determine the molecule in the water that is responsible for the spectrum. raman scattering is an inelastic process where the raman scattered photons have a different frequency than the incident photon. the amount of the frequency shift depends upon the characteristics of the scattering medium. the invention is able to observe the raman scattering from multiple ranges simultaneously.
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l/we claim: 1. a system for determining vibrational raman spectra of water at multiple depths, comprising: a collimated light source configured to illuminate a body of water, wherein collimated light from the light source is at least partially scattered by the water so as to generate scattered light directed out of the body of water; a light receiving element configured to collect the scattered light directed out of the body of water; at least one dispersing element configured to disperse the collected scattered light to generate at least a raman spectrum; at least one detector array configured to receive and detect at least the raman spectrum resulting from the dispersed scattered light; and a processing circuit operatively connected to the detector array and configured at least to generate at least a temperature profile with respect to depth of the body of water in response to the raman spectrum resulting from the dispersed scattered light, wherein the scattered light directed out of the body of water is scattered in response to characteristics of the body of water or air including at least one of depth, temperature, water salinity , water freshness, water phase, and other substances with emissions that can be detected within the spectral range of the instrument. 2. a system according to claim 1, further comprising: a bandpass filter configured to receive the scattered light and to reduce the background illumination therefrom. 3. a system according to claim 1, further comprising: an image plane configured to receive the raman spectrum resulting from the dispersed scattered light generated by the dispersing element, wherein the detector element is operatively connected to receive the dispersed scattered light imaged on the image plane. a system according to claim 3, further comprising: an optical lens assembly configured to receive and focus the dispersed light from the dispersing element onto the image plane. a system according to claim 1, wherein the processing circuit includes a display operatively connected and configured to at least generate a graphical representation of the temperature profile with respect to depth of the body of water in response to the raman. a method for remote sensing of water temperature at different ranges by analysis of the raman spectra emitted by different ranges, comprising the steps of: providing a raman spectra detecting device including at least a collimated light source configured to illuminate a body of water, a dispersing element configured to disperse scattered light, and a detector array; directing the collimated light source at the body of water so as to generate light scattered by and directed out of the body of water; receiving and dispersing the scattered light in the dispersing element to generate a raman spectrum; detecting the raman spectrum resulting from the dispersed scattered light; generating at least a temperature profile of the body of water in response to the raman spectrum resulting from the dispersed scattered light, wherein the scattered light directed out of the body of water is scattered in response to characteristics of the body of water including at least one of depth, temperature, water salinity, water freshness, water phase, and other constituent concentrations. a method according to claim 6, wherein the step of generating at least a temperature profile of the body of water includes determining temperatures at the different ranges by simultaneous measurement of raman spectra from each depth in the water column. a method according to claim 6, wherein the step of generating at least a temperature profile of the body of water includes determining temperatures at the different ranges by simultaneous measurement of raman spectra and incorporating supplemental information from external sources. a method according to claim 6, wherein the step of generating at least a temperature profile of the body of water or trace amounts of water in air includes determining temperatures at the different ranges by a form of analytical or numerical or machine learning solutions. a system for determining vibrational raman spectra of a fluid medium at multiple depths, comprising: a collimated light source configured to illuminate a body of fluid medium, wherein collimated light from the light source is at least partially scattered by the fluid medium so as to generate scattered light directed out of the body of fluid medium; a light receiving element configured to collect the scattered light directed out of the body of fluid medium; at least one dispersing element configured to disperse the collected scattered light to generate at least a raman spectrum; at least one detector array configured to receive and detect at least the raman spectrum resulting from the dispersed scattered light; and a processing circuit operatively connected to the detector array and configured at least to generate at least a temperature profile with respect to depth of the body of fluid medium in response to the raman spectrum resulting from the dispersed scattered light, wherein the scattered light directed out of the body of fluid medium is scattered in response to characteristics of the body of fluid medium or air including at least one of depth, temperature, concentration of a component in the fluid medium, fluid medium freshness, fluid medium phase, and other substances with emissions that can be detected within the spectral range of the instrument. a system according to claim 10, further comprising: a bandpass filter configured to receive the scattered light and to reduce the background illumination therefrom. a system according to claim 10, further comprising: an image plane configured to receive the raman spectrum resulting from the dispersed scattered light generated by the dispersing element, wherein the detector element is operatively connected to receive the dispersed scattered light imaged on the image plane. a system according to claim 12, further comprising: an optical lens assembly configured to receive and focus the dispersed light from the dispersing element onto the image plane. a system according to claim 10, wherein the processing circuit includes a display operatively connected and configured to at least generate a graphical representation of the temperature profile with respect to depth of the body of fluid medium in response to the raman. a method for remote sensing of a temperature of a fluid medium at different ranges by analysis of the raman spectra emitted by different ranges, comprising the steps of: providing a raman spectra detecting device including at least a collimated light source configured to illuminate a body of fluid medium, a dispersing element configured to disperse scattered light, and a detector array; directing the collimated light source at the body of fluid medium so as to generate light scattered by and directed out of the body of fluid medium; receiving and dispersing the scattered light in the dispersing element to generate a raman spectrum; detecting the raman spectrum resulting from the dispersed scattered light; generating at least a temperature profile of the body of fluid medium in response to the raman spectrum resulting from the dispersed scattered light, wherein the scattered light directed out of the body of fluid medium is scattered in response to characteristics of the body of fluid medium including at least one of depth, temperature, concentration of a component in the fluid medium, fluid medium freshness, fluid medium phase, and other constituent concentrations. a method according to claim 15, wherein the step of generating at least a temperature profile of the body of fluid medium includes determining temperatures at the different ranges by simultaneous measurement of raman spectra from each depth in the fluid medium column. a method according to claim 15, wherein the step of generating at least a temperature profile of the body of fluid medium includes determining temperatures at the different ranges by simultaneous measurement of raman spectra and incorporating supplemental information from external sources. a method according to claim 15, wherein the step of generating at least a temperature profile of the body of fluid medium or trace amounts of fluid medium in air includes determining temperatures at the different ranges by a form of analytical or numerical or machine learning solutions.
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system and method for temperature profiling with raman scattering i. background of invention scope of the invention [0001] raman scattering from fluid mediums (i.e., liquid or gas), whether the medium is in liquid gaseous or even solid form, such as liquid or solid water, can be used to provide a temperature profile as a function of the depth of the fluid medium without requiring contacting the fluid medium. the invention described herein is able to observe the raman scattering from multiple depths simultaneously. summary of the prior art [0002] thermometers, thermistors, and thermocouples have all been used to measure the temperature of water, as an example, but they must contact the water to make a temperature measurement. noncontact infrared systems can measure water temperature without contacting the water by measuring the infrared light emitted from the water's surface. however, infrared measurements are limited to the surface because the of the high absorption of water at the infrared wavelengths. measurements at the near infrared wavelengths are not practical as the black body radiation spectrum drops off so rapidly that there is not enough signal to make reliable measurements. contact and non-contact temperature measurement systems also lack the ability to simultaneously measure other environmental parameters of interest such as phase state of the fluid or concentrations of other fluids or gases of interest. ii. summary of the invention [0003] this invention is based on knowing how the raman scattering spectral shape changes with temperature and the concentration of components in the fluid medium. in particular, using water as an example, the invention is based on raman scattering spectral shape changing with temperature and salinity. data on the salinity of the water of interest (i.e., freshwater or saltwater) is provided by the user. raman scattering is an inelastic process where the raman scattered photons have a different frequency than the incident photon. the amount of the frequency shift depends upon the characteristics of the scattering medium. a raman spectrum can be analyzed to determine the molecule that is responsible for the spectrum. [0004] instruments that utilize raman scattering typically operate at shorter wavelengths when compared to the infrared sensors due to an increase in raman scattering efficiency with shorter incident wavelengths. in an embodiment used for measuring water, as an example, the laser wavelength is 405 nm and is close to the peak water transmission allowing one to see further into the water. in this embodiment, the laser beam and receiving optics are arranged so that the object plane is angled so that it is in focus along the image plane, as was first described by scheimpflug and as is well known in the art of optics. iii. brief description of the drawings [0005] the present invention is illustrated in the accompanying drawings, wherein: figure 1 illustrates how the raman spectrum shape changes as the temperature changes; figure 2 shows a sensor schematic; figure 3 is a block diagram showing the operations of an active range resolved raman spectroscopy; figure 4a a cross section of the receiver optics consisting of a field lens, entrance slit, collimator, grating, focusing lens, and camera sensor; figure 4b is a block diagram showing how the collected optical signal is processed into a hyperspectral image; figure 5a shows how the elastic scatter a single line and raman scatter broader area; figure 5b is an image where the dark indicates more signal while the lighter areas have less signal; and figure 5c is an example where the spectroscopy can capture the raman spectra in addition to the fluorescent or absorption spectra. iv. description of the preferred embodiment [0006] the embodiments of the present invention will be described hereinbelow in conjunction with the above-described drawings. in addition, the embodiments will be described using water as the example fluid medium, though other fluid mediums, whether they be in their liquid, gas or solid forms, are equally applicable to the present invention. accordingly using water as the example, the change in the liquid water raman spectrum for temperatures of 20° c and 3° c with illumination by a laser emitting at 405 nm is shown in figure 1. in calculating the raman spectral shape, the water's salinity or freshness must be included in the mathematical characterization of the raman spectrum so as to fit to a specific temperature uniquely. [0007] the shape of the spectrum can indicate the phase of the water and if the air temperature is known can indicate if the liquid water is in a supercritical state. as the temperature changes the water spectrum, which is typically considered a superposition of multiple emission peaks of unequal intensities, transitions from a spectrum where emission peaks corresponding to water in a monomer form at higher liquid temperatures to a spectrum where the emission peak originating from water molecules in a polymer solid form e.g. ice. water vapor raman emission occurs at shorter wavelengths near the liquid/solid water raman spectrum. thus by measurement of the spectrum the user can match the spectrum to that of water of a specific phase and temperature. [0008] a schematic of the raman temperature sensor 10 according to the present invention is shown in figure 2. the light source is a laser 100 that outputs a nearly collimated laser beam 110. the laser beam 110 illuminates the water 200 where most of the light is transmitted, wherein some of the laser beam is scattered by the water 200. in the scattered laser beam light, changes in the energy of the photons occur at different levels; some photon energies do not change even after scattering. thus, there are two components of photons with different energy levels in the scattered light 120. specifically, the light scattered by the raman effect produces photons that are both higher in energy and lower in energy. the lower energy photons are referred to as stokes and the higher energy photons are referred to as anti-stokes. the raman temperature sensor 10 according to the present invention uses the stokes component as it is stronger than the anti-stokes. [0009] in operation, the raman temperature sensor 10 collects data on multiple raman spectra resulting from light scattered from different depths simultaneously, while the light from the laser 100 is directed through the volume of the water 200. as illustrated in figure 2, the light scattered from a point along the laser beam 110 (i.e., at a particular depth) travels through and out of the water, and then encounters a bandpass filter 130 of the raman temperature sensor 10 that is used to reduce the background illumination. the filtered scattered light then goes through a dispersing element 140 where the light is dispersed to produce a raman spectrum. the lens 150 focuses the dispersed light onto an image plane 170. a more detailed diagram describing the principle of operation of the sensor and the receiver collection optics are shown in figures 3 and 4, respectively. [0010] a detector array 160, such as a camera or other similar optical device, is physically offset from the light source and positioned to be able to view a length of the focused light that passes through the lens 150 on the image plane 170. the focused light that reaches the image plane 170 is elastic scattering 180 that is imaged through the dispersing element 140, such as a transmission grating, which disperses the light orthogonal to the direction of light beam propagation before being focused by the lens 150. as represented in figure 2, the elastic scatter 180 represents the scattered laser energy detected by the raman temperature sensor 10 that does not undergo any change in the energy of the scattered photons. [0011] figure 5a shows how the elastic scattering 180 that reaches the image plane 170 from the dispersing element 140 would be graphically translated by a processing circuit 220 connected to receive data signals from the image plane 170 and then shown on a display 240. specifically, the signal from elastic scattering 180 resulting from the particular depth and light scattering through the water that is detected on the image plane 170 produces an image of the beam in the water column in one area of the detector array 160. that image is represented by the heavy line on the left of figure 3a. the box outlined by the dashed line shows how the raman emission 190 appears separated from the elastic scattering 180 on the detector array image plane 170. each row in the image pertains to a unique distance from the camera, which enables the raman emission 190 to be analyzed independently for each depth in the field of view and the corresponding temperature calculated. [0012] figure 5b shows an actual image of the elastic scatter 180 and the raman scatter 190. in this image, the intensity is represented in the reverse, wherein a brighter section appears darker, and the lower signal level is lighter. the elastic scatter 180 appears to be wider than the raman scatter 190 image because it is so much stronger than the raman signal that it appears to be wider. however, the spectrum of the laser is much narrower than the raman scatter bandwidth. [0013] figure 5c shows when configured to span a larger spectral range than that corresponding to water alone, the instrument can measure the emission of other raman and fluorescence wavelengths for the quantification of other trace gas or liquid components mixed in the volume being measured. these spectral features can be measured simultaneously with the water measurements provided the spectral range of the instrument spans those emission features corresponding to a gas of interest such as oxygen. [0014] although the present invention has been fully described in connection with the preferred embodiment thereof with reference to the accompanying drawings, it is to be noted that various changes and modifications will be apparent to those skilled in the art. such changes and modifications are to be understood as included within the scope of the present invention as defined by the appended claims unless they depart therefrom.
|
119-889-738-910-778
|
US
|
[
"US"
] |
B60P1/43,B60P1/26,B62D33/03,E05F11/04
| 2007-10-18T00:00:00 |
2007
|
[
"B60",
"B62",
"E05"
] |
cargo door/ramp lift assist system
|
a lift assist system for cargo door ramps of trucks and trailers or other pivotal closures which includes a spring assembly containing a compressible spring element which is compressed when a cargo door is moved into an open position. as the compressible spring is compressed it stores up kinetic energy that is released to assist in lifting the cargo door is moved into a closed position.
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1 . a lift assist system for a cargo door ramp that comprises: a door ramp; a hinge that pivotally connects the door ramp to a support structure; at least one spring assembly fixed to the support structure and containing a compressible spring element; and a cable coupled between the door ramp and spring assembly whereby when the door ramp is pivoted into an open position the cable compresses the spring in the spring assembly and when the door ramp is pivoted into a closed position, kinetic energy stored in the compressed spring assists in closing the door ramp. 2 . a lift assist system for a cargo door ramp according to claim 1 , further comprising a pulley system through which the cable is coupled between the door ramp and spring assembly. 3 . a lift assist system for a cargo door ramp according to claim 1 , wherein the pulley system comprises two or more pulleys. 4 . a lift assist system for a cargo door ramp according to claim 1 , wherein the at least one spring assembly is provided at or vertically below the hinge. 5 . a lift assist system for a cargo door ramp according to claim 1 , wherein the spring assembly comprises a housing that houses the compressible spring element. 6 . a lift assist system for a cargo door ramp according to claim 1 , wherein the door ramp comprises a vehicle door. 7 . a lift assist system for a cargo door ramp according to claim 1 , wherein the door ramp comprises a trailer door. 8 . a lift assist system for a cargo door ramp according to claim 1 , wherein the support structure comprises a body, frame or chassis of a vehicle. 9 . a lift assist system for a cargo door ramp according to claim 8 , wherein the vehicle comprises a motorized vehicle. 10 . a lift assist system for a cargo door ramp according to claim 1 , wherein the at least one spring assembly is fixed below the support structure. 11 . a lift assist system for a cargo door ramp according to claim 2 , wherein the pulley system includes a pulley support that is mounted to a horizontal structure of the support structure. 12 . a lift assist system for a cargo door ramp according to claim 2 , wherein the pulley system includes a pulley support that is mounted to a vertical structure that is coupled to the support structure. 13 . a lift assist system for a pivotal closure that comprises: a pivotal closure; a hinge that pivotally connects the pivotal closure to a support structure so that the pivotal closure pivots downward into an open position and upward to a closed position; at least one spring assembly fixed to the support structure and containing a compressible spring element; and a cable coupled between the pivotal closure and spring assembly whereby when the pivotal closure is pivoted into an open position the cable compresses the spring in the spring assembly and when the pivotal closure is pivoted into a closed position, kinetic energy stored in the compressed spring assists in closing the pivotal closure. 14 . a lift assist system for a pivotal closure according to claim 13 , further comprising a pulley system through which the cable is coupled between the pivotal closure and spring assembly. 15 . a lift assist system for a pivotal closure according to claim 13 , wherein the pulley system comprises two or more pulleys. 16 . a lift assist system for a pivotal closure according to claim 13 , wherein the spring assembly comprises a housing that houses the compressible spring element. 17 . a lift assist system for a pivotal closure according to claim 13 , wherein the support structure comprises a portion of a vehicle. 18 . a lift assist system for a pivotal closure according to claim 13 , wherein support structure comprises a portion of a trailer. 19 . a lift assist system for a pivotal closure according to claim 17 , wherein support structure comprises a body, frame or chassis of a vehicle. 20 . a lift assist system for a pivotal closure according to claim 13 , wherein support structure comprises a portion of a non-mobile assembly.
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related applications the present application is based upon and claims priority under 35 u.s.c. §120 to u.s. provisional patent application ser. no. 60/981,047, filed oct. 18, 2007, the complete disclosure of which is hereby expressly incorporated herein by reference. technical field the present invention relates to vehicles and trailers that carry various types of cargo that is typically loaded and unloaded with the use of a ramp. more particularly, the present invention is directed to a lift assist system for vehicles and trailers that have cargo door that pivot downward and function as loading/unloading ramps. background art there are numerous vehicles that are used to haul cargo ranging from commercial fleets of trucks, step vans, panel trucks and the like to do-it-yourself rental trucks that consumers can rent to move or haul various items. in addition there are various types of trailers that are used to haul cargo ranging from semi trailers, to trailers that are used to haul recreational vehicles such as snowmobiles, all terrain vehicles (atv), person watercraft, motorcycles and the like. in many instances a ramp is used to load and unload cargo from such vehicles and trailers. removable ramps are common and are either stored within the cargo compartment of the vehicle or trailer and unload for use and loaded after use. some vehicles provide for ramps that are stored under the cargo compartment. in other instances, the rear or cargo door of the vehicles and trailers can be pivoted downward and used as a ramp; however, it can be difficult, especially in the case of large, heavy cargo doors, for an individual to lift the cargo door back into its closed position. lift assist systems have been developed extensively for pickup truck tailgates as exemplified by u.s. pat. no. 3,336,070 to jackson, u.s. pat. no. 4,143,904 to cooper et al., u.s. pat. no. 5,358,301 to konchan et al., u.s. pat. no. 5,988,724 to wolda, u.s. pat. no. 6,637,796 to westerdale et al., u.s. pat. no. 6,769,729 to bruford et al., u.s. pat. no. 6,793,263 to bruford et al., u.s. pat. no. 6,796,592 to austin, u.s. pat. no. 6,846,030 to koehler et al., u.s. pat. no. 6,874,837 to bruford et al., and u.s. pat. no. 6,905,156 to miller et al. and u.s. patent application publication nos. 2004/0178651 to austin and 2005/0194808 to austin. lift assist systems that have been designed and developed for pickup tailgates are generally not suitable or adaptable for used in conjunction with ramps that are used in conjunction with cargo vehicles and trailers. in this regard, pickup truck tailgates are generally hollow which allows for the lift assist systems to be housed therein, dimensionally constrained only by the cavity within the hollow tailgates. in addition, pickup tailgates are relatively short, perhaps being only about two feet tall so there is not much of a moment arm about the axis of pivot of a tailgate. also, pickup truck tailgates are only pivoted about 90 degrees between a vertical position and a horizontal position (in which they are supported by various linkage brackets). the present invention provides for lift assist systems for use with door ramps of trucks and trailers which allows the free end of the door ramps of such vehicles and trailers to move assistedly back and forth between a vertical position and an inclined position between which positions the door ramps pivots through a obtuse angle of greater than 90 degrees so that the free end of the door ramp rests on the ground. disclosure of the invention according to various features, characteristics and embodiments of the present invention which will become apparent as the description thereof proceeds, the present invention provides a lift assist system for a cargo door ramp that includes: a door ramp; a hinge that pivotally connects the door ramp to a support structure; at least one spring assembly fixed to the support structure and containing a compressible spring element; and a cable coupled between the door ramp and spring assembly whereby when the door ramp is pivoted into an open position the cable compresses the spring in the spring assembly and when the door ramp is pivoted into a closed position, kinetic energy stored in the compressed spring assists in closing the door ramp. the present invention also provides a lift assist system for a pivotal closure that includes: a pivotal closure; a hinge that pivotally connects the pivotal closure to a support structure so that the pivotal closure pivots downward into an open position and upward to a closed position; at least one spring assembly fixed to the support structure and containing a compressible spring element; and a cable coupled between the pivotal closure and spring assembly whereby when the pivotal closure is pivoted into an open position the cable compresses the spring in the spring assembly and when the pivotal closure is pivoted into a closed position, kinetic energy stored in the compressed spring assists in closing the pivotal closure. brief description of drawings the present invention will be described with reference to the attached drawings which are given as non-limiting examples only, in which: fig. 1 a schematic view of the rear of a truck that includes a lift assist system according to one embodiment of the present invention with the door ramp in a closed position. fig. 2 a schematic view of the rear of a truck that includes a lift assist system of fig. 1 with the door ramp in a ramp position. fig. 3 a cut away schematic view of the rear of a truck of fig. 1 with the door ramp in a closed position. fig. 4 a cut away schematic view of the rear of a truck of fig. 2 with the door ramp in a ramp position. fig. 5 is a cut away schematic view of the rear of a truck with a door ramp in a closed position according to another embodiment of the present invention. fig. 6 is a cut away schematic view of the rear of a truck of fig. 5 with the door ramp in a ramp position. fig. 7 is a top cut away schematic view of the rear of a truck of fig. 5 with the door ramp in a ramp position. best mode for carrying out the invention the present invention is directed to lift assist systems for vehicles and trailers that have cargo doors that pivot downward and function as loading/unloading ramps. the term “door ramp” is used herein because the doors of the present invention function both as doors and as ramps. the bottoms of the door ramps are pivotally coupled to a stationary portion of the vehicle or trailer so that their upper or free ends can pivot between a closed position and an inclined position in which the free end can rest on the ground. the door ramps are secured in their closed positions by any suitable latch or catch mechanism. when in their closed positions, the door ramps function as doors to close, cover or seal the rear opening of a cargo compartment of a vehicle or trailer. when in their inclined positions, the door ramps function as inclined ramps along which one can carry, wheel, push, drive or otherwise transfer various types of cargo into and out of the cargo compartment. typically the door ramps are solid, non-hollow panels. however, the door ramps can be hollow composite structures so long as they are sturdy or otherwise reinforced sufficiently to support the weight of cargo while it is loaded and unloaded across the door ramps (in their inclined positions). the door ramps can include any suitable handles, straps, etc. required or desired to manually move the door ramps between their closed and inclined positions. it is also within the scope of the present invention to provide an electric or hydraulic mechanism to move the door ramps between their closed and inclined positions. the lift assist systems of the present invention are mounted between the body, frame or other solid structure of the vehicles or trailers and the door ramps. the lift assist systems include a spring assembly and a pulley system that couples a cable between the spring mechanism and a bracket that is attached to the door ramps. the spring mechanism can be attached to the body, frame or other solid structure of the vehicles or trailers in a position in which it does not interfere with loading or unloading cargo. the bracket is attached to the door ramp at a solid or reinforced portion of the door ramp. the bottom of the door ramp is pivotally coupled to the body, frame or other solid structure of the vehicle or trailer by two or more hinges through which the pivot axis of the door ramp extends. as the door ramp is moved from its closed position to its inclined position, the cable attached to the bracket is pulled through the pulley system so that the opposite end of the cable pulls against a spring element in the spring assembly and compresses the spring element. the resulting force (i.e. kinetic energy) that is built up and stored in the compressed spring is subsequently used to assist in raising the door ramp into its closed position. the invention will now be described in detail with reference made to the drawings in which common reference numerals have been used to identify similar elements when practical to simplify the description. fig. 1 a schematic view of the rear of a truck that includes a lift assist system according to one embodiment of the present invention with the door ramp in a closed position. the portion of the truck shown in fig. 1 includes a frame or chassis 1 to which an axle (not shown) having wheels (not shown) is coupled in a conventional manner. a door ramp 2 is shown in its closed position at the very rear of the truck in fig. 1 . the door ramp 2 extends horizontally between the opposed sides and vertically between the top and bottom of the rear of the truck in a conventional manner. it is noted that a similar door ramp 2 could be provided for a trailer rather than a truck according to the present invention. the door ramp 2 is pivotally coupled to the frame or chassis 1 of the truck by one or more conventional hinges 3 so that the door ramp 2 can pivot between the closed position depicted in fig. 1 and a ramp position (see fig. 2 ) in which the top of the door ramp 2 rests on the ground and the door ramp 2 extends at an inclined angle downward from the frame or chassis 1 at the rear of the truck. the door ramp 2 can be a solid panel that can be made from any suitably strong material, including wood, metals, composites, laminates, etc. alternatively, the door ramp 2 can be a hollow structure or hollow composite structure. in either case the door ramp 2 can be reinforced externally or internally to support the weight of cargo while it is loaded and unloaded across the door ramp 2 . for example, a support frame can extend at least around the periphery of the door ramp 2 . it is to be understood that the door ramp 2 can include any suitable handles, straps, etc. required or desired to manually move the door ramp 2 between its closed and inclined ramp positions. in fig. 1 the visible elements of the lift assist system include the housing 4 of the spring assembly 5 , the pulley system which includes a pulley 6 on the end of the spring assembly 5 , and intermediate pulley 7 mounted on a pulley support 8 a bracket 9 that is fastened to the cargo door 2 and a cable 10 that connects between the spring assembly 5 and bracket 9 . it is noted that one end of the cable 10 is pivotally attached to bracket 9 as shown. in the configuration depicted in fig. 1 the cargo door 2 is in its closed position and the length of the cable 10 between the spring assembly 5 and bracket 9 is short. fig. 2 a schematic view of the rear of a truck that includes a lift assist system of fig. 1 with the door ramp in a ramp position. when the door ramp 2 is opened as shown in fig. 2 the normally top portion of the door rests on the ground so that the door ramp 2 is inclined as depicted. as the door ramp 2 pivots downward about hinge(s) 3 cable 10 is pulled so that the length of the cable 10 between the spring assembly 5 and bracket 9 is extended as shown. also the end of cable 10 that is attached to bracket 9 pivots with respect to bracket 9 as can be seen by comparing figs. 1 and 2 . fig. 3 a cut away schematic view of the rear of a truck of fig. 1 with the door ramp in a closed position. as shown in fig. 3 , the housing 4 of the spring assembly 5 houses a spring element 11 . one end of the spring element 11 rests against an end of the housing 4 . the opposite end of the spring element 11 is caught or secured to a plate 12 that is coupled to an end of cable 10 . as cable 10 is pulled (when the door ramp 2 is lowered), the end of the cable that is coupled to plate 12 pulls plate 12 against spring element 11 so as to compress spring element 11 within housing 4 . fig. 4 a cut away schematic view of the rear of a truck of fig. 2 with the door ramp in a ramp position. as shown in fig. 4 , when the door ramp 2 is opened and in the ramp position, spring element 11 is compressed by the pulling force applied thereto by plate 12 which in turn is pulled by cable 10 . as a result, force is generated and stored up in spring element 11 . this forced that is generated and stored up in spring element 11 can be released and used to assist in lifting the door ramp 2 to its closed position. further, as the door ramp 2 is pivoted into the open position, the force generated and stored up in spring element 11 helps stabilize the door ramp by effectively reducing the weight thereof while supporting the weight. as show in figs. 3 and 4 , the end of cable 10 in housing 4 is coupled to plate 12 by a mechanism that allows for adjustment of the force of the spring applied to and created by cable 10 . in this regard, the embodiment shown includes a threaded member 13 that is attached the end of cable 10 and extends through a hole in plate 12 . a complementary threaded member 14 , e.g. a nut is threadedly coupled to threaded member 13 on the opposite side of plate 12 . in this configuration the position of the complementary threaded member 14 can be adjusted along threaded member 13 so as to adjust the force of the spring element 11 applied to and created by cable 10 . plate 12 needs to be configured or fixed with respect to housing 4 so that plate 12 will not rotate with threaded member 14 . in one embodiment housing 4 and plate 12 are made so that they have square cross-sectional shapes. the housing 4 can have a generally cylindrical shape or a shape that has a circular or non-circular area with either or both ends being closed or covered with removable covers to prevent dirt and debris from entering the spring assembly 5 . whereas one spring element 11 is shown in the figures, it is to be understood that more than on spring element can be provided in housing 4 . the pulley system shown includes a pulley 6 attached to an end of housing 4 and a pulley 7 attached to pulley support 8 . pulley support 8 is mounted to a portion of the truck (or trailer) such as the bed or floor of a cargo area or the body, frame, chassis or other solid structure associated with the truck (or trailer). it is to be understood that the spring assembly 5 can be located at any convenient location on, in or under a truck (or trailer) and that the pulley system can include any number of pulleys and pulley supports as desired to couple the cable 10 to bracket 9 and the spring assembly 5 . it is also within the scope of the present invention to pivotally couple one end of the spring assembly 5 to the truck (or trailer). according to one embodiment, a spring assembly 5 is provided on either side of a truck or trailer and a bracket 9 is provide on either side of the door ramp 2 in a location that minimizes interference with loading and unloading cargo. it is also possible to provide one spring assembly 5 that can be located centrally or in some other suitable position and a dual cable system that connects to two brackets 9 provided on opposite sides of the door ramp 2 . other configurations that include one, two or more spring assemblies could also be used according to the present invention. fig. 5 is a cut away schematic view of the rear of a truck with a door ramp in a closed position according to another embodiment of the present invention. fig. 6 is a cut away schematic view of the rear of a truck of fig. 5 with the door ramp in a ramp position. fig. 7 is a top cut away schematic view of the rear of a truck of fig. 5 with the door ramp in a ramp position. in the embodiment of the invention shown in figs. 5-7 the pulley supports 8 are mounted on vertical door frame members 15 in accordance with the discussion above that the pulley supports 8 can be mounted to any other solid structure associated with the truck (or trailer). the pulley supports 8 in figs. 5-7 include two brackets or plates 16 , one of which is attached to a vertical frame member 15 , by welding or other suitable means. a pulley 17 is provided between the two brackets or plates 16 on a pin or rod 18 about which the pulley 17 is free to rotate. the pulley supports 8 and brackets 9 in all the embodiments are configured and aligned so that the cable 10 can freely move without binding. for example, the pulley supports 8 in the embodiment of the invention shown in figs. 5-7 position the pulleys 17 slightly inward from the vertical frame members 15 so that the pulleys 17 are substantially aligned with brackets 9 . also as can be understood from all the figures, the pulley supports 8 are configured and positioned so that there is a clearance between the pulley supports 8 and the brackets 9 when the door ramps 2 are in their closed positions. in the embodiment of the invention shown in figs. 5-7 , pulleys 6 can also be mounted to a lower portion of the vertical frame members 15 or any sturdy structure such as the chassis or frame of the truck (or trailer). during the course of the present invention it was determined that for heavy doors, friction within the hinge(s) 3 , particularly adjacent the ends wherein the cables 10 pull between the pulleys 17 and door ramps 2 , could add resistance to lifting the door ramps 2 . this friction can be reduced by including bearings within at least the ends of the hinges 3 . such bearings could be made of any suitable bearing material such as brass or other known metallic bearing material or polymer material. it was also determined that although roller bearings were suitable for use with the pulleys, using pin or needle bearings significantly reduced friction in the pulleys. it is to be understood that the configuration of the overall lift assist system of the present invention, including the placement and alignment and number of the various elements, including the pulleys, pulley supports, brackets, and spring housing can be varied from the non-limiting examples provided in the figures. the position of the pulley support(s) can be adjusted as desired to change the forces acting on the cable(s) and spring elements. likewise the position of the brackets 9 can be adjusted as desired to change the forces acting on the cable(s) and spring elements. although one spring element 11 is shown in the housing 4 , it is possible according to the present invention to include more than on spring element 11 within housing 4 in a stacked manner. it is also possible according to the present invention to use a bank of spring elements in a common or separate housing which would allow for installation in tighter space restrictions. it is noted that while reference is generally made to a truck in figs. 1-7 , as discussed above, the lift assist system of the present invention can also be incorporated into a trailer, or even a non-mobile or stationary storage container or structure having a door or end or side that opens by pivoting downwardly. although the present invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention and various changes and modifications can be made to adapt the various uses and characteristics without departing from the spirit and scope of the present invention as described above.
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120-184-654-348-840
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US
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[
"US",
"CN"
] |
F24F12/00,F24F11/00,F24F11/02,F24F7/08,F24F11/64,F24F11/89
| 2015-11-11T00:00:00 |
2015
|
[
"F24"
] |
outside air distribution system
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an energy recovery ventilator (“erv”) connecting an outside air intake to an outside air supply for an ahu or an interior space. the erv includes a damper for controlling the outside air inflow to the ahu or the interior space. a humidity sensor and a temperature sensor can be mounted within the inlet air path proximate the damper to monitor the temperature and humidity of outside air approaching the erv through the outside air intake. the damper can be positioned to according to the measured temperature and humidity of the outside air to control the outside air being supplied to the ahu or the interior space.
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1 . an energy recovery ventilator, comprising: an outer housing defining an interior chamber, the outer housing comprising: an indoor input for receiving an indoor air outflow into the interior chamber, an indoor output through which the indoor air outflow exits the interior chamber, the indoor output being fluidly connected to an indoor outlet for venting the indoor air outflow to an outside space, an outdoor input for receiving an outdoor air inflow into the interior chamber for intermixing with the indoor air outflow, the outdoor input being fluidly connected to an outdoor inlet for receiving the outdoor air inflow from the outside space, and an outdoor output through which the outdoor air inflow exits the interior chamber; and a damper assembly coupled to the outdoor input, the damper assembly having a moveable damper plate for selectively obstructing the outdoor input to control the outdoor air inflow into the interior chamber. 2 . the energy recovery ventilator of claim 1 , further comprising: an environmental sensor array comprising at least one of a temperature sensor, a humidity sensor, and a combination thereof mounted proximate the outdoor input for monitoring conditions of the outdoor air inflow approaching the outdoor input; wherein the damper plate is positioned to obstruct the outdoor input if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. 3 . the energy recovery ventilator of claim 2 , further comprising: an outdoor air supply fan operable to draw the outdoor air inflow into the interior chamber at a predetermined flow rate. wherein the outdoor air supply fan is disabled if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. 4 . the energy recovery ventilator of claim 3 , wherein the outdoor air supply fan is operable to draw fresh outdoor air through ducting proximate the sensor array before measurement of conditions of the outdoor airflow. 5 . the energy recovery ventilator of claim 1 , wherein the damper assembly further comprising: a duct section for rotatably receiving the damper plate, wherein the duct section can comprise an engagement tab for rotatably coupling the duct section and the damper plate to the outer housing. 6 . the energy recovery ventilator of claim 1 , wherein at least one of the indoor input, the indoor output, the outdoor input, and the outdoor output comprises an extended mount, the extended mount further comprising: a port portion shaped to interface with ducting and defining an opening; an insulation collar encircling the port portion and configured to engage the ducting; wherein the insulation collar comprises an insulation material limiting thermal bridging between the port portion and the insulation collar. 7 . the energy recovery ventilator of claim 1 , further comprising: at least one l-shaped bracket including a housing portion and a support portion extending transversely from the housing portion: wherein the housing portion is configured to receive a fastener to couple the l-shaped bracket to the outer housing and the support portion is configured to receive a second fastener to couple the l-shaped bracket to a support structure. 8 . a ventilation system, comprising: an energy recovery unit comprising an outer housing defining an interior chamber, the outer housing comprising: an indoor input for receiving an indoor air outflow into the interior chamber, an indoor output through which the indoor air outflow exits the interior chamber, the indoor output being fluidly connected to an indoor outlet for venting the indoor air outflow to an outside space, an outdoor input for receiving an outdoor air inflow into the interior chamber for intermixing with the indoor air outflow, the outdoor input being fluidly connected to an outdoor inlet for receiving the outdoor air inflow from the outside space, an outdoor output through which the outdoor air inflow exits the interior chamber, and a damper assembly coupled to the outdoor input, the damper assembly having a moveable damper plate for selectively obstructing the outdoor input to control the outdoor air inflow into the interior chamber. 9 . the ventilation system of claim 8 , wherein the indoor input is operably connected at least one of an interior space and an air handling unit for receiving the indoor air outflow. 10 . the ventilation system of claim 8 , wherein the outdoor output is operably connected at least one of an interior space and an air handling unit for providing the outdoor air inflow. 11 . the ventilation system of claim 10 , wherein the indoor air outflow intermixes with the outdoor air inflow to condition the outdoor air inflow before the outdoor air inflow exits the interior chamber. 12 . the ventilation system of claim 8 , the energy recovery ventilator further comprising: an environmental sensor array comprising at least one of a temperature sensor, a humidity sensor, and a combination thereof mounted proximate the outdoor input for monitoring conditions of the outdoor air inflow approaching the outdoor input; wherein the damper plate is positioned to obstruct the outdoor input if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. 13 . the ventilation system of claim 12 , the energy recovery ventilator further comprising: an outdoor air supply fan operable to draw the outdoor air inflow into the interior chamber at a predetermined flow rate. wherein the outdoor air supply fan is disabled if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. 14 . the ventilation system of claim 13 , wherein the outdoor air supply fan is operable to draw fresh outdoor air through ducting proximate the sensor array before measurement of conditions of the outdoor airflow. 15 . the ventilation system of claim 8 , the energy recovery ventilator further comprising: a duct section for rotatably receiving the damper plate, wherein the duct section can comprise an engagement tab for rotatably coupling the duct section and the damper plate to the outer housing. 16 . the ventilation system of claim 8 , wherein at least one of the indoor input, the indoor output, the outdoor input, and the outdoor output comprises an extended mount, the extended mount further comprising: a port portion shaped to interface with ducting and defining an opening; an insulation collar encircling the port portion and configured to engage the ducting; wherein the insulation collar comprises an insulation material limiting thermal bridging between the port portion and the insulation collar. 17 . the ventilation system of claim 8 , further comprising: at least one l-shaped bracket including a housing portion and a support portion extending transversely from the housing portion; wherein the housing portion is configured to receive a fastener to couple the l-shaped bracket to the outer housing and the support portion is configured to receive a second fastener to couple the l-shaped bracket to a support structure. 18 . a method of controlling an outdoor air inflow into an interior space, comprising: providing an energy recovery ventilator defining an interior chamber and including an indoor input, an indoor output, an outdoor input, and an outdoor output; providing an indoor air outflow into interior chamber through the indoor input, wherein the indoor air inflow exits the interior chamber through the indoor output; providing an outdoor air inflow into interior chamber through the outdoor input to intermix with the indoor air outflow, wherein the outdoor air inflow exits the interior chamber through the outdoor output; moving a damper plate positioned proximate the outdoor input to selectively obstruct the outdoor input to limit outdoor air inflow into the interior chamber. 19 . the method of claim 18 , further comprising: monitoring temperature and humidity of the outdoor air inflow approaching the outdoor input; and moving the damper plate to obstruct the outdoor input to limit outdoor air inflow when at least one of the temperature and the humidity of the outdoor air inflow exceeds a predetermined threshold. 20 . the method of claim 19 , further comprising: operating an outdoor air supply fan to draw the outdoor air inflow through the outdoor input; wherein the outdoor air supply fan is disabled when at least one of the temperature and the humidity of the outdoor air inflow exceeds the predetermined threshold.
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claim of priority this patent application claims the benefit of priority, under 35 u.s.c. section 119(e), to vermette et al. u.s. patent application ser. no. 62/253,976, entitled “outside air distribution system,” filed on nov. 11, 2015 (attorney docket no. 5992.092prv) and vermette et al. u.s. patent application ser. no. 62/291,936, entitled “outside air distribution system,” filed on feb. 5, 2016 (attorney docket no. 5992.092pv2), the benefit of priority of each of which is claimed hereby, and each of which are incorporated by reference herein in its entirety. technical field this document pertains generally, but not by way of limitation, to an energy recovery ventilator configured for selectively controlling outdoor air inflow into an air handler unit. background air distribution systems for home ventilation in hot and humid climates, such as the southern us, typically include an air handler unit (“ahu”) for processing recirculated air through an interior space. typically, ducting extending from an outside port is connected to the ahu to introduce outside air into the air handler unit, where a damper in the ducting controls the entry of exterior air into the ahu. in these “air cycler” or central fan integrated systems, a controller powers the damper to control entry of outside air into the ahu and correspondingly the interior space. humidity sensors can be used to control the operation of the damper to control the humidity of the air entering and within the ahu by controlling the outside air supply to the ahu. for example, interior humidity sensors can be set to close the damper and prevent outside air from entering the ahu if the interior air humidity is too high or exterior humidity sensors can be set to close the damper if the outside air humidity differs significantly from the interior air humidity. the humidity sensors are typically set for a “worst-case” humidity scenario to close the damper whenever the outside air humidity deviates from a relatively narrow humidity band, which can cause the damper to be closed too frequently and for prolonged time periods. the frequent and prolonged closure of the damper reduces ventilation of the interior space with fresh outside air, which can cause the air in the internal space to become stale or retain pollutants within the internal space. also, the fixed thresholds for humidity sensors can hamper the effectiveness of air distribution systems as weather conditions change throughout the year. the humidity limit must be reset manually with each changing season to account for changing temperature and humidity. if the humidity limit is not properly reset, the ventilation entering the ahu can have excessive or insufficient humidity resulting in the formation of condensation within the ducting of the ahu or other problems. for example, the relatively high humidity during the hot seasons can cause the damper to be closed more frequently and for prolonged time periods, which can increase pollutant retention within the interior. similarly, interior humidity frequently increases during shoulder seasons (seasons where heating and cooling are not required) and summer, which can cause the damper to be closed more frequently thereby increasing the risk of condensation and mold formation within the ahu. an added complication is that the humidity sensors must be separately installed, operably connected to the controller or damper, and powered thereby presenting considerable installation challenges and increasing maintenance of the humidity sensors and the overall system. exterior temperature sensors can also be provided to control operation of the damper. the exterior temperature sensors can limit outside air entering the ahu if the outside temperature is too hot or cold. however, if the exterior temperature sensors are improperly mounted, the measurements of the temperature sensors can be influenced by heat sources or not be indicative of the actual air temperature entering into the ahu. while the humidity sensors and temperature sensors can selectively provide ventilation to the ahu, the remote locations of the humidity sensors and temperature sensors from the damper can complicate installation of the sensors and the overall system. also, the presets of the temperature and humidity sensors must be properly set and regularly updated to avoid condensation build up within the ahu, which can result in mold or other detrimental effects. overview the present inventors have recognized, among other things, that a problem to be solved can include the installation and maintenance challenges and potential inaccuracies of remotely positioned humidity and temperature sensors for controlling airflow into an ahu or directly to an interior space. in an example, the present subject can provide a solution to this problem, such as by an energy recovery ventilator (“erv”) connecting an outside air intake to an outside air supply for an ahu or an interior space. the erv having a damper that can be selectively closed to control the airflow from an outside space passing through the outside air intake into the outside air supply for the ahu or the interior space. a humidity sensor and a temperature sensor can be mounted within the inlet air path proximate the damper to monitor the temperature and humidity of outside air approaching the erv through the outside air intake. the damper can be selectively positioned to according to the measured temperature and humidity of the outside air to control the outside air supplied to the ahu or the interior space. the proximity of the temperature and humidity sensors more accurately measures the conditions of the outside air supplied. the proximity of the temperature and humidity sensors also simplifies installation of the erv within a new ventilation system or retrofitting of an existing ventilation system. in an example, the erv can also include an air supply fan for drawing air through the outside air intake into the erv and pushing air through the outside air supply for the ahu or the interior space. the operation of the air supply fan can be linked to the position of the damper such that the air supply fan and the damper can be operated based on the temperature and humidity of the outside air approaching the erv. in an example, the air supply fan and the damper can be operated to provide a maximum air flow through the outside air intake for a predetermined time period to purge the air within the air supply fan. the purging of air within the outside air intake with fresh outside air improves the accuracy of the temperature and humidity measurements thereby providing more accurate control of outside air supply to the ahu or interior space. in an example, the erv can include a controller configured to collect humidity and temperature information from the sensors and controlling the damper and the air supply fan. the controller can be programmed with a dew point limit level corresponding to a relative humidity of 100% for a given outside air temperature. the controller adjusts the damper and the air supply fan to shut off the outside air supply or reduce the outside air flow when the humidity sensor detects humidity in the incoming outside air for temperature measured by the temperature sensor. the dew point limit level prevents the formation of condensation within the erv, connected ducting, and/or ahu, which can cause mold to form within the ventilation system. the controller can alter the dew point limit level based on the temperature measured by the temperature sensor. if the temperature exceeds a cooling threshold corresponding to a temperature where a cooling system of the ahu will be operated to reduce the temperature of the outside air, the controller can increase the dew point limit to compensate for dehumidification capacity of the cooling system. if the temperature of the outside air measured by the temperature sensor is lowered, the dew point limit level can be adjusted by the controller to correspond to the temperature of the outside air to limit condensation as the outside air temperature drops due to night time or changing seasons. this overview is intended to provide an overview of subject matter of the present patent application. it is not intended to provide an exclusive or exhaustive explanation of the present subject matter. the detailed description is included to provide further information about the present patent application. brief description of the drawings in the drawings, which are not necessarily drawn to scale, like numerals may describe similar components in different views. like numerals having different letter suffixes may represent different instances of similar components. the drawings generally illustrate, by way of example, but not by way of limitation, various embodiments discussed in the present document. fig. 1 is a perspective view of an energy recovery ventilator according to an example of the present disclosure. fig. 2 is a top view of an energy recovery ventilator with a removed access door to access an interior chamber of the energy recovery ventilator according to an example of the present disclosure. fig. 3 is a perspective view of a ventilation system that directly feeds outdoor air inflow into an interior space according to an example of the present disclosure. fig. 4 is a perspective view of a ventilation system that feeds outdoor air inflow into an air handling unit according to an example of the present disclosure. fig. 5 is a perspective view of a ventilation system that receives an airflow from an air handling unit to condition an outdoor air inflow being fed directing into an interior space according to an example of the present disclosure. fig. 6a is a perspective view of a damper assembly according to an example of the present disclosure. fig. 6b is a perspective view of an energy recovery ventilator having a damper assembly according to an example of the present disclosure. fig. 7a is a partial cross-sectional top view of an energy recovery ventilator according to an example of the present disclosure. fig. 7b is a partial cross-sectional top view of an extended mount according to an example of the present disclosure. fig. 8a is a perspective view of an extended mount according to an example of the present disclosure. fig. 8b is a front view of the extended mount depicted in fig. 8a . fig. 8c is a side cross-sectional side view of the extended mount depicted in fig. 8c . fig. 9a is a perspective view of an energy recovery ventilator having attached l-shaped brackets wherein the energy recovery ventilator is oriented such that the l-shaped brackets extend downward according to an example of the present disclosure. fig. 9b is a perspective view of an l-shaped bracket mounted to an outer housing of an energy recovery ventilator according to an example of the present disclosure. fig. 9c is a perspective view of an energy recovery ventilator mounted a ceiling truss according to an example of the present disclosure. fig. 10a is a perspective view of an energy recovery ventilator having attached l-shaped brackets wherein the energy recovery ventilator is oriented such that the l-shaped brackets extend upward according to an example of the present disclosure. fig. 10b is a perspective view of an l-shaped bracket mounted to an outer housing of an energy recovery ventilator according to an example of the present disclosure. fig. 10c is a perspective view of an energy recovery ventilator mounted a ceiling according to an example of the present disclosure. fig. 10d is a partial cross-sectional perspective view of an energy recovery ventilator mounted a ceiling according to an example of the present disclosure. fig. 11a is a partial cross-sectional front view of energy recovery ventilator mounted within a ceiling according to an example of the present disclosure. fig. 11b is a perspective view of an access door according to an example of the present disclosure. fig. 12 is a representative control schematic according to an example of the present disclosure. detailed description as depicted in figs. 1-5 , a ventilation system 20 , according to an example of the present disclosure, can include an energy recovery ventilator (“erv”) 22 having an outer housing 24 defining an interior chamber 26 . the outer housing 24 can include an indoor input 28 and an indoor output 30 fluidly connected to an exterior outlet 32 . an indoor air outflow can exit an interior space through the indoor input 28 and exit through the exterior outlet 32 after passing through the interior chamber 26 . as depicted in fig. 5 , in an example, the indoor input 28 can be operably connected to an air handling unit (“ahu”) 40 for receiving a portion of the airflow circulating through the ahu 40 . the outer housing 24 can include an outdoor output 34 and an outdoor input 36 fluidly connected to an exterior inlet 38 . the outdoor output 34 can be fluidly connected to the ahu 40 as depicted in fig. 4 or an interior outlet 42 as depicted in fig. 3 . as illustrated in fig. 3 , an outdoor air inflow can enter through the exterior inlet 38 and pass through the interior chamber 26 such that the outdoor air inflow intermixes with the indoor air outflow within the interior chamber 26 . the indoor air outflow conditions the outdoor air inflow prior to entering the ahu 40 or the interior space through the interior outlet 42 . the ahu 40 can be a heating, ventilating, and air-conditioning system for conditioning or heating air within the interior space. the ahu 40 can be configured to recirculate air within the interior space; condition the outdoor air inflow before providing the conditioned airflow to the interior space; provide a portion of the airflow circulating through the ahu 40 to the indoor input 28 ; and intermix the outdoor air inflow with the recirculating airflow and condition the combined airflow. the indoor air outflow can condition the outdoor air inflow within the erv 22 to alter the temperature, humidity, and other environmental conditions of the outdoor airflow to more closely approximate the desired conditions within the interior space. the erv 22 reduces the energy demands of the ahu 40 to fully alter the outdoor air inflow to have the desired temperature and humidity. as depicted in figs. 1-2 and 6a-6b , the erv 22 can include a damper assembly 44 positioned at the outdoor input 36 . the damper assembly 44 can include a damper plate 46 rotatable within a duct section 48 defining an opening through which air can pass through the duct section 48 . as illustrated in fig. 6b , the damper plate 46 can be rotated to alter the effective area of the opening defined by the duct section 48 to restrict the outdoor air inflow or close off the duct section 48 to prevent the outdoor air inflow from entering the interior chamber 26 . the damper plate 46 can be positioned by a motor, a magnet, or another mechanism for rotating the damper plate 46 within the duct section 48 . as depicted in fig. 6a , in an example, the duct section 48 can include at least one engagement tab 50 such that the duct section 48 can be rotated into engagement with the outer housing 24 to couple the damper assembly 44 to the outer housing 24 . as depicted in fig. 2 , in an example, the erv 22 can include an outdoor air supply fan 52 operable to draw the outside air inflow in through the outdoor input 36 and out through the outdoor output 38 . the air supply fan 52 is configured to operate with the obstruction of the outdoor input 36 provided by the damper assembly 44 to control the airflow rate of the outdoor air inflow. in an example, the erv 22 can include an indoor air supply fan 54 operable to draw the inside air outflow in through the indoor input 28 and out through the indoor output 30 . the outdoor air supply fan 52 and the indoor air supply fan 54 can be operated simultaneously to draw the outdoor air inflow and the indoor air outflow through the interior chamber 26 for conditioning of the outdoor air inflow. as depicted in figs. 7a-b and 8 a-c, at least one of the indoor input 28 , the indoor output 30 , the outdoor input 36 , and the outdoor output 38 can include an extended mount 56 four coupling ducting to the erv 22 . the extended mount 56 can include a port portion 58 shaped to interface with ducting and defining an opening through which airflow can flow. in an example, the port portion 58 can comprise a metal such that the port portion 58 is sufficiently rigid to couple with the ducting. the portion 58 can include a skirt portion 60 that can be inserted through the indoor input 28 , the indoor output 30 , the outdoor input 36 , or the outdoor output 38 of the outer housing 24 for coupling the port portion 58 to the outer housing 24 . as depicted in figs. 8a-c , in an example, the extended mount 56 can include an insulation collar 62 encircling the port portion 58 for engaging an interior surface of the ducting to couple the ducting the extended mount 56 . the insulation collar 62 can comprise an insulating material such that the insulation collar 62 prevents or minimizes thermal bridging between the ducting and the port portion 58 , which can cause condensation to form within the opening of the port portion 58 . in an example, the insulation collar 62 can include a flange 64 extending radially outward from the insulation collar 62 . the flange 64 can be shaped and positioned to engage an end of the ducting being coupled to the port portion 58 . as depicted in figs. 9a-c , 10 a-d, and 11 a-b, the erv 22 can include at least one l-shaped bracket 66 for mounting the erv 22 to a support structure such as, but not limited to support studs, ceiling trusses, walls, or ceilings. the l-shaped bracket 66 can include a housing portion 68 and a support structure 70 extending transversely to the housing portion 68 . the housing portion 68 can define at least one opening for receiving a fastener for coupling the l-shaped bracket 66 to the outer housing 24 . the support portion 70 can include at least one opening for receiving a fastener for coupling the l-shaped bracket 66 to the support structure. the l-shaped bracket 66 can be mounted to the outer housing 24 of the erv 22 in different configurations to permit mounting of the erv 22 to different support structures. as illustrated in figs. 9a-c and 10 a-d, in one configuration, the housing portion 68 can be coupled to a sidewall of the outer housing 24 such that the support portion 70 is oriented parallel to a top side of the outer housing 24 (as shown in figs. 10a-d ) or a bottom side of the outer housing 24 (as shown in figs. 9a-c ). in this configuration, the outer housing 24 can be mounted to a ceiling or a ceiling truss below the outer housing 24 . as illustrated in fig. 11a , in another configuration, the housing portion 68 can be coupled to a front wall or a rear wall of the outer housing 24 such that the support portion 70 is oriented to a sidewall of the outer housing 24 . in this configuration, the outer housing 24 can be coupled to support structures on either side of the outer housing 24 such as wall or wall studs. in an example, the housing portion 68 can be mounted to the outer housing 24 such that the support portion 70 extends outward from the erv 22 to compensate for spacing between support structures larger than the dimensions of the outer housing 24 . as depicted in figs. 11a-b , the outer housing 24 of the erv 22 can include an access opening for accessing the internal chamber 26 . the erv 22 can include an access panel 72 that can be coupled to the outer housing 24 to cover the access opening and enclose the interior chamber 26 . the access panel 72 can include a contour frame 74 defining an edge portion extending outward from the outer housing 24 for gripping the access panel 72 when mounted to the outer housing 24 . the access panel 72 can include at least one spring latch 76 for coupling the access panel 70 to the outer housing 24 . as illustrated in fig. 11a , the outer housing 24 can be mounted ceiling such that the outer housing 24 extends through an opening in a ceiling from an interior side of the ceiling, where the access panel 70 is mounted to the outer housing 24 on an exterior side of the ceiling. in this configuration, the access panel 72 can be decoupled from the outer housing 24 to access the interior chamber 26 without decoupling the outer housing 24 from the support structure. in an example, the erv 22 can be operably linked to a sensor array comprising at least one of a humidity sensor, a temperature sensor, and a combination thereof positioned proximate the outdoor input 36 for monitoring conditions of the outdoor air entering through the outdoor input 36 . the erv 22 can include a controller for receiving the measurements from the sensors and operably controlling at least one of the damper assembly 44 and the outdoor air supply fan 52 based on the sensor measurements. the controller can close the damper assembly 44 and shut off the outdoor air supply fan 52 if the humidity and/or the temperature conditions of the outdoor air inflow exceeds predetermined thresholds. in an example, the outdoor air supply fan 52 can be operated to flush the ducting proximate the sensors to draw fresh outdoor air into the ducting. the flushing of the ducting avoids inaccuracies that can result from the measurement of stale air within the ducting, which can have different temperature and humidity conditions that of the outside air. as illustrated in fig. 12 , in an example, the controller can be programmed to control the damper assembly 44 and the outdoor air supply fan 52 according to a dew point function defining a dew point limit level for a measured outside air temperature. the controller can adjust the damper assembly 44 and the outdoor air supply fan 52 to shut off or reduce the outside air inflow when the humidity sensor detects a humidity ratio (mass of water vapor in the outside air to the mass of dry air) exceeding the dew point limit level. the dew point limit level prevents the formation of condensation within the erv, connected ducting, and/or ahu, which can cause mold to form within the ventilation system. in this configuration, the controller can regulate the outdoor air inflow conditions and being supplied to the ahu 40 or indoor space without additional sensors. as illustrated in fig. 12 , the dew point function can be changed depending on a set relative humidity (e.g. 25%, 50%, 75%, 100%). in an example, the erv 22 can include a manual controller 78 for setting the relative humidity. as illustrated in fig. 12 , in an example, the controller can be programmed with condensation zones where the controller deviates from the dew point function if outdoor air inflow conditions are within temperature and humidity ranges. if the temperature and humidity ratios are within predetermined temperature and humidity ranges, the controller can adjust the damper assembly 44 and the outdoor air supply fan 52 to shut off or reduce the outside air inflow. for example, if the outdoor air inflow has a temperature exceeding 77° f. and a humidity ratio exceeding 0.02, the outdoor air inflow can be reduced, or shut off as cooling functions of the ahu 40 are often operated at this temperature. the combined cooling features of the ahu 40 and high temperature and humidity of the outdoor air inflow can result in the formation of condensation within the ahu 40 . in another example, if the outdoor air inflow has a temperature between 58° f. and 73° f. and a humidity ratio exceeding 0.02, the outdoor air inflow can be reduced or shut off as the temperature corresponds to a “shoulder” season (e.g. spring or fall) where neither the heating nor cooling functions of the ahu 40 are operated. the controller can maintain the humidity ratio of the outdoor air inflow below a predetermined threshold to avoid the formation of condensation that are normally controlled by the heating and cooling functions of the ahu 40 . various notes & examples example 1 is an energy recovery ventilator, comprising: an outer housing defining an interior chamber, the outer housing comprising: an indoor input for receiving an indoor air outflow into the interior chamber, an indoor output through which the indoor air outflow exits the interior chamber, the indoor output being fluidly connected to an indoor outlet for venting the indoor air outflow to an outside space, an outdoor input for receiving an outdoor air inflow into the interior chamber for intermixing with the indoor air outflow, the outdoor input being fluidly connected to an outdoor inlet for receiving the outdoor air inflow from the outside space, and an outdoor output through which the outdoor air inflow exits the interior chamber; and a damper assembly coupled to the outdoor input, the damper assembly having a moveable damper plate for selectively obstructing the outdoor input to control the outdoor air inflow into the interior chamber. in example 2, the subject matter of example 1 optionally includes an environmental sensor array comprising at least one of a temperature sensor, a humidity sensor, and a combination thereof mounted proximate the outdoor input for monitoring conditions of the outdoor air inflow approaching the outdoor input; wherein the damper plate is positioned to obstruct the outdoor input if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. in example 3, the subject matter of example 2 optionally includes an outdoor air supply fan operable to draw the outdoor air inflow into the interior chamber at a predetermined flow rate. in example 4, the subject matter of example 3 optionally includes wherein the outdoor air supply fan is operable to draw fresh outdoor air through ducting proximate the sensor array before measurement of conditions of the outdoor airflow. in example 5, the subject matter of any one or more of examples 1-4 optionally include wherein the damper assembly further comprising: a duct section for rotatably receiving the damper plate, wherein the duct section can comprise an engagement tab for rotatably coupling the duct section and the damper plate to the outer housing. in example 6, the subject matter of any one or more of examples 1-5 optionally include wherein at least one of the indoor input, the indoor output, the outdoor input, and the outdoor output comprises an extended mount, the extended mount further comprising: a port portion shaped to interface with ducting and defining an opening; an insulation collar encircling the port portion and configured to engage the ducting; wherein the insulation collar comprises an insulation material limiting thermal bridging between the port portion and the insulation collar. in example 7, the subject matter of any one or more of examples 1-6 optionally include at least one l-shaped bracket including a housing portion and a support portion extending transversely from the housing portion; wherein the housing portion is configured to receive a fastener to couple the l-shaped bracket to the outer housing and the support portion is configured to receive a second fastener to couple the l-shaped bracket to a support structure. example 8 is a ventilation system, comprising: an energy recovery unit comprising an outer housing defining an interior chamber, the outer housing comprising: an indoor input for receiving an indoor air outflow into the interior chamber, an indoor output through which the indoor air outflow exits the interior chamber, the indoor output being fluidly connected to an indoor outlet for venting the indoor air outflow to an outside space, an outdoor input for receiving an outdoor air inflow into the interior chamber for intermixing with the indoor air outflow, the outdoor input being fluidly connected to an outdoor inlet for receiving the outdoor air inflow from the outside space, an outdoor output through which the outdoor air inflow exits the interior chamber, and a damper assembly coupled to the outdoor input, the damper assembly having a moveable damper plate for selectively obstructing the outdoor input to control the outdoor air inflow into the interior chamber. in example 9, the subject matter of example 8 optionally includes wherein the indoor input is operably connected at least one of an interior space and an air handling unit for receiving the indoor air outflow. in example 10, the subject matter of any one or more of examples 8-9 optionally include wherein the outdoor output is operably connected at least one of an interior space and an air handling unit for providing the outdoor air inflow. in example 11, the subject matter of example 10 optionally includes wherein the indoor air outflow intermixes with the outdoor air inflow to condition the outdoor air inflow before the outdoor air inflow exits the interior chamber. in example 12, the subject matter of any one or more of examples 8-11 optionally include the energy recovery ventilator further comprising: an environmental sensor array comprising at least one of a temperature sensor, a humidity sensor, and a combination thereof mounted proximate the outdoor input for monitoring conditions of the outdoor air inflow approaching the outdoor input; wherein the damper plate is positioned to obstruct the outdoor input if the monitored conditions of the outdoor air inflow exceed a predetermined threshold. in example 13, the subject matter of example 12 optionally includes the energy recovery ventilator further comprising: an outdoor air supply fan operable to draw the outdoor air inflow into the interior chamber at a predetermined flow rate. in example 14, the subject matter of example 13 optionally includes wherein the outdoor air supply fan is operable to draw fresh outdoor air through ducting proximate the sensor array before measurement of conditions of the outdoor airflow. in example 15, the subject matter of any one or more of examples 8-14 optionally include the energy recovery ventilator further comprising: a duct section for rotatably receiving the damper plate, wherein the duct section can comprise an engagement tab for rotatably coupling the duct section and the damper plate to the outer housing. in example 16, the subject matter of any one or more of examples 8-15 optionally include wherein at least one of the indoor input, the indoor output, the outdoor input, and the outdoor output comprises an extended mount, the extended mount further comprising: a port portion shaped to interface with ducting and defining an opening; an insulation collar encircling the port portion and configured to engage the ducting; wherein the insulation collar comprises an insulation material limiting thermal bridging between the port portion and the insulation collar. in example 17, the subject matter of any one or more of examples 8-16 optionally include at least one l-shaped bracket including a housing portion and a support portion extending transversely from the housing portion; wherein the housing portion is configured to receive a fastener to couple the l-shaped bracket to the outer housing and the support portion is configured to receive a second fastener to couple the l-shaped bracket to a support structure. example 18 is a method of controlling an outdoor air inflow into an interior space, comprising: providing an energy recovery ventilator defining an interior chamber and including an indoor input, an indoor output, an outdoor input, and an outdoor output; providing an indoor air outflow into interior chamber through the indoor input, wherein the indoor air inflow exits the interior chamber through the indoor output; providing an outdoor air inflow into interior chamber through the outdoor input to intermix with the indoor air outflow, wherein the outdoor air inflow exits the interior chamber through the outdoor output; moving a damper plate positioned proximate the outdoor input to selectively obstruct the outdoor input to limit outdoor air inflow into the interior chamber. in example 19, the subject matter of example 18 optionally includes monitoring temperature and humidity of the outdoor air inflow approaching the outdoor input; and moving the damper plate to obstruct the outdoor input to limit outdoor air inflow when at least one of the temperature and the humidity of the outdoor air inflow exceeds a predetermined threshold. in example 20, the subject matter of example 19 optionally includes operating an outdoor air supply fan to draw the outdoor air inflow through the outdoor input; wherein the outdoor air supply fan is disabled when at least one of the temperature and the humidity of the outdoor air inflow exceeds the predetermined threshold. each of these non-limiting examples can stand on its own, or can be combined in any permutation or combination with any one or more of the other examples. the above detailed description includes references to the accompanying drawings, which form a part of the detailed description. the drawings show, by way of illustration, specific embodiments in which the present subject matter can be practiced. these embodiments are also referred to herein as “examples.” such examples can include elements in addition to those shown or described. however, the present inventors also contemplate examples in which only those elements shown or described are provided. moreover, the present inventors also contemplate examples using any combination or permutation of those elements shown or described (or one or more aspects thereof), either with respect to a particular example (or one or more aspects thereof), or with respect to other examples (or one or more aspects thereof) shown or described herein. in the event of inconsistent usages between this document and any documents so incorporated by reference, the usage in this document controls. in this document, the terms “a” or “an” are used, as is common in patent documents, to include one or more than one, independent of any other instances or usages of “at least one” or “one or more.” in this document, the term “or” is used to refer to a nonexclusive or, such that “a or b” includes “a but not b,” “b but not a,” and “a and b,” unless otherwise indicated. in this document, the terms “including” and “in which” are used as the plain-english equivalents of the respective terms “comprising” and “wherein.” also, in the following claims, the terms “including” and “comprising” are open-ended, that is, a system, device, article, composition, formulation, or process that includes elements in addition to those listed after such a term in a claim are still deemed to fall within the scope of that claim. moreover, in the following claims, the terms “first,” “second,” and “third,” etc. are used merely as labels, and are not intended to impose numerical requirements on their objects. method examples described herein can be machine or computer-implemented at least in part. some examples can include a computer-readable medium or machine-readable medium encoded with instructions operable to configure an electronic device to perform methods as described in the above examples. an implementation of such methods can include code, such as microcode, assembly language code, a higher-level language code, or the like. such code can include computer readable instructions for performing various methods. the code may form portions of computer program products. further, in an example, the code can be tangibly stored on one or more volatile, non-transitory, or non-volatile tangible computer-readable media, such as during execution or at other times. examples of these tangible computer-readable media can include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (e.g., compact disks and digital video disks), magnetic cassettes, memory cards or sticks, random access memories (rams), read only memories (roms), and the like. the above description is intended to be illustrative, and not restrictive. for example, the above-described examples (or one or more aspects thereof) may be used in combination with each other. other embodiments can be used, such as by one of ordinary skill in the art upon reviewing the above description. the abstract is provided to comply with 37 c.f.r. §1.72(b), to allow the reader to quickly ascertain the nature of the technical disclosure. it is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. also, in the above detailed description, various features may be grouped together to streamline the disclosure. this should not be interpreted as intending that an unclaimed disclosed feature is essential to any claim. rather, inventive subject matter may lie in less than all features of a particular disclosed embodiment. thus, the following claims are hereby incorporated into the detailed description as examples or embodiments, with each claim standing on its own as a separate embodiment, and it is contemplated that such embodiments can be combined with each other in various combinations or permutations. the scope of the present subject matter should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
|
121-018-639-207-516
|
JP
|
[
"EP",
"JP",
"DE",
"US"
] |
C30B25/02,C30B25/10,C30B25/18,C30B29/06,C30B29/08,H01L21/205
| 1988-11-11T00:00:00 |
1988
|
[
"C30",
"H01"
] |
epitaxial growth process and growing apparatus.
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purpose:to form an si single crystal thin film on a single crystal substrate at a low temperature by using silicon hydride gas and silicon fluoride gas and carrying out the cleaning of a substrate surface and the epitaxial growth of the crystal with ultraviolet irradiation. constitution:a substrate 11 is placed in a vacuum reaction chamber 2 and irradiated with ultraviolet radiation 12 while introducing silicon fluoride gas into the chamber. the natural oxide film is etched by reduction reaction and the surface of the substrate 11 is cleaned by this process. after the cleaning treatment, a gaseous silicon hydride [sinh2n+2 (n is 2, 3 or 4)] and a gaseous silicon fluoride [sinf2n+2 (n is 1, 2...)] are passed through the chamber at the same time. the silicon hydride is decomposed by the reaction excited by ultraviolet light to form an si single crystal thin film on an si or ge single crystal substrate.
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1. a process of epitaxially growing a silicon-germanium single crystal layer on a semiconductor single crystal substrate, comprising the steps of: cleaning the substrate surface by allowing a fluoride gas to flow over the substrate, wherein the fluoride gas is silicon fluoride, germanium fluoride, boron fluoride, arsenic fluoride or phosphorus fluoride; applying ultraviolet light to decompose the fluoride gas; allowing a silicon hydride of the formula si n h 2n + 2 (n = 2, 3, 4), a germanium hydride of the formula ge m h 2m+2 (m = 1, 2, 3), and the fluoride gas to flow simultaneously over the substrate; and decomposing the gases by ultraviolet light excitation, to deposit the layer on the surface of the substrate. 2. a process of epitaxially growing a silicon single crystal layer on a semiconductor single crystal substrate, comprising the steps defined in claim 1, except that neither germanium fluoride nor the germanium hydride is used. 3. a process of epitaxially growing a germanium single crystal layer on a semiconductor single crystal substrate, comprising the steps defined in claim 1, except that neither silicon fluoride nor the silicon hydride is used. 4. a process according to any preceding claim, wherein the substrate is at 250 to 400 ° c during the decomposition step. 5. a process according to any preceding claim, wherein the substrate is silicon or germanium. 6. a process according to any preceding claim, wherein the substrate is maintained at ambient temperature to 500 °c during the cleaning step. 7. a process according to any preceding claim, wherein the ultraviolet light has a wavelength of from 250 to 150 nm. 8. a process according to claim 7, wherein the ultraviolet light is irradiated from a laser or from a high-pressure mercury lamp. 9. apparatus for epitaxially growing a semiconductor single crystal layer on a semiconductor single crystal substrate, comprising: a reactor having a susceptor for said substrate and a window allowing passage of ultraviolet light; an ultraviolet light source; a first inlet pipe for feeding a fluoride gas, which pipe is provided with a spray end portion thereof located above and close to the substrate; and a second inlet pipe for feeding a gas comprising the raw material for the layer, which branches into a first branch pipe having a first valve and joined to the first inlet pipe, and a second branch pipe having a second valve and leading into a region within the reactor not irradiatable with the ultraviolet light.
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background of the invention 1. field of the invention the present invention relates to an epitaxial growing of a semiconductor single crystal layer, and more particularly, to a process of forming an epitaxially grown layer on a single crystal silicon substrate by photo-decomposing a gas raw material with an irradiation of ultraviolet laser light or lamp light, and an apparatus for carrying out the process. the present invention is applied to an epitaxial growth of a silicon (si), germanium (ge) or silicon-germanium (sige) single crystal layer (thin film). 2. description of the related art in a production of semiconductor devices such as bipolar transistors and mos field effect transistors (fets), an epitaxial growth temperature must be lowered when growing a single crystal epitaxial layer of si, ge or sige, to avoid the generation of lattice defects, and variations in the impurity diffusion profile in a single crystal (e.g., si) substrate (wafer), to enable the miniaturization of a semiconductor device, such as a very-large-scale integration (vlsi) device. recently, instead of a thermal decomposition (hydrogen reduction) process having a growing temperature of 950 °c or more, a photo cvd process using a photoexciting reaction has been proposed for an epitaxial growth at a temperature lower than the above-mentioned cvd processes. in this case, the epitaxial growth of, e.g., si, is performed at a temperature of from 600 to 900 ° c. the photo cvd process however, requires a high temperature annealing treatment (at 900 °c or more) in an ultrahigh vacuum or a hydrogen atmosphere, for removing (cleaning) a natural oxide layer formed on the substrate surface prior to the epitaxial growth, and requires an addition of hydrogen gas to prevent the formation of an oxide layer during the epitaxial growth. patent abstracts of japan, vol. 11, no. 273 (c-455) [2720], 4th september 1987, equivalent to jp-a-6278191, discloses a method of forming on a substrate, at up to 300 ° c, a n-type or p-type single crystal thin film, by photolysis, using uv-light, of a mixed gas of hydrogen, a fluorosilane and a silane. when the high temperature annealing treatment for removing the natural oxide layer is applied to a substrate in which impurity-doped (diffused) regions have been formed, the regions (i.e. diffusion profiles) are undesirably expanded. since the use of hydrogen gas is potentially dangerous (e.g. an explosion could occur) in the operation of an epitaxial growth apparatus, it is preferable to avoid the use of hydrogen gas. analogous procedures, additionally using b 2 h 6 and ph 3 or ash 3 , respectively, are disclosed in patent abstracts of japan, vol. 11, no. 273 (c-455) [2720], equivalent to jp-a-6278192 and jp-a-6278193. yamada et al, japanese journal of applied physics; supplement (18th int. conf. on solid state devices and materials, tokyo 1986), 20th-22nd august 1986, pages 217-220, tokyo, japan; discloses the photochemical vapour deposition of single crystal silicon on single crystal si wafers from sih 6 + sih 2 f 2 or sih 4 + sih 2 f 2 + h 2 at a temperature of 100 to 300 °c, using an ultraviolet light source emitting uv-light having a wavelength of 184.9 nm and 253.7 nm. the procedure using si2 h6 + sih 2 f 2 + h 2 and uv light at a wavelength of 184.9 nm is also disclosed by nishida et al, applied physics letters, vol. 49, no. 2, july 1986, pages 79-81, american institute of physics, new york, usa. sih 2 f 2 gas is added in the hydrogen gas to generate sif radicals therefrom at low temperature, 100 to 300 °c; these radicals accelerate the removal of the natural oxide layer. furthermore, the addition of sih 2 f 2 gas to the gas raw material generates sif radicals which prevent the formation of the oxide layer during the epitaxial growth. sih 2 f 2 gas,however, is spontaneously combustible and is potentially more dangerous than hydrogen. summary of the invention according to the present invention, a process of epitaxially growing a silicon-germanium single crystal layer on a semiconductor single crystal substrate, comprises the steps of: cleaning the substrate surface by allowing a fluoride gas to flow over the substrate, wherein the fluoride gas is silicon fluoride, germanium fluoride, boron fluoride, arsenic fluoride or phosphorus fluoride; applying ultraviolet light to decompose the fluoride gas; allowing a silicon hydride of the formula si n h 2n+2 (n = 2, 3, 4), a germanium hydride of the formula ge m h 2m+2 (m = 1, 2, 3), and the fluoride gas to flow simultaneously over the substrate; and decomposing the gases by ultraviolet light excitation, to deposit the layer on the surface of the substrate. according to further aspects of the invention, a silicon or germanium single crystal layer is grown epitaxially on a semiconductor single crystal substrate, by the steps defined above, with the proviso that neither germanium fluoride nor the germanium hydride is used if a silicon single crystal layer is grown, and that neither silicon chloride nor the silicon hydride is used if a germanium single crystal layer is grown. description of the invention preferably, the substrate is at 250-400 °c during the decomposition step. the substrate is preferably silicon or germanium. when the ultraviolet light irradiates the silicon hydride gas (and/or germanium hydride gas), the gas is decomposed to deposit si (and/or ge) on the si or ge substrate, with the result that the si (and/or ge) layer is epitaxially grown. when the ultraviolet light irradiates the fluoride gas of si, ge, b, as and/or p, the gas is decomposed to generate fluoride radicals of sif, gef, bf, asf and/or pf which remove oxide to the inclusion of the oxide in the growing layer during the epitaxial growth period. this oxide is usually generated by a reaction with oxygen remaining within a reactor and is diffused through walls of the reactor and other parts of the apparatus. furthermore, the fluoride radicals can be decomposed to generate elements of si, ge, b, as and p. the elements of si and ge contribute to the growth of the epitaxial layer, and the elements of b, as and p are contained in the epitaxial layer and serve as dopants for determining the conductivity type. the addition of the fluoride gas in the raw material gas in the photo cvd process for epitaxial growth enables the epitaxial temperature to be made lower than that used in a conventional photo cvd process. prior to the above-mentioned epitaxial growth of the si, ge or sige layer, the surface of the semiconductor single crystal substrate should be cleaned, i.e., a natural oxide layer formed on the substrate surface should be removed (etched out) by allowing the above-mentioned fluoride gas to flow over the substrate kept at a temperature of from a room temperature to 500 ° c and by irradiating the ultraviolet light onto the fluoride gas to decompose the gas by to a photoexitation. namely, the decomposition of the fluoride gas generates the fluoride radicals which remove (etch) the natural oxide layer. the silicon fluoride (sif, si 2 fe) gas, germanium fluoride (gef 4 ) gas, boron fluoride (bf 3 ) gas, arsenic fluoride (asf 3 , asfs) gas, and phosphorus fluoride (pf 3 , pfs) gas used instead of the sih 2 f 2 gas are incombustible, and thus are safer than the sih 2 f 2 gas. the germanium fluoride gas should not be used, prior to the epitaxial growth of the si layer, and the silicon fluoride gas should not be used prior to the epitaxial growth of the ge layer. preferably, the ultraviolet light has a wavelength of from 250 to 150 nm, suitable for photoexciting the above-mentioned gases, and is irradiated by a laser or a high pressure mercury lamp. according to the present invention, the fluoride radicals such as sif radicals are utilized in the epitaxial growth and the cleaning of the substrate surface. if the radical generation is interrupted, between the cleaning step and the epitaxial growth step, a natural oxide layer may be formed on the substrate to prevent the epitaxial growth. therefore, in practice, such an interruption must be avoided by continuously feeding the fluoride gas and by adding the raw material hydride gas to the flowing fluoride gas during the epitaxial growth period. since, however, the gas flow rate is usually controlled by a mass flow controller, several seconds must pass before reaching a preset value of the flow rate, from the start of the flow of the raw material hydride gas. taking this time-lag into consideration, the raw material hydride gas is fed at a flow rate larger than the preset value for several seconds from the start of the flow, and as a result, the deposition rate of the semiconductor single crystal layer may be temporarily increased: in the worst case, the epitaxial growth may be hampered. another object of the present invention is to provide an epitaxial growth apparatus by which a procedure from the substrate surface cleaning to the photo cvd epitaxial growth is stably carried out without difficulty. the above-mentioned object is attained by providing an apparatus for epitaxially growing a semiconductor single crystal layer on a semiconductor single crystal substrate,comprising a reactor having a susceptor for said substrate and a window allowing a passage of ultraviolet light; an ultraviolet light source; a first inlet pipe for feeding a fluoride gas, which pipe is provided with a spray end portion thereof located above and close to the substrate; a second inlet pipe for feeding a raw material gas for the layer, which pipe is branched into a first branch pipe having a first valve and joined to said first inlet pipe, and a second branch pipe having a second valve and introduced into a region within the reactor not irradiated with the ultraviolet light. in the apparatus, the spray end portion for feeding the gases used for the cleaning and the epitaxial growth is placed above and close to the substrate, to generate a slight pressure difference between that in the vicinity of the substrate and other regions within the reactor chamber. during the cleaning and epitaxial growth processes, the raw material gas is first fed into the not irradiated region to adjust and stabilize the flow rate thereof, and is then fed to the close vicinity of the substrate together with the fluoride gas, by closing the second valve and simultaneously opening the first valve, whereby a stable photo cvd epitaxial growth is realized. brief description of the drawings the present invention will become more apparent from the description of the preferred embodiments set forth below with reference to the accompanying drawings, in which: fig. 1 is a schematic view of an epitaxial growth apparatus in a photo cvd system according to the present invention; fig. 2 is a schematic sectional view of a hetero-junction bipolar transistor; and fig. 3 is a schematic sectional view of another bipolar transistor description of the preferred embodiments referring to fig. 1, an epitaxial growth apparatus having an improved pipeline system is used for epitaxially growing (depositing, forming) a semiconductor single crystalline layer on an semiconductor single crystal substrate by utilizing a photoexcitation reaction caused by an ultraviolet irradiation in accordance with the present invention. the apparatus comprises a vacuum reactor chamber 2 with a transparent window 1 allowing a passage of ultraviolet light 12, and an ultraviolet light generator 3 (e.g., arf excimer laser, a high pressure mercury lamp or the like). the reactor chamber 2 is communicated to a vacuum exhaust system (e.g., vacuum pump) 4 and is provided with an x-y stage 5, a heating susceptor 6, and a pipe guide 7 for the ultraviolet light within the chamber 2. gas inlet pipes 8 and 9 for feeding an inert gas (e.g., nitrogen (n 2 ) gas) are fixed to the reactor chamber 2. a first inlet pipe 22 for feeding a fluoride gas (e.g., si 2 fe, gef, bf or the like) and having a mass flow controller 23 is set such that a spray end portion 24 thereof is located above and close to a semiconductor substrate (wafer) 11 set on the susceptor 6. the spray end portion 24 is provided with spraying pores distributed in a space corresponding to the size of the substrate 11 and arranged at a position at which it will not obstruct the ultraviolet irradiation. a second inlet pipe 15 for feeding a material hydride gas (e.g., si2 h6 , geh) is provided with a mass flow controller 16 and is branched, downstream of the controller 16, in a first branch pipe 17 with a first valve 19 and a second branch pipe 18 with a second valve 20. the first branch pipe 17 is joined to the first inlet pipe 22, to spray the hydride gas together with the fluoride gas through the spray end portion 24. the end portion of the second branch pipe 18 is open in a region within the reactor chamber 2 not irradiated with the ultraviolet light, to provide a bypass feed of the hydride gas into the reactor chamber 2. example 1 according to the process of the present invention, a si single crystalline layer is formed on a si single crystalline substrate 11 in the following manner. first, the si substrate 11 is placed on the heating susceptor 6, the reactor chamber 2 is then exhausted by the vacuum exhaust system 4 to generate a vacuum and pressure of approximately 0.133 mpa (1 x 10- 6 torr), and nitrogen (n 2 ) gas having a flow rate of 10 sccm is continuously introduced into the reaction chamber 2 through the pipes 8 and 9 to form an inert gas atmosphere having a pressure of 4 torr. the si substrate 11 is heated and kept at a temperature of 400 °c and silicon fluoride (si 2 f 6 ) gas is continuously fed at a flow rate of 15 sccm through the first inlet pipe 22 and the spray end portion 24. under the above-mentioned conditions, an arf excimer laser device 4 as the ultraviolet light generator irradiates a laser ray (wavelength: 193 nm) 12 over the whole surface of the si substrate 11 through a transparent window 1. the laser irradiation is performed for 10 minutes to etch (remove) a natural oxide layer formed on the si substrate surface by a reduction of sif radicals generated from the si 2 fe gas, whereby the surface of the si substrate 11 is cleaned. just before the end of the surface cleaning process, si2 h6 gas as a raw material gas is passed into a not irradiated region within the reactor chamber 2 through the second branch pipe 18 from the second inlet pipe 15, by opening the second valve 20, at a flow rate of 0.2 sccm. at this time, since the si 2 fe gas flows out of the spray end portion 24, the introduced si2 h6 gas does not flow on the si substrate 11. when the flow rate of the si 2 h 6 gas becomes stable, the second valve 20 is closed, and simultaneously the first valve 19 is opened, to feed the si2 h6 gas into the first inlet pipe 22 to flow together with the si 2 f 6 gas onto the si substrate 11. when the si 2 h 6 gas is irradiated with the arf excimer laser ray 12 and decomposed by photo excitation, si is deposited on the cleaned surface of the si substrate to epitaxially grow a si single crystal layer thereon. this epitaxial growth of si after the cleaning forms an si layer having a thickness of approximately 0.4 µm, in 10 minutes. the single crystallizability of the formed si layer is confirmed by an electron channeling pattern (ecp) technique. during the epitaxial growth, it is possible to prevent an inclusion of oxide contaminants (particles) generated by a reaction of si with oxygen diffused out of the walls of the reactor chamber 2 in the growing si layer, by both the reduction effect of sif radicals and the direct reduction effect of ultraviolet irradiation on the oxide particles. the sif radicals are generated not only directly by a photo-decomposition of the ultraviolet light of si 2 f 6 gas but also indirectly by the effect of other radicals generated by the photo-decomposition of si 2 h 6 gas. example 2 in the formation process of the si layer of the above-mentioned example 1, a ge single crystal substrate is used instead of the si single crystal substrate. namely, the cleaning process and the epitaxial growth process are performed under the same conditions as example 1, but the semiconductor material of the substrate is different. as a result, an si single crystal layer is obtained (epitaxially grown). example 3 in the formation process of the si layer of the above-mentioned example 1, a mixture of si 2 h 6 gas (50 vol%) and si 3 h 8 gas (50 vol%) is used instead of si2 h6 gas only, as the raw material gas. in this case, the si single crystal layer is also obtained (epitaxially grown) on the si substrate. example 4 in the formation process of the si layer of example 1, a boron fluoride (bf 2 ) gas is used instead of the si 2 fe gas. in this case, the si single crystal layer is obtained (epitaxially grown) on the si substrate and contains a boron dopant therein, and thus has a p-type conductivity. comparative example a an si layer is formed on a si single crystal substrate under the same conditions as those of the above-mentioned example 1 except that the cleaning process is omitted. in this case, the si substrate is heated at 400 ° c and the si 2 f 6 gas (15 sccm) and si2 h6 gas (0.2 sccm) are simultaneously fed through the spray end portion 24. thereafter, the arf excimer laser ray 12 is irradiated to deposit si and to form a si layer on the si substrate 11. when the formed si layer was examined by the epc technique, it was confirmed that the si layer was not a single crystal layer. example 5 according to the process of the present invention, a ge single crystal layer is formed on a si single crystal substrate by using the apparatus shown in fig. 1, in the following manner. first, the si substrate 11 is placed on the heating susceptor 6, then reactor chamber 2 is the exhausted to reach a pressure of approximately 0.133 mpa (1 x 10- 6 torr), and n 2 gas is continuously fed at a flow rate of 10 sccm into the reaction chamber 2 to form an inert gas atmosphere at a pressure of 533 pa (4 torr). the si substrate 11 is heated and held at a temperature of 250 - 400 °c, and germanium fluoride (gef 4 ) gas is continuously fed at a flow rate of 5 sccm through the spray end portion 24. the arf laser ray 12 is incident on the si substrate 11 through the window 1 to remove a natural oxide layer from the si substrate surface, for 60 minutes. next, geh 4 gas (0.1 sccm) is first fed into a not irradiated region in the reaction chamber 2 through the second branch pipe 18, and then fed into the first inlet pipe 2 to flow geh 4 gas and gef 4 gas over the si substrate 11 through the spray end portion 24 by controlling the first and second valves 19 and 20, as explained in example 1. as a result, geh 4 gas is photo-excited to be compressed, and thus ge is deposited on the cleaned si substrate surface to epitaxially grow a ge single crystal layer having a thickness of approximately 10 nm, in 10 minutes. the single crystallinity of the formed ge layer is conformed by the ecp technique. example 6 in the formation process of ge layer of the above-mentioned example 5, a ge single crystalline substrate is used instead of the si substrate. in this case, the ge single crystal layer is also obtained (epitaxially grown). comparative example b a ge layer is formed on the si substrate under the same conditions as those of example 4, except that the cleaning process is omitted. in this case, the si substrate is heated at 250 - 400 ° c, and the gef 4 gas (5 sccm) and geh 4 gas (0.1 sccm) are simultaneously fed through the spray end portion 24. thereafter, the arf excimer laser ray 12 is irradiated to deposit ge and form the ge layer on the si substrate 11. when the formed ge layer was examined by the epc technique, it was confirmed that the ge layer was not a single crystalline layer. example 7 according to the process of the present invention, an sige single crystal layer is formed on an si single crystal substrate by using the above-mentioned epitaxial growth apparatus, in the following manner. the si substrate 11 is placed on the heating susceptor 6, the reactor chamber 2 is then exhausted, and n 2 gas is continuously fed at a flow rate of 10 sccm into the reactor chamber 2 to form an inert atmosphere at a pressure of 533 pa (4 torr). the si substrate 11 is heated and held at 250 - 400 ° c and a mixed fluoride gas (5 sccm) of si 2 fe gas (50 vol%) and gef 4 gas (50 vol%) is continuously fed through the spray end portion 24. a high pressure mercury lamp 3 irradiates an ultraviolet light 12 on the si substrate 11 through the window 1 to remove a natural oxide layer from the si substrate surface, for 60 minutes. next, a mixed hydride gas (5 sccm) of si 2 h 6 gas (50 vol%) and geh 4 gas (50 vol%) is fed into a not irradiated region through the second branch pipe 18 and then fed into the first inlet pipe 22 to pass the mixed gas of the above-mentioned four gases over the si substrate 11 through the spray end portion 24 by controlling the valves 19 and 20, as explained in example 1. as a result, the hydride gases are photoexcited to be decomposed, whereby si and ge are deposited on the clean si substrate surface to epitaxially grow the sige single crystal layer having a thickness of approximately 10 nm, in 10 minutes. the formed sige layer is confirmed by the epc technique to be a single crystal. comparative example c a sige layer is formed on the si substrate under the same conditions as those of example 7 except that the cleaning process is omitted. the formed sige layer is examined by the ecp technique to confirm that the sige layer is not a single crystal layer. as mentioned above, the cleaning process of the substrate surface and the epitaxial growth process of the si, ge or sige layer are performed at a temperature lower than in a conventional case, by using a specific fluoride gas and hydride gas without hydrogen gas and utilizing ultraviolet irradiation to cause a photoexcitation of the gases. the semiconductor single crystal layer epitaxially grown in accordance with the process of the present invention can be used in semiconductor devices. e.g., bipolar transistors, as shown in figs. 2 and 3. in fig. 2, a hetero-junction bipolar transistor (hbt) comprises an si single crystal collector substrate 26, an sige single crystal base layer 27, and a si single crystal emitter layer 28. the sige layer 27 is epitaxially grown on the si substrate 26 in a similar manner to that of example 7, according to the present invention. the si layer 28 is also epitaxially grown on the sige layer 27, by stopping the feeding of the germanium fluoride gas and germanium hydride gas and by continuously feeding the silicon fluoride gas and silicon hydride gas under the ultraviolet light irradiation. after the formation of the si layer 28, the si layer 28 and the sige layer 27 are selectively etched to form a mesa portion of the si layer 28 and a portion of the sige layer 27, as shown in fig. 2. then suitable insulating layers and electrodes are formed in a conventional manner. in fig. 3, a bipolar transistor comprises an n-type si single crystal collector substrate 31, a p-type si single crystal base layer 32a, and an n-type impurity doped emitter region 33. the si substrate 31 is selectively and thermally oxidized to form a field oxide (si0 2 ) layer 34. then the si layer 32a is epitaxially grown on the si substrate 31 in a similar manner to that of example 1 according to the present invention. in this case, a boron fluoride (bf 2 ) gas is added to the si2 f6 gas for p-type doping, and at the same time, a si polycrystal layer 32b is formed on the oxide layer 34. the si polycrystalline layer 32b is patterned by a conventional sective etching process to form a conductive line for a base electrode. an insulating layer 35 is formed over the whole surface and selectively etched to open an emitter contact hole, and as (or p) ions are doped in the si layer 32a through the emitter contact hole by an ion-implantation process to form the n-type emitter region 33. the insulating layer 35 is selectively etched to open a base contact hole. then a metal (ai-si-cu alloy) is formed over the whole surface and is patterned to form an emitter electrode 36, a base electrode 37, and a collector electrode indicated by a symbol "c".
|
122-886-867-459-375
|
US
|
[
"KR",
"CN",
"BR",
"WO",
"JP",
"US",
"HK",
"EP"
] |
A43B23/02,A43B23/04,A43C1/00,A43B1/04,D04B1/10,D04B1/12,A43B23/16,A43C11/00,A43B23/00,A43B23/07,A43B/,A43C/,D04B/,A43D11/00
| 2011-04-04T00:00:00 |
2011
|
[
"A43",
"D04"
] |
article of footwear having a knit upper with a polymer layer
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an article of footwear (10) has an upper (30) and a sole structure (20)secured to the upper. the upper includes a knitted component (40) and a polymer layer (50). the knitted component is formed of unitary knit construction and extends along a lateral side of the upper, along a medial side of the upper, over a forefoot region of the upper, and around a heel region of the upper. the polymer layer is bonded to the knitted component and may form a majority of an exterior surface of the upper. the polymer layer may be formed from a thermoplastic polymer material.the knitted component (40) includes threads (43) and different tubes (42) positioned inside.
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1. an article of footwear having an upper and a sole structure secured to the upper, the upper comprising: a knitted component formed of unitary knit construction, the knitted component including a tubular structure, the tubular structure comprising a first knitted layer and a second knitted layer that are overlapping and joined along opposite edges to form an unsecured central area of the tubular structure; a strand having a configuration of a one-dimensional material, the strand extending through at least a portion of a length of the unsecured central area of the tubular structure; a polymer layer bonded to the knitted component and forming a majority of an exterior surface of the upper; and wherein the polymer layer infiltrates and bonds to the first knitted layer of the tubular structure and remains unsecured to the second knitted layer of the tubular structure. 2. the article of footwear recited in claim 1 , wherein the knitted component and the polymer layer extend along a lateral side of the upper, along a medial side of the upper, over a forefoot region of the upper, and around a heel region of the upper. 3. the article of footwear recited in claim 2 , wherein the tubular structure is located on the lateral side of the upper and is oriented to extend upward from an area proximal the sole structure, and the strand extends outward from an end of the tubular structure to form a loop that receives a lace. 4. the article of footwear recited in claim 3 , wherein the loop is located between the knitted component and the polymer layer. 5. the article of footwear recited in claim 3 , wherein the knitted component defines an aperture positioned adjacent to the loop, and the lace extends through the aperture. 6. the article of footwear recited in claim 1 , wherein the polymer layer is formed from a thermoplastic polymer material. 7. the article of footwear recited in claim 1 , wherein the polymer layer is a non-woven textile formed from a thermoplastic polymer material. 8. the article of footwear recited in claim 1 , wherein a first area of the knitted component has a first knit type and a second area of the knitted component has a second knit type, the first knit type being different than the second knit type. 9. the article of footwear recited in claim 1 , wherein a first area of the knitted component has a first strand type and a second area of the knitted component has a second strand type, the first strand type being different than the second strand type. 10. an article of footwear having an upper and a sole structure secured to the upper, the upper comprising: a knitted component formed of unitary knit construction and extending along a lateral side of the upper, along a medial side of the upper, over a forefoot region of the upper, and around a heel region of the upper; a plurality of tubular structures disposed on the knitted component, the plurality of tubular structures including a first tubular structure and a second tubular structure disposed on at least one of the lateral side and the medial side of the upper, the first tubular structure and the second tubular structure being disposed adjacent to each other on the same side of the upper; at least one strand located within the knitted component on one of the lateral side and the medial side, the strand extending upward through the first tubular structure from an area proximal the sole structure, the strand extending downward through the second tubular structure towards the area proximal the sole structure, and the strand extending outward from the knitted component between the first tubular structure and the second tubular structure to form one of a lateral loop on the lateral side and a medial loop on the medial side; a lace extending through at least one of the lateral loop and the medial loop; a polymer layer bonded to the knitted component and forming a majority of an exterior surface of the upper; and wherein at least one of the lateral loop and the medial loop are located between the polymer layer and the knitted component. 11. the article of footwear recited in claim 10 , wherein the polymer layer comprises a plurality of apertures that expose portions of the knitted component on the exterior surface of the upper. 12. the article of footwear recited in claim 10 , wherein the polymer layer comprises a polymer resin that has been applied onto a surface of the knitted component. 13. the article of footwear recited in claim 10 , wherein a position of at least one of the lateral loop and the medial loop on the knitted component is secured by the polymer layer. 14. the article of footwear recited in claim 10 , wherein the knitted component defines apertures positioned adjacent to the lateral loop and the medial loop, and the lace extends through the apertures. 15. the article of footwear recited in claim 10 , wherein the knitted component forms a first knitted layer and a second knitted layer that are at least partially coextensive with each other and formed of unitary knit construction, the first tubular structure and the second tubular structure being formed by the first knitted layer and the second knitted layer overlapping and being joined along opposite edges to form an unsecured central area, and the strand extends through the unsecured central area between the first knitted layer and the second knitted layer of the first tubular structure and the second tubular structure. 16. the article of footwear recited in claim 10 , wherein the polymer layer is formed from a thermoplastic polymer material. 17. the article of footwear recited in claim 10 , wherein the polymer layer is a non-woven textile formed from a thermoplastic polymer material. 18. the article of footwear recited in claim 10 , wherein a first area of the knitted component has a first knit type and a second area of the knitted component has a second knit type, the first knit type being different than the second knit type. 19. the article of footwear recited in claim 10 , wherein a first area of the knitted component has a first strand type and a second area of the knitted component has a second strand type, the first strand type being different than the second strand type. 20. the article of footwear recited in claim 1 , wherein the polymer layer has a substantially similar shape as the knitted component. 21. the article of footwear recited in claim 1 , wherein the polymer layer has the configuration of a sheet of polymer material. 22. the article of footwear recited in claim 1 , wherein the polymer layer comprises a polymer resin that is sprayed onto the knitted component.
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background conventional articles of footwear generally include two primary elements, an upper and a sole structure. the upper is secured to the sole structure and forms a void on the interior of the footwear for comfortably and securely receiving a foot. the sole structure is secured to a lower surface of the upper so as to be positioned between the upper and the ground. in some articles of athletic footwear, for example, the sole structure may include a midsole and an outsole. the midsole may be formed from a polymer foam material that attenuates ground reaction forces to lessen stresses upon the foot and leg during walking, running, and other ambulatory activities. the outsole is secured to a lower surface of the midsole and forms a ground-engaging portion of the sole structure that is formed from a durable and wear-resistant material. the sole structure may also include a sockliner positioned within the void and proximal a lower surface of the foot to enhance footwear comfort. the upper generally extends over the instep and toe areas of the foot, along the medial and lateral sides of the foot, and around the heel area of the foot. in some articles of footwear, such as basketball footwear and boots, the upper may extend upward and around the ankle to provide support or protection for the ankle. access to the void on the interior of the upper is generally provided by an ankle opening in a heel region of the footwear. a lacing system is often incorporated into the upper to adjust the fit of the upper, thereby permitting entry and removal of the foot from the void within the upper. the lacing system also permits the wearer to modify certain dimensions of the upper, particularly girth, to accommodate feet with varying dimensions. in addition, the upper may include a tongue that extends under the lacing system to enhance adjustability of the footwear, and the upper may incorporate a heel counter to limit movement of the heel. various materials are conventionally utilized in manufacturing the upper. the upper of athletic footwear, for example, may be formed from multiple material elements. the materials may be selected based upon various properties, including stretch-resistance, wear-resistance, flexibility, air-permeability, compressibility, and moisture-wicking, for example. with regard to an exterior of the upper, the toe area and the heel area may be formed of leather, synthetic leather, or a rubber material to impart a relatively high degree of wear-resistance. leather, synthetic leather, and rubber materials may not exhibit the desired degree of flexibility and air-permeability for various other areas of the exterior. accordingly, the other areas of the exterior may be formed from a synthetic textile, for example. the exterior of the upper may be formed, therefore, from numerous material elements that each impart different properties to the upper. an intermediate or central layer of the upper may be formed from a lightweight polymer foam material that provides cushioning and enhances comfort. similarly, an interior of the upper may be formed of a comfortable and moisture-wicking textile that removes perspiration from the area immediately surrounding the foot. the various material elements and other components may be joined with an adhesive or stitching. accordingly, the conventional upper is formed from various material elements that each impart different properties to various areas of the footwear. summary an article of footwear is disclosed below as having an upper and a sole structure secured to the upper. the upper includes a knitted component and a polymer layer. the knitted component is formed of unitary knit construction and extends along a lateral side of the upper, along a medial side of the upper, over a forefoot region of the upper, and around a heel region of the upper. the polymer layer is bonded to the knitted component and may form a majority of an exterior surface of the upper. the polymer layer may be formed from a thermoplastic polymer material. a method of manufacturing an article of footwear is also disclosed. the method includes utilizing a flat knitting process to form a knitted component having a first surface and an opposite second surface. a polymer layer is bonded to the first surface of the knitted component. additionally, the knitted component and the polymer layer are incorporated into an upper of the article of footwear. the advantages and features of novelty characterizing aspects of the invention are pointed out with particularity in the appended claims. to gain an improved understanding of the advantages and features of novelty, however, reference may be made to the following descriptive matter and accompanying figures that describe and illustrate various configurations and concepts related to the invention. figure descriptions the foregoing summary and the following detailed description will be better understood when read in conjunction with the accompanying figures. fig. 1 is a perspective view of an article of footwear. fig. 2 is a lateral side elevational view of an article of footwear. fig. 3 is a medial side elevational view of the article of footwear. fig. 4 is a top plan view of the article of footwear. figs. 5a-5d are cross-sectional views of the article of footwear, as respectively defined by section lines 5 a- 5 d in fig. 2 . fig. 6 is a top plan view of an upper component that forms a portion of an upper of the article of footwear. fig. 7 is an exploded top plan of the upper component. figs. 8a-8c are side elevational views corresponding with fig. 2 and depicting further configurations of the article of footwear. detailed description the following discussion and accompanying figures disclose an article of footwear having an upper that includes a knitted component and a polymer layer. the article of footwear is disclosed as having a general configuration suitable for walking or running. concepts associated with the footwear, including the upper, may also be applied to a variety of other athletic footwear types, including baseball shoes, basketball shoes, cross-training shoes, cycling shoes, football shoes, tennis shoes, soccer shoes, sprinting shoes, and hiking boots, for example. the concepts may also be applied to footwear types that are generally considered to be non-athletic, including dress shoes, loafers, sandals, and work boots. the concepts disclosed herein apply, therefore, to a wide variety of footwear types. general footwear structure an article of footwear 10 is depicted in figs. 1-5d as including a sole structure 20 and an upper 30 . for reference purposes, footwear 10 may be divided into three general regions: a forefoot region 11 , a midfoot region 12 , and a heel region 13 . forefoot region 11 generally includes portions of footwear 10 corresponding with the toes and the joints connecting the metatarsals with the phalanges. midfoot region 12 generally includes portions of footwear 10 corresponding with an arch area of the foot. heel region 13 generally corresponds with rear portions of the foot, including the calcaneus bone. footwear 10 also includes a lateral side 14 and a medial side 15 , which extend through each of regions 11 - 13 and correspond with opposite sides of footwear 10 . more particularly, lateral side 14 corresponds with an outside area of the foot (i.e. the surface that faces away from the other foot), and medial side 15 corresponds with an inside area of the foot (i.e., the surface that faces toward the other foot). regions 11 - 13 and sides 14 - 15 are not intended to demarcate precise areas of footwear 10 . rather, regions 11 - 13 and sides 14 - 15 are intended to represent general areas of footwear 10 to aid in the following discussion. in addition to footwear 10 , regions 11 - 13 and sides 14 - 15 may also be applied to sole structure 20 , upper 30 , and individual elements thereof. sole structure 20 is secured to upper 30 and extends between the foot and the ground when footwear 10 is worn. the primary elements of sole structure 20 are a midsole 21 , an outsole 22 , and an sockliner 23 . midsole 21 is secured to a lower surface of upper 30 and may be formed from a compressible polymer foam element (e.g., a polyurethane or ethylvinylacetate foam) that attenuates ground reaction forces (i.e., provides cushioning) when compressed between the foot and the ground during walking, running, or other ambulatory activities. in further configurations, midsole 21 may incorporate a fluid-filled bladder that supplements the ground reaction force attenuation properties, or midsole 21 may be primarily formed from the fluid-filled bladder. outsole 22 is secured to a lower surface of midsole 21 and may be formed from a wear-resistant rubber material that is textured to impart traction. sockliner 23 is located within upper 30 and is positioned to extend under a lower surface of the foot. although this configuration for sole structure 20 provides an example of a sole structure that may be used in connection with upper 30 , a variety of other conventional or nonconventional configurations for sole structure 20 may also be utilized. accordingly, the structure and features of sole structure 20 or any sole structure utilized with upper 30 may vary considerably. upper 30 defines a void within footwear 10 for receiving and securing a foot relative to sole structure 20 . the void is shaped to accommodate the foot and extends along the lateral side of the foot, along the medial side of the foot, over the foot, around the heel, and under the foot. access to the void is provided by an ankle opening 31 located in at least heel region 13 . a lace 32 extends through portions of upper 30 , as described in greater detail below, and permits the wearer to modify dimensions of upper 30 to accommodate the proportions of the foot. more particularly, lace 32 permits the wearer to tighten upper 30 around the foot, and lace 32 permits the wearer to loosen upper 30 to facilitate entry and removal of the foot from the void (i.e., through ankle opening 31 ). in addition, upper 30 includes a tongue 33 that extends under lace 32 . a majority of upper 30 is formed from a knitted component 40 and a polymer layer 50 . knitted component 40 may, for example, be manufactured through a flat knitting process and extends through each of regions 11 - 13 , along both lateral side 14 and medial side 15 , over forefoot region 11 , and around heel region 13 . in addition, knitted component 40 forms an interior surface of upper 30 . as such, knitted component 40 defines at least a portion of the void within upper 30 . in some configurations, knitted component 40 may also extend under the foot. for purposes of example in the various figures, however, a strobel sock 34 is secured to knitted component 40 and forms a majority of the portion of upper 30 that extends under the foot. in this configuration, sockliner 23 extends over strobel sock 34 and forms a surface upon which the foot rests. polymer layer 50 forms an exterior surface of upper 30 and is secured to an exterior area of knitted component 40 . in general, polymer layer 50 lays adjacent to knitted component 40 and is secured to knitted component 40 to form the exterior surface of upper 30 . as with knitted component 40 , polymer layer 50 extends through each of regions 11 - 13 , along both lateral side 14 and medial side 15 , over forefoot region 11 , and around heel region 13 . although polymer layer 50 may extend into footwear 10 and over other areas of knitted component 40 , polymer layer 50 is depicted as being primarily located to form the exterior surface of upper 30 . although polymer layer 50 is depicted as forming a majority of the exterior surface of upper 30 , polymer layer 50 may be absent in various areas to expose portions of knitted component 40 . the combination of knitted component 40 and polymer layer 50 provides various advantages to footwear 10 . as an example, the combination of knitted component 40 and polymer layer 50 imparts a relatively tight and glove-like fit to upper 30 . when formed as a soccer shoe, for example, the relatively tight and glove-like fit may provide the wearer with enhanced feel and control of a ball. polymer layer 50 may also be utilized to reinforce areas of upper 30 . for example, polymer layer 50 may inhibit stretch in knitted component 40 and may enhance the wear-resistance or abrasion-resistance of upper 30 . polymer layer 50 may also impart water-resistance to footwear 10 . additionally, forming footwear 10 in this configuration may provide uniform fit and conformance to the foot, a seamless interior with enhanced comfort for the wearer, a relatively light weight, and support for the foot without overlays. knitted component configuration knitted component 40 incorporates various knit types that impart different properties to separate areas of upper 30 . as an example that is depicted in figs. 1 , 4 , and 5 a, knitted component 40 forms various apertures 41 that extend through upper 30 in forefoot region 11 , whereas many other areas of upper 30 have a more continuous or less-apertured configuration. in addition to imparting greater permeability, which allows air to circulate within upper 30 , apertures 41 may increase both the flexibility and stretch of upper 30 in forefoot region 11 . in order to facilitate many of these advantages, polymer layer 50 may also have various apertures that correspond in location with apertures 41 . as further examples, other properties that may be varied through selecting particular knit types for a particular area of knitted component 40 include permeability to liquids, the directions in which knitted component 40 stretches or resists stretch, the stiffness of knitted component 40 , and the compressibility of knitted component 40 . additional examples of knitted components for footwear uppers that have areas with different knit types to impart different properties may be found in u.s. pat. no. 6,931,762 to dua and u.s. pat. no. 7,347,011 to dua, et al., both of which are entirely incorporated herein by reference. as a related matter, the density of the knit within knitted component 40 may vary among separate areas of upper 30 to, for example, make less-permeable or stiffer portions. accordingly, knitted component 40 may exhibit various properties in separate areas depending upon the particular knit type that is selected for the areas. knitted component 40 may also incorporate various yarn types that impart different properties to separate areas of upper 30 . moreover, by combining various yarn types with various stitch types, knitted component 40 may impart a range of different properties to separate areas of upper 30 . the properties that a particular type of yarn will impart to an area of knitted component 40 partially depend upon the materials that form the various filaments and fibers within the yarn. cotton, for example, provides a soft hand, natural aesthetics, and biodegradability. elastane and stretch polyester each provide substantial stretch and recoverability, with stretch polyester also providing recyclability. rayon provides high luster and moisture absorption. wool also provides high moisture absorption, in addition to insulating properties. nylon is a durable and abrasion-resistant material with high strength. polyester is a hydrophobic material that also provides relatively high durability. in addition to materials, other aspects relating to the yarn may affect the properties of upper 30 . for example, the yarn may be a monofilament yarn or a multifilament yarn. the yarn may also include separate filaments that are each formed of different materials. the yarn may also include filaments that are each formed of two or more different materials, such as a bicomponent yarn with filaments having a sheath-core configuration or two halves formed of different materials. different degrees of twist and crimping, as well as different deniers, may affect the properties of upper 30 where the yarn is located. accordingly, both the materials forming the yarn and other aspects of the yarn may be selected to impart a variety of properties to separate areas of upper 30 . in addition to knit types and yarn types, knitted component 40 may incorporate various knitted structures. referring to figs. 2 and 3 , for example, knitted component 40 includes various tubes 42 in which strands 43 are located. tubes 42 are generally hollow structures formed by two overlapping and at least partially coextensive layers of knitted material, as depicted in figs. 5b and 5c . although the sides or edges of one layer of the knitted material forming tubes 42 may be secured to the other layer, a central area is generally unsecured such that another element (e.g., strands 43 ) may be located between the two layers of knitted material and pass through tubes 42 . an additional example of knitted components for footwear uppers that have overlapping or at least partially coextensive layers may be found in u.s. patent application publication 2008/0110048 to dua, et al., which is incorporated herein by reference. tubes 42 extend upward along lateral side 14 and medial side 15 . each tube 42 is adjacent to at least one other tube 42 to form a tube pair. in general, one of strands 43 passes through a first tube 42 of a tube pair, extends outward from an upper end of the first tube 42 , forms a loop 44 , extends into an upper end of a second tube 42 of the tube pair, and passes through the second tube 42 . that is, each strand 43 passes through at least two tubes 42 , and an exposed portion of the strand 43 forms a loop 44 . note that loops 44 are located between knitted component 40 and polymer layer 50 , as depicted in fig. 5b . in this configuration, polymer layer 50 effectively secures the positions of loops 44 around apertures 41 through which lace 32 passes. that is, loops 44 extend around lace apertures 41 in knitted component 40 , polymer layer 50 secures the positions of loops 44 around the lace apertures 41 , and lace 32 may pass through both loops 44 and the lace apertures 41 to form a lacing system in footwear 10 . an individual strand 43 may only pass through two adjacent tubes 42 (i.e., a single tube pair) such that the strand 43 forms a single loop 44 . in this configuration, end portions of the strand 43 exit lower ends of the two adjacent tubes 42 and may be secured to sole structure 20 under strobel sock 34 , for example, to prevent the end portions from being pulled through one of tubes 42 . the presence of polymer layer 50 may also be utilized to secure the positions of the end portions. in another configuration, an individual strand 43 may pass through each of tubes 42 , thereby passing through multiple tube pairs and forming multiple loops 44 . in yet another configuration, one strand 43 may pass through each of tubes 42 located on lateral side 14 , and another strand 43 may pass through each of tubes 42 located on medial side 15 . in general, therefore, an individual strand 43 passes through at least one tube pair to form at least one loop 44 , but may pass through multiple tube pairs to form multiple loops 44 . referring to figs. 1-4 , lace 32 extends through each of loops 44 and also passes through various apertures 41 that are formed in knitted component 40 adjacent to each of loops 44 . as discussed above, loops 44 are located between knitted component 40 and polymer layer 50 , and polymer layer 50 effectively secures the positions of loops 44 around apertures 41 through which lace 32 passes. the combination of lace 32 , the apertures 41 through which lace 32 extends, the various tubes 42 on both lateral side 14 and medial side 15 , strands 43 , and loops 44 provide an effective lacing system for upper 30 . when lace 32 is placed in tension (i.e., when the wearer is tying lace 32 ), tension may also be induced in strands 43 . in the absence of strands 43 , other portions of knitted component 40 would bear the tension and resulting stresses from tying lace 32 . the presence of strands 43 , however, provides a separate element to bear the tension and stresses. moreover, a majority of knitted component 40 may be generally formed through selection of knit type and yarn type to stretch when placed in tension, thereby allowing upper 30 to conform with the contours of the foot. strands 43 , however, may be generally non-stretch in comparison with upper 30 . strands 43 may be formed from a variety of materials and may have the configurations of a rope, thread, webbing, cable, yarn, filament, or chain, for example. in some configurations, strands 43 are located within tubes 42 during the knitting process that forms knitted component 40 . as such, strands 43 may be formed from any generally one-dimensional material that may be utilized in a knitting machine or other device that forms knitted component 40 . as utilized with respect to the present invention, the term “one-dimensional material” or variants thereof is intended to encompass generally elongate materials exhibiting a length that is substantially greater than a width and a thickness. accordingly, suitable materials for strands 43 include various filaments, fibers, and yarns, that are formed from rayon, nylon, polyester, polyacrylic, silk, cotton, carbon, glass, aramids (e.g., para-aramid fibers and meta-aramid fibers), ultra high molecular weight polyethylene, and liquid crystal polymer. in addition to filaments and yarns, other one-dimensional materials may be utilized for strands 43 . although one-dimensional materials will often have a cross-section where width and thickness are substantially equal (e.g., a round or square cross-section), some one-dimensional materials may have a width that is somewhat greater than a thickness (e.g., a rectangular, oval, or otherwise elongate cross-section). despite the greater width, a material may be considered one-dimensional if a length of the material is substantially greater than a width and a thickness of the material. another structure formed by knitted component 40 is a padded collar 45 that extends at least partially around ankle opening 31 . referring to figs. 1-3 , collar 45 exhibits a greater thickness than many other portions of knitted component 40 . in general, collar 45 is formed by two overlapping and at least partially coextensive layers of knitted material (i.e., a tubular structure) and a plurality of floating yarns 46 extending between the layers, as depicted in fig. 5d . although the sides or edges of one layer of knitted material forming collar 45 may be secured to the other layer of knitted material, a central area is generally unsecured. as such, the layers of knitted material effectively form a tube or tubular structure similar to tubes 42 , and floating yarns 46 may be located or laid-in between the two layers of knitted material to pass through the tubes. that is, floating yarns 46 extend between the layers of knitted material, are generally parallel to surfaces of the knitted material, and also pass through and fill an interior volume between the layers. whereas a majority of knitted component 40 is formed from yarns that are mechanically-manipulated to form a knitted structure, floating yarns 46 are generally free or otherwise laid-in within the interior volume between the layers of knitted material forming the exterior of collar 45 . whereas tubes 42 include a single strand 43 , collar 45 includes a plurality of floating yarns 46 that extend through the area between the layers of knitted material. accordingly, knitted component 40 may form generally tubular structures having one or multiple yarns within the tubular structures. moreover, floating yarns 46 may be formed from a variety of materials and may be located within collar 45 during the knitting process that forms knitted component 40 . as such, floating yarns 46 may be formed from any generally one-dimensional material that may be utilized in a knitting machine or other device that forms knitted component 40 . the presence of floating yarns 46 imparts a compressible aspect to collar 45 , thereby enhancing the comfort of footwear 10 in the area of ankle opening 31 . many conventional articles of footwear incorporate polymer foam elements or other compressible materials into a collar area. in contrast with the conventional articles of footwear, collar 45 utilizes floating yarns 46 to provide a compressible structure. the combination of tubes 42 and strands 43 provides upper 30 with a structural element that, for example, resists stretch in a lacing system. similarly, the combination of collar 45 and floating yarns 46 provides upper 30 with a structural element that, for example, compresses to impart greater comfort around ankle opening 31 . although these knitted structures provide different benefits to upper 30 , these knitted structures are similar in that each includes (a) a tubular structure formed from two overlapping and at least partially coextensive layers of knitted material formed of unitary knit construction and (b) at least one yarn, strand, or other one-dimensional material that is laid-in or otherwise located within the tubular structure and extends through at least a portion of a length of the tubular structure. flat knitting process a flat knitting process may be utilized to manufacture knitted component 40 . flat knitting is a method for producing a knitted material that is turned periodically (i.e., the material is knitted from alternating sides). the two sides (otherwise referred to as faces) of the material are conventionally designated as the right side (i.e., the side that faces outwards, towards the viewer) and the wrong side (i.e., the side that faces inwards, away from the viewer). although flat knitting provides a suitable manner for forming knitted component 40 , other knitting processes may also be utilized, depending upon the features that are incorporated into knitted component 40 . examples of other knitting processes that may be utilized include wide tube circular knitting, narrow tube circular knit jacquard, single knit circular knit jacquard, double knit circular knit jacquard, warp knit tricot, warp knit raschel, and double needle bar raschel. an advantage to utilizing a flat knitting process to manufacture knitted component 40 is that each of the features discussed above may be imparted to knitted component 40 through the flat knitting process. that is, a flat knitting process may form knitted component 40 to have, for example, (a) various knit types that impart different properties to separate areas of upper 30 , (b) various yarn types that impart different properties to separate areas of upper 30 , (c) knitted components with the configuration of overlapping knitted layers in tubes 42 , (d) a material such as strand 43 that is laid into tubes 42 , (e) knitted components with the configuration of overlapping knitted layers in collar 45 , and (f) floating yarns between layers of knitted material in collar 45 . moreover, each of these features, as well as other features, may be incorporated into knitted component 40 through a single flat knitting process. as such, a flat knitting process may be utilized to substantially form upper 30 to have various properties and structural features that are advantageous to footwear 10 . although one or more yarns may be mechanically-manipulated by an individual to form knitted component 40 (i.e., knitted component 40 may be formed by hand), flat-knitting machines may provide an efficient manner of forming relatively large numbers of knitted component 40 . the flat-knitting machines may also be utilized to vary the dimensions of knitted component 40 to form uppers 30 that are suitable for footwear with different sizes based on one or both of the length and width of a foot. additionally, the flat-knitting machines may be utilized to vary the configuration of knitted component 40 to form uppers 30 that are suitable for both left and right feet. various aspects of knitted component 40 may also be varied to provide a custom fit for individuals. accordingly, the use of mechanical flat-knitting machines may provide an efficient manner of forming multiple knitted components 40 having different sizes and configurations. knitted component 40 incorporates various features and structures formed of unitary knit construction. in general, the features and structures are formed of unitary knit construction when incorporated into knitted component 40 through the flat knitting process, rather than other processes (e.g., stitching, bonding, shaping) that are performed after the flat knitting process. as an example, tubes 42 and portions of collar 45 are formed from overlapping and at least partially coextensive layers of knitted material, and sides or edges of one layer may be secured to the other layer. the two layers of knitted material are generally formed during the flat knitting process and do not involve supplemental stitching, bonding, or shaping processes. the overlapping layers are, therefore, formed of unitary knit construction through the flat knitting process. as another example, the regions of knitted component 40 formed from knit types that define apertures 41 are formed of unitary knit construction through the flat knitting process. as yet another example, floating yarns 46 are formed of unitary knit construction. a further advantage of utilizing a flat knitting process to form knitted component 40 is that three-dimensional aspects may be incorporated into upper 30 . upper 30 has a curved or otherwise three-dimensional structure that extends around the foot and conforms with a shape of the foot. the flat knitting process may, for example, form areas of knitted component 40 with some curvature in order to complement the shape of the foot. examples of knitted components for footwear uppers that have three-dimensional aspects may be found in u.s. patent application publication 2008/0110048 to dua, et al., which is incorporated herein by reference. knitted component 40 and polymer layer 50 are depicted separate from footwear 10 in figs. 6 and 7 . whereas edges of many textile materials are cut to expose ends of the yarns forming the textile materials, knitted component 40 may be formed to have a finished configuration. that is, flat-knitting or other knitting techniques may be utilized to form knitted component 40 such that ends of the yarns within knitted component 40 are substantially absent from the edges of knitted component 40 . an advantage of the finished configuration formed through flat-knitting is that the yarns forming the edges of knitted component 40 are less likely to unravel, which is an inherent issue with weft knit materials. by forming finished edges, the integrity of knitted component 40 is strengthened and fewer or no post-processing steps are required to prevent unraveling. in addition, loose yarns are also less likely to inhibit the aesthetic appearance of upper 30 . in other words, the finished configuration of knitted component 40 may enhance the durability and aesthetic qualities of upper 20 , while increasing manufacturing efficiency. knitted component 40 provides one example of a configuration that is suitable for upper 30 of footwear 10 . depending upon the intended use of an article of footwear, the desired properties of the article of footwear, and advantageous structural attributes of the article of footwear, for example, a knitted component similar to knitted component 40 may be formed through flat knitting to have the desired features. that is, flat knitting may be utilized to (a) locate specific knit types in desired areas of the knitted component, (b) locate specific yarn types in desired areas of the knitted component, (c) form overlapping knitted layers similar to tubes 42 and collar 45 in desired areas of the knitted component, (d) place strands or floating yarns similar to strands 43 and floating yarns 46 between the knitted layers, (e) form three-dimensional aspects in the knitted component, and (f) impart finished edges. more particularly, any of the features discussed above, for example, may be mixed and matched within a knitted component to form specific properties or structural attributes for a footwear upper. polymer layer configuration polymer layer 50 lays adjacent to knitted component 40 and is secured to knitted component 40 to form the exterior surface of upper 30 . a variety of structures may be utilized for polymer layer 50 , including polymer films, polymer meshes, polymer powders, and non-woven textiles, for example. with any of these structures, a variety of polymer materials may be utilized for polymer layer 50 , including polyurethane, polyester, polyester polyurethane, polyether polyurethane, and nylon. although polymer layer 50 may be formed from a thermoset polymer material, many configurations of polymer layer 50 are formed from thermoplastic polymer materials (e.g., thermoplastic polyurethane). in general, a thermoplastic polymer material melts when heated and returns to a solid state when cooled. more particularly, the thermoplastic polymer material transitions from a solid state to a softened or liquid state when subjected to sufficient heat, and then the thermoplastic polymer material transitions from the softened or liquid state to the solid state when sufficiently cooled. as such, the thermoplastic polymer material may be melted, molded, cooled, re-melted, re-molded, and cooled again through multiple cycles. thermoplastic polymer materials may also be welded or thermal bonded, as described in greater detail below, to textile elements, such as knitted component 40 . although many thermoplastic polymer materials may be utilized for polymer layer 50 , an advantage to utilizing thermoplastic polyurethane relates to thermal bonding and colorability. in comparison with various other thermoplastic polymer materials (e.g., polyolefin), thermoplastic polyurethane is relatively easy to bond with other elements, as discussed in greater detail below, and colorants may be added to thermoplastic polyurethane through various conventional processes. as noted above, polymer layer 50 may be formed from a non-woven textile. an example of a non-woven textile with thermoplastic polymer filaments that may be bonded to knitted component 40 is disclosed in u.s. patent application publication 2010/0199406 to dua, et al., which is incorporated herein by reference. a thermoplastic polymer material forming polymer layer 50 may be utilized to secure polymer layer 50 to knitted component 40 . as discussed above, a thermoplastic polymer material melts when heated and returns to a solid state when cooled sufficiently. based upon this property of thermoplastic polymer materials, thermal bonding processes may be utilized to form a thermal bond that joins portions of polymer layer 50 to knitted component 40 . as utilized herein, the term “thermal bonding” or variants thereof is defined as a securing technique between two elements that involves a softening or melting of a thermoplastic polymer material within at least one of the elements such that the materials of the elements are secured to each other when cooled. similarly, the term “thermal bond” or variants thereof is defined as the bond, link, or structure that joins two elements through a process that involves a softening or melting of a thermoplastic polymer material within at least one of the elements such that the materials of the elements are secured to each other when cooled. as examples, thermal bonding may involve (a) the melting or softening of polymer layer 50 such that the thermoplastic polymer materials intermingle with materials of knitted component 40 and are secured together when cooled and (b) the melting or softening of polymer layer 50 such that the thermoplastic polymer material extends into or infiltrates the structure of knitted component 40 (e.g., extends around or bonds with filaments or fibers in knitted component 40 ) to secure the elements together when cooled. additionally, thermal bonding does not generally involve the use of stitching or adhesives, but involves directly bonding elements to each other with heat. in some situations, however, stitching or adhesives may be utilized to supplement the thermal bond or the joining of elements through thermal bonding. a needlepunching process may also be utilized to join the elements or supplement the thermal bond. manufacturing processes a variety of methods may be utilized to manufacture upper 30 . in general, knitted component 40 is manufactured through the knitting processes discussed above. polymer layer 50 is then secured (e.g., bonded or thermal bonded) to knitted component 40 . for example, knitted component 40 and polymer layer 50 may be placed between portions of a heat press that compress and heat the elements, thereby bonding them together. in some configurations, polymer layer 50 may be a sheet or film of polymer material that is compressed and heated with knitted component 40 . in another configuration, polymer layer 50 may be a non-woven textile element that is compressed and heated with knitted component 40 . the compression and heating may melt the non-woven textile element to form a polymer film on the exterior of knitted component 40 , or portions of the non-woven textile element may remain fibrous to impart breathability or air permeability. details relating to the non-woven textile element may be found in u.s. patent application publication 2010/0199406 to dua, et al., which is incorporated herein by reference. in yet another configuration, polymer layer 50 may be a polymer powder that is compressed and heated with knitted component 40 , and the compression and heating may melt the powder to form a polymer film on the exterior of knitted component 40 . as another example, a polymer resin may be sprayed or otherwise applied to knitted component 40 to form polymer layer 50 . accordingly, various methods may be utilized to form the combination of knitted component 40 and polymer layer 50 . further configurations the features of upper 30 discussed above, including both knitted component 40 and polymer layer 50 , provide one example of a suitable configuration for footwear 10 . a variety of other configurations may also be utilized. as an example, fig. 8a depicts a configuration wherein tubes 42 and strands 43 are absent from knitted component 40 . although polymer layer 50 may extend over substantially all of knitted component 40 and is depicted as forming a majority of the exterior surface of upper 30 , polymer layer 50 may be absent in various areas to expose portions of knitted component 40 . for example, fig. 8b depicts a configuration wherein polymer layer 50 is primarily located in midfoot region 12 and exposes knitted component 40 in both of regions 11 and 13 . in further configurations, polymer layer 50 may be absent in other areas. as an example, fig. 8c depicts a configuration wherein polymer layer 50 defines various apertures throughout upper 30 that expose areas of knitted component 40 . various features of knitted component 40 may also vary. further examples of variations for knitted component 40 may be found in u.s. patent application publication 2010/0154256 to dua, which is incorporated herein by reference. additionally, u.s. patent application ser. no. 13/048,514, which was filed in the u.s. patent and trademark office on 15 mar. 2011 and entitled article of footwear incorporating a knitted component, which is incorporated herein by reference, discloses additional configurations that may be utilized for knitted component 40 . manufacturing efficiency the upper of conventional athletic footwear, for example, may be formed from multiple material elements that each impart different properties to various areas of the footwear. in order to manufacture a conventional upper, the material elements are cut to desired shapes and then joined together, usually with stitching or adhesive bonding. as the number and types of material elements incorporated into an upper increases, the time and expense associated with transporting, stocking, cutting, and joining the material elements may also increase. waste material from cutting and stitching processes also accumulates to a greater degree as the number and types of material elements incorporated into the upper increases. moreover, footwear with a greater number of materials, material elements, and other components may be more difficult to recycle than uppers formed from few elements and materials. by decreasing the number of elements and materials utilized in an upper, therefore, waste may be decreased while increasing the efficiency of manufacture and recyclability. whereas conventional uppers require a variety of manufacturing steps involving a plurality of material elements, upper 30 may be formed through the combination of (a) a flat knitting process for knitted component 40 and (b) a bonding process for securing polymer layer 50 . following the flat knitting and bonding processes, a relatively small number of steps are required to incorporate knitted component 40 and polymer layer 50 into footwear 10 . more particularly, strobel sock 34 is joined to edges of knitted component 40 , two edges in heel region 13 are joined, lace 32 is incorporated, and the substantially completed upper 30 is secured with sole structure 20 . in comparison with conventional manufacturing processes, the use of knitted component 40 and polymer layer 50 may reduce the overall number of manufacturing steps. additionally, waste may be decreased while increasing recyclability. the invention is disclosed above and in the accompanying figures with reference to a variety of configurations. the purpose served by the disclosure, however, is to provide an example of the various features and concepts related to the invention, not to limit the scope of the invention. one skilled in the relevant art will recognize that numerous variations and modifications may be made to the configurations described above without departing from the scope of the present invention, as defined by the appended claims.
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124-969-799-756-728
|
US
|
[
"AU",
"WO"
] |
G06F/,G06Q30/00,G06Q40/00
| 2000-11-17T00:00:00 |
2000
|
[
"G06"
] |
profile-based pricing
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dynamically updated profiles (110) for an initiator and/or one or more bidders in an online auction allows pricing or other auction variables to be altered during or after an auction to be adjusted based on information gathered (108) with regard to one or more profile fields in the profiles (106). additionally, limits can be dynamically set as to who can participate in an auction (112) using the information in the profiles (104). multi-variable bidding may be accomplished by applying weights (118) to certain variables at the end of an auction along with any modifications outlined in any relevant profile fields (120) in order to determine a winner or winners of the auction.
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claims what is claimed is: 1. a method for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator, including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said initiator and for each of said bidders from a profile database, each of said profiles having one or more profile fields; gathering information regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 2. the method of claim 1, wherein one of said profiles corresponds to multiple bidders within a single corporation. 3. the method of claim 1, wherein said information is the percentage of time one or more companies is on-time in payments. 4. the method of claim 1, wherein said information is the percentage of time one or more companies is on-time in deliveries. 5. the method of claim 1, wherein said information is how good one or more companies are at supplying certain countries. 6. the method of claim 1, wherein said information is how many items one or more companies is currently bidding on. 7. the method of claim 3, further including excluding any bidders whose on-time percentage is below a predefined level. 8. the method of claim 4, further including excluding any bidders whose on-time percentage is below a predefined level. 9. the method of claim 3, further including charging a fixed percentage more to any bidders whose on-time percentage is below a predefined level. 10. the method of claim 4, further including charging a fixed percentage more to any bidders whose on-time percentage is below a predefined level. 11. a method for determining which of one or more potential bidders may be allowed to participate in an online auction including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for each of said potential bidders from a profile database, each of said profiles having one or more profile fields, one of said profile fields indicating the percentage of time the corresponding bidder has paid on-time; gathering information regarding said one or more potential bidders with regard to how often said potential bidders have paid on-time in said profiles by using an information collection unit; dynamically updating said on-time profile field in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; and excluding any potential bidders whose on-time percentage as contained in said on-time profile field in said profiles is less than a percentage specified in a profile for an initiator of said auction. 12. a method for providing profile-based pricing in an online auction, said online auction having one or more buyers and a seller, including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields; gathering information regarding said seller or said one or more buyers with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 13. a method for providing profile-based pricing in an online auction, said online auction having one or more buyers and a seller, including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields; gathering information regarding said seller or said one or more buyers with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 14. a method for providing profile-based pricing in an online auction, said online auction haying one or more buyers and a seller, including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields, one of said profile fields indicating the percentage of time the corresponding bidder has paid on-time; gathering information regarding said one or more potential bidders with regard to how often said potential bidders have paid on-time in said profiles by using an information collection unit; dynamically updating said on-time profile field in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; and adding a fixed percentage to the bids of any potential bidders whose on-time percentage as contained in said on-time profile field in said profiles is less than a percentage specified in a profile for an initiator of said auction. 15. a method for providing a multi-variable online auction, said online auction having one or more bidders and an initiator, including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said initiator and for each of said bidders from a profile database, each of said profiles having one or more profile fields, said profile for the initiator having weights assigned to each of one or more variables; gathering information regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; executing the auction by applying said weights to corresponding variables and computing the results along with any modifications outlined in any relevant profile fields at the close of the auction in order to determine a winner or winners of the auction. 16. an apparatus for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator, including: an online auction rules database; an online auction rules retriever coupled to said online auction rules database; a profile database; a profile accessor coupled to said profile database; an information gathering unit coupled to said online auction rules retriever; and a dynamic profile updater coupled to said online auction rules retriever, said profile accessor, and said online auction rules retriever. 17. the apparatus of claim 16, further including a fixed percentage charger coupled to said information gathering unit and to said dynamic profile updater. 18. the apparatus of claim 16, further including a bidder excluder coupled to said information gathering unit and to said dynamic profile updater. 19. an apparatus for determining which of one or more potential bidders may be allowed to participate in an online auction including: i an online auction rules database; an online auction rules retriever coupled to said online auction rules database; a profile database; a profile accessor coupled to said profile database; an information gathering unit coupled to said online auction rules retriever; a dynamic profile updater coupled to said online auction rules retriever, said profile accessor, and said online auction rules retriever; and a bidder excluder coupled to said information gathering unit and to said dynamic profile updater. 20. an apparatus for providing a multi-variable online auction, said online auction having one or more bidders and an initiator, including: an online auction rules database; an online auction rules retriever coupled to said online auction rules database; a profile database; a profile accessor coupled to said profile database; an information gathering unit coupled to said online auction rules retriever; a dynamic profile updater coupled to said online auction rules retriever, said profile accessor, and said online auction rules retriever; and an auction executor coupled to said information gathering unit and to said dynamic profile updater; said auction executor including a variable weigther coupled to a profile field/variable weight combiner. 21. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said initiator and for each of said bidders from a profile database, each of said profiles having one or more profile fields; gathering information regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 22. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for determining which of one or more potential bidders may be allowed to participate in an online auction, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for each of said potential bidders from a profile database, each of said profiles having one or more profile fields, one of said profile fields indicating the percentage of time the corresponding bidder has paid on-time; gathering information regarding said one or more potential bidders with regard to how often said potential bidders have paid on-time in said profiles by using an information collection unit; dynamically updating said on-time profile field in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; and excluding any potential bidders whose on-time percentage as contained in said on-time profile field in said profiles is less than a percentage specified in a profile for an initiator of said auction. 23. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for providing profile-based pricing in an online auction, said online auction having one or more buyers and a seller, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields; gathering information regarding said seller or said one or more buyers with regard to one of said one or more- profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 24. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for providing profile-based pricing in an online auction, said online auction having one or more buyers and a seller, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields; gathering information regarding said seller or said one or more buyers with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. 25. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for providing profile-based pricing in an online auction, said online auction having one or more buyers and a seller, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said seller and for each of said buyers from a profile database, each of said profiles having one or more profile fields, one of said profile fields indicating the percentage of time the corresponding bidder has paid on-time; gathering information regarding said one or more potential bidders with regard to how often said potential bidders have paid on-time in said profiles by using an information collection unit; dynamically updating said on-time profile field in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; and adding a fixed percentage to the bids of any potential bidders whose on-time percentage as contained in said on-time profile field in said profiles is less than a percentage specified in a profile for an initiator of said auction. 26. a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine for providing a multi-variable online auction, said online auction having one or more bidders and an initiator, the method including: retrieving a set of rules governing said online auction from a rules database, said rules including at least one rule involving a profile field; accessing profiles for said initiator and for each of said bidders from a profile database, each of said profiles having one or more profile fields, said profile for the initiator having weights assigned to each of one or more variables; gathering information regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit; dynamically updating said one or more profile fields in said profiles by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction; executing the auction by applying said weights to corresponding variables and computing the results along with any modifications outlined in any relevant profile fields at the close of the auction in order to determine a winner or winners of the auction.
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s p e c if i c a t i o n title of the invention profile-based pricing cross reference to related application this application claims priority based on provisional application serial no. 60/249,671, entitled, "profile-based pricing", filed on november 17, 2000, by ramesh balwani. field of the invention the present invention relates to the field of internet-based auctions. more specifically, the present invention relates to profile-based pricing in an internet-based auction. background of the invention internet auctions have exploded into one of the most popular forms of electronic commerce (e-commerce) on the internet. online auctions began with individuals selling personal items to other individuals but in recent years there has been a dramatic rise in the number of business-to-business (b2b) auctions conducted via the internet. a process that once required laborious paperwork and endless committees within a company has now been outsourced to a web site which does most of the leg work. b2b auctions typically have different parameters than non-business auctions. they normally involve a large number of goods and a great deal more money. there are also special business needs which must be accounted for, such as the reluctance of many companies to do business with brand new companies that have no track record with regard to delivery or payment reliability. thus, typically business-to-business auctions have been non-binding or only partially binding, thus allowing the seller or buyer to back out if the ultimate "winner" of the auction is not satisfactory to him. additionally, in the past, businesses have altered the "rules" governing whom they sell goods to and how they sell the goods depending on the buyer. for example, a company selling 100,000 units of product a may give 10% off to a certain company in order to make up for a prior shipment in which 1000 of the units shipped turned out to be defective. alternatively, a company selling 100,000 units of product a may charge 10% more to a company who has been late with its payments in the past. there currently is no mechanism to integrate these important bits of information into the rules of an internet auction. thus, currently b2b auctions are normally non- binding or only partially binding (or limit the field of bidders as to ensure only reputable companies bid). what is needed is a solution which allows for this type of information to be incorporated into the auction itself, thus simplifying the auction process and allowing true online b2b auctions. brief description of the invention dynamically updated profiles for an initiator and/or one or more bidders in an online auction allows pricing or other auction variables to be altered during or after an auction to be adjusted based on information gathered with regard to one or more profile fields in the profiles. additionally, limits can be dynamically set as to who can participate in an auction using the information in the profiles. multi-variable bidding may be accomplished by applying weights to certain variables at the end of an auction along with any modifications outlined in any relevant profile fields in order to determine a winner or winners of the auction. brief description of the drawings fig. 1 is a block diagram illustrating a web-based auction system in accordance with a specific embodiment of the present invention. fig. 2 is a flow diagram illustrating a method for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator in accordance with a specific embodiment of the present invention. fig. 3 is a block diagram illustrating an apparatus for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator in accordance with a specific embodiment of the present invention. detailed description of the invention in the following description, a preferred embodiment of the invention is described with regard to preferred process steps and data structures. however, those skilled in the art will recognize, after perusal of this application, that embodiments of the invention may be implemented using at least one general purpose computer operating under program control, and that modification of the general purpose computer to implement the components, process steps, and/or data structures described herein would not require undue invention. the present invention utilizes dynamically updated profiles in an auction system in order to allow auctions to incorporate additional factors into its rules. fig. 1 is a block diagram illustrating a web-based auction system in accordance with a specific embodiment of the present invention. the auction engine 2 executes rules stored in a rules database 4. the rules indicate how the auction is to be run. examples of rules that may be defined in the rules database include the length of the auction, the type of the auction, and how the winner is determined. in auctions, there is generally one party who initiates the auction process. in traditional auction, this is generally the seller, who places a good or service up for auction, at which point one or more buyers bid on the good or service. however, given the large variety of auction models, this initiator may not be a seller. reverse auctions have gained in popularity in recent years so it is quite possible now to have the initiator of the auction be a potential buyer rather than a seller. additionally, it is also conceivable that there may be auctions where there are both multiple sellers and multiple buyers participating. for purposes of this specification, the term initiator will be used to represent the party that controls the rules of the auctions. thus, while in traditional auctions the initiator may be limited to a single buyer, for purposes of this specification, the initiator may be a buyer, a seller, or multiple buyers or sellers. before, after, or during the auction it may be necessary to alter the auction based on profiles for the buyer or seller. a profile processing unit 6 accesses a profile database 8 to retrieve appropriate profiles for the auction. the profiles need not have any specific format or include any particular fields. hence, they can be dynamically altered to change information, or add or remove fields. profiles may be stored for either sellers or buyers or both. additionally, profiles may be stored on corporations on top of individuals. for example, there may be multiple parties within a large corporation that bid on parts using an auction system (an automobile manufacturer may use a separate buyer for brake pads as for tires). thus profiles may be stored for each buyer within the corporation and/or the corporation itself (covering all the buyers within the corporation). the profile processing unit 6 is coupled to an information collection unit 10. the information collection unit 10 gathers information relevant to the profile. in a first embodiment of the present invention, the information collection unit 10 gathers information as to the percentage of time the companies having profiles are on-time in either payments or delivery (depending on whether they are buyers or sellers, respectively). in a second embodiment of the present invention, the information collection unit 10 gathers information as to how good the company is at supplying certain countries. the profiles may then be created by combining generalized rules for the auction from the rules database 4 with information gathered by the information collection unit. in a first embodiment of the present invention, there is a rule in the rules database indicating how bidders are treated based on the percentage of time they are on time in either payments or deliveries. for example, the rule may indicate that only companies who have an 80% on time rate are allowed to bid. another example is that the rule may indicate that companies who have less than an 80% on time rate must pay 5% more for goods. thus, the profile for a company with less than an 80% on time rate would contain a field indicating that they must pay 5% more for goods. one of the main advantages of the present invention is that it is dynamic. thus, the information collection unit is constantly gathering data on company performance. therefore, as soon as the company rises above an 80% on time rate, their profile would dynamically change and immediately their 5% penalty would be removed. another possibility is to lower the price of the items being bid on if there are more bidders. this is especially helpful for auctions in which a seller has access a great many identical items for sale. the seller may then be able to get quantity discounts from his supplier if there are enough bidders. thus, for example, the price could be reduced by 5% after the number of bidders reaches 1,000, by 20% after the number of bidders reaches 10,000, etc. the profiles may also be used to implement multi-variable auctions. auctions typically have only one variable: the price of the bid. the profiles, however, allow a seller to assign weights to a number of different variables. thus, determining the winner of the auction may be more complex than simply looking at who bid the highest (or lowest in the case of reverse auctions). variables such as quantity of good bid on, location of the bidder, type of payment, etc. may all be factored into a "smart" auction process. fig. 2 is a flow diagram illustrating a method for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator in accordance with a specific embodiment of the present invention. at 50, a set of rules governing said online auction is retrieved from a rules database, said rules including at least one rule involving a profile field. the profiles may correspond to individual buyers or sellers, or even multiple buyers or sellers within a single corporation. at 52, profiles for said initiator and for each of said bidders are accessed from a profile database, each of said profiles having one or more profile fields. at 54, information is gathered regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit. types of possible information include the percentage of time one or more companies is on-time in payments, percentage of time one or more companies is on-time in deliveries, how good one or more companies are at supplying certain countries, and how many items one or more companies is bidding on. at 56, said one or more profile fields in said profiles are dynamically updated by using said information gathered from said information collection unit and combining it with one or more rules from said set of rules governing said online auction. fig. 3 is a block diagram illustrating an apparatus for providing profile-based pricing in an online auction, said online auction having one or more bidders and an initiator in accordance with a specific embodiment of the present invention. an online auction rules retriever 100 coupled to an online auction rules database 102 retrieves a set of rules governing said online auction from the online auction rules database 102, said rules including at least one rule involving a profile field. the profiles may correspond to individual buyers or sellers, or even multiple buyers or sellers within a single corporation. a profile accessor 104 coupled to a profile database 106 accesses profiles for said initiator and for each of said bidders the profile database 106, each of said profiles having one or more profile fields. an information collection unit 108 gathers information regarding said initiator or said one or more bidders with regard to one of said one or more profile fields in said profiles by using an information collection unit. types of possible information include the percentage of time one or more companies is on-time in payments, percentage of time one or more companies is on-time in deliveries, how good one or more companies are at supplying certain countries, and how many items one or more companies is bidding on. a dynamic profile updater 110 coupled to said information gathering unit 108, said online auction rules retriever 100 and said profile accessor 104 dynamically updates the one or more profile fields in said profiles using said information gathered from said information collection unit 108 and combining it with one or more rules from said set of rules governing said online auction. a bidder excluder 112 coupled to the dynamic profile updater 110 and the information gathering unit 108 may exclude certain bidders based upon information in their profiles, such as excluding all bidders whose on-time percentage is less than 80%. a fixed percentage charger 114 coupled to the dynamic profile updater 110 and the information gathering unit 108 may charge a fixed percentage more for any bidder based upon information in their profiles, such as charging 5% more to all bidders whose on- time percentage is less than 80%. an auction executor 116 coupled to the dynamic profile updater 110 and the information gathering unit 112 may execute the auction using a variable weighter 118 to apply weights to corresponding variables and a profile field/variable weight combiners 120 to compute the results along with any modifications outlined in any relevant profile fields at the close of the auction in order to determine a winner or winners of the auction. this allows for multi-variable bidding. while embodiments and applications of this invention have been shown and described, it would be apparent to those skilled in the art having the benefit of this disclosure that many more modifications than mentioned above are possible without departing from the inventive concepts herein. the invention, therefore, is not to be restricted except in the spirit of the appended claims.
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125-796-677-574-313
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EP
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[
"US"
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H04R25/00
| 2012-12-28T00:00:00 |
2012
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[
"H04"
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hearing aid with improved localization
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a hearing aid includes: a cue filter having an input that is provided with an output from the bte sound input transducer; an adaptive feedback canceller configured to provide an output modelling a feedback path between the output transducer and the bte sound input transducer, wherein the output modelling the feedback path is provided to a subtractor for subtraction of the output modelling the feedback path from the output of the bte sound input transducer to obtain a difference, the subtractor outputting the difference to the cue filter; and a feedback and cue controller connected to the adaptive feedback canceller and the cue filter, wherein the feedback and cue controller is configured to control the cue filter to reduce a difference between an output of the ite microphone and a combined output that is obtained using at least the cue filter.
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1. a hearing aid comprising: a behind-the-ear (bte) hearing aid housing configured to be worn behind a pinna of a user; at least one bte sound input transducer accommodated in the bte hearing aid housing, each of which is configured for conversion of acoustic sound into a respective audio sound signal; an in-the-ear (ite) microphone housing configured to be positioned in an outer ear of the user; at least one ite microphone accommodated in the ite microphone housing, each of which is configured for conversion of acoustic sound into a respective audio sound signal; at least one adaptive cue filter, each of which having an input that is provided with an output from the at least one bte sound input transducer, wherein filter coefficients of the at least one adaptive cue filter are adapted so that a difference between an output of the at least one ite microphone and a combined output of the at least one adaptive cue filter is reduced; a processor configured to generate a hearing loss compensated output signal based on output by the at least one cue filter; an output transducer for conversion of the hearing loss compensated output signal to an auditory output signal that can be received by a human auditory system; an adaptive feedback canceller for feedback suppression and having an input connected to the processor for reception of the hearing loss compensated output signal, wherein the adaptive feedback canceller is configured to provide at least one output modelling a feedback path between the output transducer and the at least one bte sound input transducer, wherein the at least one output modelling the feedback path is provided to a subtractor for subtraction of the at least one output modelling the feedback path from the output of the at least one bte sound input transducer to obtain a difference, the subtractor outputting the difference to the at least one adaptive cue filter; and a feedback and cue controller connected to the adaptive feedback canceller and the at least one adaptive cue filter, wherein the feedback and cue controller is configured to control the at least one adaptive cue filter so that the difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter is reduced. 2. the hearing aid according to claim 1 , wherein the filter coefficients of the at least one adaptive cue filter are adapted towards a solution of: wherein s iec (f,t) is a short time spectrum at time t of the output signal of the at least one ite microphone, and s 1 btec (f,t), s 2 btec (f,t), . . . , s n btec (f,t) are short time spectra at time t of the output of the at least one bte sound input transducer, and g 1 btec (f,t), g 2 btec (f,t), . . . , g n btec (f,t) are transfer functions of pre-processing filters connected to respective output(s) of the at least one bte sound input transducer, and h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) transfer functions of feedback path associated with the n'th bte microphone of the at least one bte microphone, p is a norm factor, w(f) is a frequency dependent weighting factor, α is a weighting factor balancing spatial cue accuracy and feedback performance, and btec represents a behind-the-ear-component. 3. the hearing aid according to claim 1 , wherein the filter coefficients of the at least one adaptive cue filter are adapted towards a solution of: subject to a condition that wherein s iec (f,t) is a short time spectrum at time t of the output signal of the at least one ite microphone, and s 1 btec (f,t), s 2 btec (f,t), . . . , s n btec (f,t) are short time spectra at time t of the output of the at least one bte sound input transducer, and g 1 btec (f,t), g 2 btec (f,t), . . . , g n btec (f,t) are transfer functions of pre-processing filters connected to respective output(s) of the at least one bte sound input transducer, h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) are transfer functions of feedback path associated with the n'th bte microphone of the at least one bte microphone, p is a norm factor, msg(f) is a maximum stable gain, and btec represents a behind-the-ear-component. 4. the hearing aid according to claim 1 , wherein the filter coefficients of the at least one adaptive cue filter comprise sets of filter coefficients, and wherein the hearing aid further comprises a memory for accommodation of the sets of filter coefficients of the at least one adaptive cue filter, each of the sets of filter coefficients is for a specific direction of arrival with relation to the hearing aid. 5. the hearing aid according to claim 4 , wherein the at least one adaptive cue filter is loaded with the set of filter coefficients that provides a minimum difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter. 6. the hearing aid according to claim 5 , wherein the at least one adaptive cue filter is allowed to further adapt after the at least one adaptive cue filter is loaded with the set of filter coefficients that provides the minimum difference. 7. the hearing aid according to claim 1 , wherein the at least one adaptive cue filter is prevented from further adapting when changes of values of the filter coefficients are below a prescribed threshold. 8. the hearing aid according to claim 1 , wherein the audio sound signals from the at least one bte and the at least one ite are divided into a plurality of frequency channels, and wherein the at least one adaptive cue filter is configured for individually processing the audio sound signals in one or more of the frequency channels. 9. the hearing aid according to claim 8 , wherein the at least one bte sound input transducer is disconnected from the processor in one or more of the frequency channels so that hearing loss compensation is based solely on the output of the at least one ite microphone. 10. the hearing aid according to claim 1 , wherein: the at least one bte sound input transducer comprises a first bte sound input transducer and a second bte sound input transducer; the at least one adaptive cue filter comprises a first adaptive cue filter and a second adaptive cue filter; the first adaptive cue filter has an input that is provided with an output signal from the first bte sound input transducer; and filter coefficients of the first adaptive cue filter are adapted so that a difference between the output of the at least one ite microphone and a combined output of the first and second adaptive cue filters is reduced. 11. the hearing aid according to claim 10 , wherein: the second adaptive cue filter has an input that is provided with an output signal from the second bte sound input transducer, and filter coefficients of the second adaptive cue filter are adapted so that a difference between the output of the at least one ite microphone and a combined output of the first and second adaptive cue filters is reduced. 12. the hearing aid according to claim 2 , wherein a is frequency dependent. 13. the hearing aid according to claim 2 , wherein w(f)=1. 14. the hearing aid according to claim 2 , wherein p=2. 15. the hearing aid according to claim 1 , wherein the filter coefficients of the at least one adaptive cue filter are adapted so that the difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter is minimized. 16. the hearing aid according to claim 1 , further comprising: a sound signal transmission member for transmission of a sound signal from a sound output in the bte hearing aid housing at a first end of the sound signal transmission member to an ear canal of the user at a second end of the sound signal transmission member; and an earpiece configured to be inserted in the ear canal of the user for fastening and retaining the sound signal transmission member in its intended position in the ear canal of the user.
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related application data this application claims priority to, and the benefit of, danish patent application no. pa 2012 70836, filed dec. 28, 2012, and european patent application no. 12199761.3, filed dec. 28, 2012. the disclosures of all of the above applications are expressly incorporated by reference in their entireties herein. field a new hearing aid is provided with improved localization of sound sources with relation to the wearer of the hearing aid. background hearing aid users have been reported to have poorer ability to localize sound sources when wearing their hearing aids than without their hearing aids. this represents a serious problem for the mild-to-moderate hearing impaired population. furthermore, hearing aids typically reproduce sound in such a way that the user perceives sound sources to be localized inside the head. the sound is said to be internalized rather than being externalized. a common complaint for hearing aid users when referring to the “hearing speech in noise problem” is that it is very hard to follow anything that is being said even though the signal to noise ratio (snr) should be sufficient to provide the required speech intelligibility. a significant contributor to this fact is that the hearing aid reproduces an internalized sound field. this adds to the cognitive loading of the hearing aid user and may result in listening fatigue and ultimately that the user removes the hearing aid(s). thus, there is a need for a new hearing aid with improved localization of sound sources, i.e. the new hearing aid preserves information of the directions and distances of respective sound sources in the sound environment with relation to the orientation of the head of the wearer of the hearing aid. human beings detect and localize sound sources in three-dimensional space by means of the human binaural sound localization capability. the input to the hearing consists of two signals, namely the sound pressures at each of the eardrums, in the following termed the binaural sound signals. thus, if sound pressures at the eardrums that would have been generated by a given spatial sound field are accurately reproduced at the eardrums, the human auditory system will not be able to distinguish the reproduced sound from the actual sound generated by the spatial sound field itself. it is not fully known how the human auditory system extracts information about distance and direction to a sound source, but it is known that the human auditory system uses a number of cues in this determination. among the cues are spectral cues, reverberation cues, interaural time differences (itd), interaural phase differences (ipd) and interaural level differences (ild). the transmission of a sound wave from a sound source positioned at a given direction and distance in relation to the left and right ears of the listener is described in terms of two transfer functions, one for the left ear and one for the right ear, that include any linear distortion, such as coloration, interaural time differences and interaural spectral differences. such a set of two transfer functions, one for the left ear and one for the right ear, is called a head-related transfer function (hrtf). each transfer function of the hrtf is defined as the ratio between a sound pressure p generated by a plane wave at a specific point in or close to the appertaining ear canal (p l in the left ear canal and p r in the right ear canal) in relation to a reference. the reference traditionally chosen is the sound pressure p i that would have been generated by a plane wave at a position right in the middle of the head with the listener absent. the hrtf contains all information relating to the sound transmission to the ears of the listener, including diffraction around the head, reflections from shoulders, reflections in the ear canal, etc., and therefore, the hrtf varies from individual to individual. in the following, one of the transfer functions of the hrtf will also be termed the hrtf for convenience. the hearing aid related transfer function is defined similar to a hrtf, namely as the ratio between a sound pressure p generated by the hearing aid at a specific point in the appertaining ear canal in response to a plane wave and a reference. the reference traditionally chosen is the sound pressure p i that would have been generated by a plane wave at a position right in the middle of the head with the listener absent. the hrtf changes with direction and distance of the sound source in relation to the ears of the listener. it is possible to measure the hrtf for any direction and distance and simulate the hrtf, e.g. electronically, e.g. by filters. if such filters are inserted in the signal path between a playback unit, such as a tape recorder, and headphones used by a listener, the listener will achieve the perception that the sounds generated by the headphones originate from a sound source positioned at the distance and in the direction as defined by the transfer functions of the filters simulating the hrtf in question, because of the true reproduction of the sound pressures in the ears. binaural processing by the brain, when interpreting the spatially encoded information, results in several positive effects, namely better signal-to-noise ratio (snr); direction of arrival (doa) estimation; depth/distance perception and synergy between the visual and auditory systems. the complex shape of the ear is a major contributor to the individual spatial-spectral cues (itd, ild and spectral cues) of a listener. devices which pick up sound behind the ear will, hence, be at a disadvantage in reproducing the hrtf since much of the spectral detail will be lost or heavily distorted. this is exemplified in figs. 1 and 2 where the angular frequency spectrum of an open ear, i.e. non-occluded, measurement is shown in fig. 1 for comparison with fig. 2 showing the corresponding measurement on the front microphone on a behind the ear device (bte) using the same ear. the open ear spectrum shown in fig. 1 is rich in detail whereas the bte result shown in fig. 2 is much more blurred and much of the spectral detail is lost. summary it is therefore desirable to position one or more microphones of the hearing aid at position(s) with relation to a user wearing the hearing aid in which spatial cues of sounds arriving at the user is preserved. it is for example advantageous to position a microphone in the outer ear of the user in front of the pinna, for example at the entrance to the ear canal; or, inside the ear canal, in order to preserve spatial cues of sounds arriving at the ear to a much larger extent than what is possible with the microphone behind the ear. a position below the triangular fossa has also proven advantageous with relation to preservation of spatial cues. positioning of a microphone at the entrance to the ear canal or inside the ear canal leads to the problem that the microphone is moved close to the sound emitting device of the hearing aid, whereby the risk of feedback generation is increased, which in turn limits the maximum stable gain which can be prescribed with the hearing aid. the standard way of solving this problem is to completely seal off the ear canal using a custom mould. this, however, introduces the occlusion effect as well as comfort issues with respect to moisture and heat. for comparison, the maximum stable gain of a bte hearing aid with front and rear microphones positioned behind the ear, and an in-the-ear (ite) hearing aid with an open fitted microphone positioned in the ear canal is shown in fig. 2 . it can be seen that the ite hearing aid has much lower maximum stable gain (msg) than the front and rear bte microphones for nearly all frequencies. in the new hearing aid, output signals of an arbitrary configuration of microphones undergo signal processing in such a way that spatial cues are preserved and conveyed to the user of the hearing aid. the output signals are filtered with filters that are configured to preserve spatial cues. the new hearing aid provides improved localization to the user by providing, in addition to conventionally positioned microphones as in a bte hearing aid, at least one ite microphone intended to be positioned in the outer ear of the user in front of the pinna, e.g. at the entrance to the ear canal or immediately below the triangular fossa; or, inside the ear canal, when in use in order to record sound arriving at the ear of the user and containing the desired spatial information relating to localization of sound sources in the sound environment. the processor of the new hearing aid combines an audio signal of the at least one ite microphone residing in the outer ear of the user with the microphone signal(s) of the conventionally positioned microphone(s) as in a bte hearing aid in such a way that spatial cues are preserved. an audio signal of the at least one ite microphone may be formed as a weighted sum of the output signals of each microphone of the at least one ite microphone. other forms of signal processing may be included in the formation of the audio signal of the at least one ite microphone. thus, a hearing aid is provided, comprising a bte hearing aid housing configured to be worn behind the pinna of a user, at least one bte sound input transducer, such as an omni-directional microphone, a directional microphone, a transducer for an implantable hearing aid, a telecoil, a receiver of a digital audio datastream, etc., accommodated in the bte hearing aid housing, each of which is configured for conversion of sound into a respective audio signal, an ite microphone housing configured to be positioned in the outer ear of the user for fastening and retaining, in its intended position, at least one ite microphone accommodated in the ite microphone housing, each of which is configured for conversion of acoustic sound into a respective audio signal, at least one adaptive cue filter, each of which having an input that is provided with an output signal from a respective one of the at least one bte sound input transducer, and the filter coefficients of which are adapted so that the difference between an output of the at least one ite microphone and a combined output of the at least one adaptive cue filter is minimized, or substantially minimized, or reduced, a processor configured to generate a hearing loss compensated output signal based on a combination of the filtered audio signals output by the at least one cue filter, an output transducer for conversion of the hearing loss compensated output signal to an auditory output signal that can be received by the human auditory system, an adaptive feedback canceller for feedback suppression and having an input connected to an output of the processor for reception of the hearing loss compensated output signal, at least one output modelling the feedback path from the output of the output transducer to the respective at least one bte microphone and connected to a subtractor for subtraction of the at least one output from the output of the respective at least one bte microphone and outputting the difference to the respective at least one adaptive cue filter. the hearing aid further comprises a feedback and cue controller with inputs connected to the at least one output of the adaptive feedback canceller and the output of the at least one adaptive cue filter, and configured to control the at least one adaptive cue filter so that the difference between an output of the at least one ite microphone and a combined output of the at least one adaptive cue filter is reduced, preferably minimized, taking feedback into account. the hearing aid may further have a sound signal transmission member for transmission of a sound signal from a sound output in the bte hearing aid housing at a first end of the sound signal transmission member to the ear canal of the user at a second end of the sound signal transmission member, and an earpiece configured to be inserted in the ear canal of the user for fastening and retaining the sound signal transmission member in its intended position in the ear canal of the user. throughout the present disclosure, the “output signals of the at least one ite microphone” may be used to identify any analogue or digital signal forming part of the signal path from the output of the at least one ite microphone to an input of the processor, including pre-processed output signals of the at least one ite microphone. likewise, the “output signals of the at least one bte sound input transducer” may be used to identify any analogue or digital signal forming part of the signal path from the at least one bte sound input transducer to an input of the processor, including pre-processed output signals of the at least one bte sound input transducer. in use, the at least one ite microphone is positioned so that the output signal of the at least one ite microphone generated in response to the incoming sound has a transfer function that constitutes a good approximation to the hrtfs of the user. for example, the at least one ite microphone may be constituted by a single microphone positioned at the entrance to the ear canal. the processor conveys the directional information contained in the output signal of the at least one ite microphone to the resulting hearing loss compensated output signal of the processor so that the hearing loss compensated output signal of the processor also attains a transfer function that constitutes a good approximation to the hrtfs of the user whereby improved localization is provided to the user. bte (behind-the-ear) hearings aids are well-known in the art. a bte hearing aid has a bte housing that is shaped to be worn behind the pinna of the user. the bte housing accommodates components for hearing loss compensation. a sound signal transmission member, i.e. a sound tube or an electrical conductor, transmits a signal representing the hearing loss compensated sound from the bte housing into the ear canal of the user. in order to position the sound signal transmission member securely and comfortably at the entrance to the ear canal of the user, an earpiece, shell, or earmould may be provided for insertion into the ear canal of the user constituting an open solution. in an open solution, the earpiece, shell, or earmould does not obstruct the ear canal when it is positioned in its intended operational position in the ear canal. rather, there will be a passageway through the earpiece, shell, or earmould or, between a part of the ear canal wall and a part of the earpiece, shell, or earmould, so that sound waves may escape from behind the earpiece, shell, or earmould between the ear drum and the earpiece, shell, or earmould through the passageway to the surroundings of the user. in this way, the occlusion effect is substantially eliminated. typically, the earpiece, shell, or earmould is individually custom manufactured or manufactured in a number of standard sizes to fit the user's ear to sufficiently secure the sound signal transmission member in its intended position in the ear canal and prevent the earpiece from falling out of the ear, e.g., when the user moves the jaw. the output transducer may be a receiver positioned in the bte hearing aid housing. in this event, the sound signal transmission member comprises a sound tube for propagation of acoustic sound signals from the receiver positioned in the bte hearing aid housing and through the sound tube to an earpiece positioned and retained in the ear canal of the user and having an output port for transmission of the acoustic sound signal to the eardrum in the ear canal. the output transducer may be a receiver positioned in the earpiece. in this event, the sound signal transmission member comprises electrical conductors for propagation of audio signals from the output of a processor in the bte hearing aid housing through the conductors to a receiver positioned in the earpiece for emission of sound through an output port of the earpiece. the ite microphone housing accommodating at least one ite microphone may be combined with, or be constituted by, the earpiece so that the at least one microphone is positioned proximate the entrance to the ear canal when the earpiece is fastened in its intended position in the ear canal. the ite microphone housing may be connected to the bte hearing aid housing with an arm, possibly a flexible arm that is intended to be positioned inside the pinna, e.g. around the circumference of the conchae abutting the antihelix and at least partly covered by the antihelix for retaining its position inside the outer ear of the user. the arm may be pre-formed during manufacture, preferably into an arched shape with a curvature slightly larger than the curvature of the antihelix, for easy fitting of the arm into its intended position in the pinna. in one example, the arm has a length and a shape that facilitate positioning of the at least one ite microphone in an operating position immediately below the triangular fossa. the processor may be accommodated in the bte hearing aid housing, or in the ear piece, or part of the processor may be accommodated in the bte hearing aid housing and part of the processor may be accommodated in the ear piece. there is a one-way or two-way communication link between circuitry of the bte hearing aid housing and circuitry of the earpiece. the link may be wired or wireless. likewise, there is a one-way or two-way communication link between circuitry of the bte hearing aid housing and the at least one ite microphone. the link may be wired or wireless. the processor operates to perform hearing loss compensation while maintaining spatial information of the sound environment for optimum spatial performance of the hearing aid and while at the same time providing as large maximum stable gain as possible. the output signal of the at least one ite microphone of the earpiece may be a combination of several pre-processed ite microphone signals or the output signal of a single ite microphone of the at least one ite microphone. the short time spectrum for a given time instance of the output signal of the at least one ite microphone of the earpiece is denoted s iec (f,t) (iec=in the ear component). one or more output signals of the at least one bte sound input transducers are provided. the spectra of these signals are denoted s 1 btec (f,t)t), and s 2 btec (f,t), etc (btec=behind the ear component). the output signals may be pre-processed. pre-processing may include, without excluding any form of processing; adaptive and/or static feedback suppression, adaptive or fixed beamforming and pre-filtering. adaptive cue filters may be configured to adaptively filter the audio signals of the at least one bte sound input transducer so that they correspond to the output signal of the at least one ite microphone as closely as possible. the adaptive cue filters g 1 , g 2 , . . . , g n have the respective transfer functions: g 1 (f,t), g 2 (f,t), . . . , g n (f,t). the at least one ite microphone may operate as monitor microphone(s) for generation of an audio signal with the desired spatial information of the current sound environment. each output signal of the at least one bte sound input transducer is filtered with a respective adaptive cue filter, the filter coefficients of which are adapted to provide a combined output signal of the adaptive cue filter(s) that resembles the audio signal provided by the at least one ite microphone as closely as possible. the filter coefficients are adapted to obtain an exact or approximate solution to the following minimization problem: min g 1 (f,t) . . . g n (f,t) ∥s iec ( f,t )− g 1 ( f,t ) s 1 btec ( f,t )− . . . − g n ( f,t ) s n btec ( f,t )∥ p (1) wherein p is the norm. preferably p=2. the algorithm controlling the adaption could (without being restricted to) e.g. be based on least mean square (lms) or recursive least squares (rls), possibly normalized, optimization methods in which p=2. various weights may be incorporated into the minimization problems above so that the solution is optimized as specified by the values of the weights. for example, frequency weights w(f) may optimize the solution in certain one or more frequency ranges while information in other frequency ranges may be disregarded. thus, the minimization problem may be modified into: min g 1 (f,t) . . . g n (f,t) ∥w ( f )(( s iec ( f,t )− g 1 ( f,t ) s 1 btec ( f,t )− . . . − g n ( f,t ) s n btec ( f,t ))∥ p (2) further, in one or more selected frequency ranges, only magnitude of the transfer functions may be taken into account during minimization while phase is disregarded, i.e. in the one or more selected frequency range, the transfer function is substituted by its absolute value. subsequent to the adaptive cue filtering, the combined output signal of the adaptive cue filter(s) is passed on for further hearing loss compensation processing, e.g. with a compressor. in this way, only signals from the at least one bte sound input transducer is possibly amplified as a result of hearing loss compensation while the audio signal of the alt least one ite microphone is not included in the hearing loss compensation processing, whereby possible feedback from the output transducer to the at least one ite microphone is reduced, preferably minimized, and a large maximum stable gain can be provided. for example, in a hearing aid with one ite microphone, and two bte microphones constituting the at least one bte sound input transducer, and in the event that the incident sound field consist of sound emitted by a single speaker, the emitted sound having the short time spectrum x(f,t); then, under the assumption that no pre-processing is performed with relation to the ite microphone signal and that the ite microphone reproduces the actual hrtf perfectly then the following signals are provided: s iec ( f,t )=hrtf( f ) x ( f,t ) (3) s 1,2 btec ( f,t )= h 1,2 ( f ) x ( f,t ) (4) where h 1,2 (f) are the hearing aid related transfer functions of the two bte microphones. after sufficient adaptation, the hearing aid impulse response convolved with the resulting adapted filters and summed will be equal the actual hrtf so that lim t→∞ g 1 ( f,t ) h 1 ( f )+ g 2 ( f,t ) h 2 ( f )=hrtf( f ) (5) if the speaker moves and thereby changes the hrtf, the adaptive cue filters, i.e. the algorithm adjusting the filter coefficients, adapt towards the new minimum of minimization problem (2). the time constants of the adaptation are set to appropriately respond to changes of the current sound environment. feedback may be taken into account by performing the solution of the minimization problem (2) subject to the condition that the gain of the feedback loops must be less than one, i.e. subject to the condition that wherein h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) are the transfer functions of the feedback path associated with the n'th bte microphone of the at least one bte microphone, and msg(f) is the maximum stable gain, in this way, it is ensured that a desired maximum stable gain will be available. alternatively, the requirement of spatial cue preservation and feedback cancellation may be balanced by solving: wherein p is the norm factor, e.g. p=2, and α is a weighting factor balancing spatial cue accuracy and feedback performance. α may be frequency dependent so that in a frequency range with low probability of feedback, α may be of low value, and in a frequency range with high probability of feedback, α may be of high value in order to take feedback appropriately into account in the frequency range in question. the transfer functions h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) of the feedback paths may be modelled or approximated by an adaptive feedback cancellation circuit well-known in the art. various weights may be incorporated into the minimization problems above so that the solution is optimized as specified by the values of the weights. for example, frequency weights w(f) may optimize the solution in certain one or more frequency ranges. thus, the minimization problem may be modified into: subject to the condition that the target transfer function need not be defined by the hrtf for the various directions i. any transfer function that includes spatial cues may be used as the target transfer function. as used herein, the terms “processor”, “signal processor”, “controller”, “system”, etc., are intended to refer to cpu-related entities, either hardware, a combination of hardware and software, software, or software in execution. for example, a “processor”, “signal processor”, “controller”, “system”, etc., may be, but is not limited to being, a process running on a processor, a processor, an object, an executable file, a thread of execution, and/or a program. by way of illustration, the terms “processor”, “signal processor”, “controller”, “system”, etc., designate both an application running on a processor and a hardware processor. one or more “processors”, “signal processors”, “controllers”, “systems” and the like, or any combination hereof, may reside within a process and/or thread of execution, and one or more “processors”, “signal processors”, “controllers”, “systems”, etc., or any combination hereof, may be localized on one hardware processor, possibly in combination with other hardware circuitry, and/or distributed between two or more hardware processors, possibly in combination with other hardware circuitry. the hearing aid may be a multi-channel hearing aid in which signals to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels. the adaptive feedback cancellation circuitry may also be divided into the plurality of frequency channels; or, the adaptive feedback cancellation circuitry may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels, than the other circuitry is divided into. the processor may be configured for processing the output signals of the at least one ite microphone and the at least one bte sound input transducer in such a way that the hearing loss compensated output signal substantially preserves spatial cues in a selected frequency band. the selected frequency band may comprise one or more of the frequency channels, or all of the frequency channels. the selected frequency band may be fragmented, i.e. the selected frequency band need not comprise consecutive frequency channels. the plurality of frequency channels may include warped frequency channels, for example all of the frequency channels may be warped frequency channels. outside the selected frequency band, the at least one ite microphone may be connected conventionally as an input source to the processor of the hearing aid and may cooperate with the processor of the hearing aid in a well-known way. in this way, the at least one ite microphone supplies the input to the hearing aid at frequencies where the hearing aid is capable of supplying the desired gain with this configuration. in the selected frequency band, wherein the hearing aid cannot supply the desired gain with this configuration, the microphones of bte hearing aid housing are included in the signal processing as disclosed above. in this way, the gain can be increased while simultaneously maintain the spatial information about the sound environment provided by the at least one ite microphone. the hearing aid may for example comprise a first filter connected between the processor input and the at least one ite microphone, and a second complementary filter connected between the processor input and a combined output of the at least one bte sound input transducer, the filters passing and blocking frequencies in complementary frequency bands so that one of the at least one ite microphone and the combined output of at least one bte sound input transducer constitutes the main part of the input signal supplied to the processor input in one frequency band, and the other one of the at least one ite microphone and the combined output of at least one bte sound input transducer constitutes the main part of the input signal supplied to the processor input in the complementary frequency band. in this way, the at least one ite microphone may be used as the sole input source to the processor in a frequency band wherein the required gain for hearing loss compensation can be applied to the output signal of the at least one ite microphone. outside this frequency band, the combined output signal of the at least one bte sound input transducer is applied to the processor for provision of the required gain. the combination of the signals could e.g. be based on different types of band pass filtering. a hearing aid includes: a bte hearing aid housing configured to be worn behind a pinna of a user; at least one bte sound input transducer accommodated in the bte hearing aid housing, each of which is configured for conversion of acoustic sound into a respective audio sound signal; an ite microphone housing configured to be positioned in an outer ear of the user; at least one ite microphone accommodated in the ite microphone housing, each of which is configured for conversion of acoustic sound into a respective audio sound signal; at least one adaptive cue filter, each of which having an input that is provided with an output from the at least one bte sound input transducer, wherein filter coefficients of the at least one adaptive cue filter are adapted so that a difference between an output of the at least one ite microphone and a combined output of the at least one adaptive cue filter is reduced; a processor configured to generate a hearing loss compensated output signal based on output by the at least one cue filter; an output transducer for conversion of the hearing loss compensated output signal to an auditory output signal that can be received by a human auditory system; an adaptive feedback canceller for feedback suppression and having an input connected to the processor for reception of the hearing loss compensated output signal, wherein the adaptive feedback canceller is configured to provide at least one output modelling a feedback path between the output transducer and the at least one bte sound input transducer, wherein the at least one output modelling the feedback path is provided to a subtractor for subtraction of the at least one output modelling the feedback path from the output of the at least one bte sound input transducer to obtain a difference, the subtractor outputting the difference to the at least one adaptive cue filter; and a feedback and cue controller connected to the adaptive feedback canceller and the at least one adaptive cue filter, wherein the feedback and cue controller is configured to control the at least one adaptive cue filter so that the difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter is reduced. optionally, the filter coefficients of the at least one adaptive cue filter may be adapted towards a solution of: wherein s iec (f,t) is a short time spectrum at time t of the output signal of the at least one ite microphone, and s 1 btec (f,t)t), s 2 btec (f,t), . . . , s n btec (f,t) are short time spectra at time t of the output of the at least one bte sound input transducer, and g 1 btec (f,t), g 2 btec (f,t), . . . , g n btec (f,t) are transfer functions of pre-processing filters connected to respective output(s) of the at least one bte sound input transducer, and h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) are transfer functions of feedback path associated with the n'th bte microphone of the at least one bte microphone, p is a norm factor, w(f) is a frequency dependent weighting factor, and α is a weighting factor balancing spatial cue accuracy and feedback performance. optionally, the filter coefficients of the at least one adaptive cue filter may be adapted towards a solution of: min g 1 btec (f,t) . . . g n btec (f,t) ∥w ( f )( s iec ( f,t )− g 1 btec ( f,t ) s 1 btec ( f,t )− . . . − g n ( f,t ) s n btec ( f,t ))∥ p subject to a condition that wherein s iec (f,t) is a short time spectrum at time t of the output signal of the at least one ite microphone, and s 1 btec (f,t), s 2 btec (f,t), . . . , s n btec (f,t) are short time spectra at time t of the output of the at least one bte sound input transducer, and g 1 btec (f,t), g 2 btec (f,t), . . . , g n btec (f,t) are transfer functions of pre-processing filters connected to respective output(s) of the at least one bte sound input transducer, h fb,1 btec (f), h fb,2 btec (f), . . . , h fb,n btec (f) are transfer functions of feedback path associated with the n'th bte microphone of the at least one bte microphone, p is a norm factor, and msg(f) is a maximum stable gain. optionally, the filter coefficients of the at least one adaptive cue filter may comprise sets of filter coefficients, and wherein the hearing aid further comprises a memory for accommodation of the sets of filter coefficients of the at least one adaptive cue filter, each of the sets of filter coefficients is for a specific direction of arrival with relation to the hearing aid. optionally, the at least one adaptive cue filter may be loaded with the set of filter coefficients that provides a minimum difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter. optionally, the at least one adaptive cue filter may be allowed to further adapt after the at least one adaptive cue filter is loaded with the set of filter coefficients that provides the minimum difference. optionally, the at least one adaptive cue filter may be prevented from further adapting when changes of values of the filter coefficients are below a prescribed threshold. optionally, the audio sound signals from the bte and the ite may be divided into a plurality of frequency channels, and wherein the at least one adaptive cue filter may be configured for individually processing the audio sound signals in one or more of the frequency channels optionally, the at least one bte sound input transducer may be disconnected from the processor in one or more of the frequency channels so that hearing loss compensation is based solely on the output of the at least one ite microphone. optionally, the at least one bte sound input transducer may comprise a first bte sound input transducer and a second bte sound input transducer, and the at least one adaptive cue filter may comprise a first adaptive cue filter and a second adaptive cue filter; the first adaptive cue filter may have an input that is provided with an output signal from the first bte sound input transducer; and filter coefficients of the first adaptive cue filter may be adapted so that a difference between the output of the at least one ite microphone and a combined output of the first and second adaptive cue filters is reduced. optionally, the second adaptive cue filter may have an input that is provided with an output signal from the second bte sound input transducer, and filter coefficients of the second adaptive cue filter may be adapted so that a difference between the output of the at least one ite microphone and a combined output of the first and second adaptive cue filters is reduced. optionally, α may be frequency dependent. optionally, w(f) may be equal to 1. optionally, p may be equal to 2. optionally, the filter coefficients of the at least one adaptive cue filter may be adapted so that the difference between the output of the at least one ite microphone and the combined output of the at least one adaptive cue filter is minimized. optionally, the hearing aid may further include: a sound signal transmission member for transmission of a sound signal from a sound output in the bte hearing aid housing at a first end of the sound signal transmission member to the ear canal of the user at a second end of the sound signal transmission member; and an earpiece configured to be inserted in the ear canal of the user for fastening and retaining the sound signal transmission member in its intended position in the ear canal of the user. a hearing aid includes: a bte hearing aid housing; a bte sound input transducer accommodated in the bte hearing aid housing; an ite microphone housing; an ite microphone accommodated in the ite microphone housing; a cue filter having an input that is provided with an output from the bte sound input transducer; a processor configured to generate a hearing loss compensated output signal based on an output by the cue filter; an output transducer for conversion of the hearing loss compensated output signal to an auditory output signal; an adaptive feedback canceller configured to provide an output modelling a feedback path between the output transducer and the bte sound input transducer, wherein the output modelling the feedback path is provided to a subtractor for subtraction of the output modelling the feedback path from the output of the bte sound input transducer to obtain a difference, the subtractor outputting the difference to the cue filter; and a feedback and cue controller connected to the adaptive feedback canceller and the cue filter, wherein the feedback and cue controller is configured to control the cue filter to reduce a difference between an output of the ite microphone and a combined output that is obtained using at least the cue filter. optionally, the combined output may be obtained using the output from the cue filter and another output from another cue filter. optionally, the feedback and cue controller may be configured to control the cue filter to minimize the difference between the output of the ite microphone and the combined output. optionally, the cue filter may comprise sets of filter coefficients, and wherein the hearing aid may further comprise a memory for accommodation of the sets of filter coefficients, each of the sets of filter coefficients is for a specific direction of arrival with relation to the hearing aid. optionally, the cue filter may be loaded with the set of filter coefficients that provides a minimum difference between the output of the ite microphone and the combined output. optionally, the cue filter may be allowed to further adapt after the cue filter is loaded with the set of filter coefficients that provides the minimum difference. optionally, the cue filter may be prevented from further adapting when a change of filter coefficient value is below a prescribed threshold. other and further aspects and features will be evident from reading the following detailed description of the embodiments. brief description of the drawings the drawings illustrate the design and utility of embodiments, in which similar elements are referred to by common reference numerals. these drawings are not necessarily drawn to scale. in order to better appreciate how the above-recited and other advantages and objects are obtained, a more particular description of the embodiments will be rendered, which are illustrated in the accompanying drawings. these drawings depict only exemplary embodiments and are not therefore to be considered limiting in the scope of the claims. fig. 1 shows a plot of the angular frequency spectrum of an open ear, fig. 2 shows a plot of the angular frequency spectrum of a bte front microphone worn at the same ear, fig. 3 shows plots of maximum stable gain of a bte front and rear microphones and an open fitted ite microphone positioned in the ear canal, fig. 4 schematically illustrates an exemplary new hearing aid, fig. 5 schematically illustrates another exemplary new hearing aid, fig. 6 shows in perspective a new hearing aid with an ite-microphone in the outer ear of a user, fig. 7 shows a schematic block diagram of a new hearing aid with adaptive cue filters, fig. 8 shows a schematic block diagram of the hearing aid of fig. 7 with added feedback cancellation, fig. 9 shows a schematic block diagram of a new hearing aid with an arbitrary number of microphones, fig. 10 shows a schematic block diagram of a new hearing aid, fig. 11 shows a schematic block diagram of the hearing aid of fig. 10 with added feedback cancellation, and fig. 12 shows a schematic block diagram of the hearing aid of fig. 11 with added adaptive filtering. detailed description various embodiments are described hereinafter with reference to the figures. it should be noted that the figures are not necessarily drawn to scale and that elements of similar structures or functions are represented by like reference numerals throughout the figures. it should also be noted that the figures are only intended to facilitate the description of the embodiments. they are not intended as an exhaustive description of the claimed invention or as a limitation on the scope of the claimed invention. in addition, an illustrated embodiment needs not have all the aspects or advantages shown. an aspect or an advantage described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced in any other embodiments even if not so illustrated, or if not so explicitly described. fig. 4 schematically illustrates a bte hearing aid 10 comprising a bte hearing aid housing 12 (not shown—outer walls have been removed to make internal parts visible) to be worn behind the pinna 100 of a user. the bte housing 12 accommodates at least one bte sound input transducer 14 , 16 with a front microphone 14 and a rear microphone 16 for conversion of a sound signal into a microphone audio signal, optional pre-filters (not shown) for filtering the respective microphone audio signals, a/d converters (not shown) for conversion of the respective microphone audio signals into respective digital microphone audio signals that are input to a processor 18 configured to generate a hearing loss compensated output signal based on the input digital audio signals. the hearing loss compensated output signal is transmitted through electrical wires contained in a sound signal transmission member 20 to a receiver 22 for conversion of the hearing loss compensated output signal to an acoustic output signal for transmission towards the eardrum of a user and contained in an earpiece 24 that is shaped (not shown) to be comfortably positioned in the ear canal of a user for fastening and retaining the sound signal transmission member in its intended position in the ear canal of the user as is well-known in the art of bte hearing aids. the earpiece 24 also holds one ite microphone 26 that is positioned at the entrance to the ear canal when the earpiece is positioned in its intended position in the ear canal of the user. the ite microphone 26 is connected to an a/d converter (not shown) and optional to a pre-filter (not shown) in the bte housing 12 , with electrical wires (not visible) contained in the sound transmission member 20 . the bte hearing aid 10 is powered by battery 28 . various possible functions of the processor 18 are disclosed above and some of these in more detail below. fig. 5 schematically illustrates another bte hearing aid 10 similar to the hearing aid shown in fig. 1 , except for the difference that in fig. 5 , the receiver 22 is positioned in the hearing aid housing 12 and not in the earpiece 24 , so that acoustic sound output by the receiver 22 is transmitted through the sound tube 20 and towards the eardrum of the user when the earpiece 24 is positioned in its intended position in the ear canal of the user. the positioning of the ite microphone 26 proximate the entrance to the ear canal of the user when the bte hearing aids 10 of figs. 4 and 5 are used is believed to lead to a good reproduction of the hrtfs of the user. fig. 6 shows a bte hearing aid 10 in its operating position with the bte housing 12 behind the ear, i.e. behind the pinna 100 , of the user. the illustrated bte hearing aid 10 is similar to the hearing aids shown in figs. 4 and 5 except for the fact that the ite microphone 26 is positioned in the outer ear of the user outside the ear canal at the free end of an arm 30 . the arm 30 is flexible and the arm 30 is intended to be positioned inside the pinna 100 , e.g. around the circumference of the conchae 102 behind the tragus 104 and antitragus 106 and abutting the antihelix 108 and at least partly covered by the antihelix for retaining its position inside the outer ear of the user. the arm may be pre-formed during manufacture, preferably into an arched shape with a curvature slightly larger than the curvature of the antihelix 104 , for easy fitting of the arm 30 into its intended position in the pinna. the arm 30 contains electrical wires (not visible) for interconnection of the ite microphone 26 with other parts of the bte hearing aid circuitry. in one example, the arm 30 has a length and a shape that facilitate positioning of the ite microphone 26 in an operating position below the triangular fossa. fig. 7 is a block diagram illustrating one example of signal processing in the new hearing aid 10 . the illustrated hearing aid 10 has a front microphone 14 and a rear microphone 16 accommodated in the bte hearing aid housing configured to be worn behind the pinna of the user, for conversion of sound signals arriving at the microphones 14 , 16 into respective audio signals 33 , 35 . further, the illustrated hearing aid 10 has an ite microphone 26 accommodated in an earpiece (not shown) to be positioned in the outer ear of the user, for conversion of sound signals arriving at the microphone 26 into audio signal 31 . the microphone audio signals 31 , 33 , 35 are digitized and pre-processed, such as pre-filtered, in respective pre-processors 32 , 34 , 36 . the pre-processed audio signals 38 , 40 of the front and rear microphones 14 , 16 are filtered in respective adaptive cue filters 42 , 44 , and the adaptively filtered signals 46 , 48 are added to each other in adder 50 and the combined signal 52 is input to processor 18 for hearing loss compensation. the hearing loss compensated signal 54 is output to the receiver 22 that converts the signal 54 to an acoustic output signal for transmission towards the ear drum of the user. adaptation of the filter coefficients of adaptive cue filters 42 , 44 are controlled by adaptive controller 56 that controls the adaptation of the filter coefficients to reduce, and preferably eventually minimize, the difference 58 between the output 52 of adder 46 and the pre-processed ite microphone audio signal 60 , output by subtractor 62 . in this way, the input signal 52 to the processor 18 models the microphone audio signal 60 of the ite microphone 26 , and thus also substantially models the hrtfs of the user. the pre-processed output signal 60 of the ite microphone 26 of the earpiece has a short time spectrum denoted s iec (f,t) (iec=in the ear component). the spectra of the pre-processed audio signals 38 , 40 of the front and rear microphones 14 , 16 are denoted s 1 btec (f,t), and s 2 btec (f,t) (btec=behind the ear component). pre-processing may include, without excluding any form of processing; adaptive and/or static feedback suppression, adaptive or fixed beamforming and pre-filtering. the adaptive controller 56 is configured to control the filter coefficients of adaptive cue filters 42 , 44 so that their summed output 52 corresponds to the pre-processed output signal 60 of the ite microphone 26 as closely as possible. the adaptive cue filters 42 , 44 have the respective transfer functions: g 1 (f,t), and g 2 (f,t) the ite microphone 26 operates as monitor microphone for generation of an audio signal 60 with the desired spatial information of the current sound environment due to its positioning in the outer ear of the user. thus, the filter coefficients of the adaptive cue filters 42 , 44 are adapted to obtain an exact or approximate solution to the minimization problem: min g 1 (f,t),g 2 (f,t)∥ s iec ( f,t )− g 1 ( f,t ) s 1 btec ( f,t )− g 2 ( f,t ) s n btec ( f,t )∥ p (11) wherein p is the norm-factor. the algorithm controlling the adaption could (without being restricted to) e.g. be based on least mean square (lms) or recursive least squares (rls), possibly normalized, optimization methods in which p=2. subsequent to the adaptive cue filtering, the combined output signal 52 of the adaptive cue filters 42 , 44 is passed on for further hearing loss compensation processing, e.g. in a compressor. in this way, only signals from the front and rear microphones 14 , 16 are possibly amplified as a result of hearing loss compensation while the audio signal 60 of the ite microphone 26 is not processed in the processor 18 configured for hearing loss processing, whereby possible feedback from the output transducer 22 to the ite microphone 26 is reduced, preferably minimized, and a large maximum stable gain can be provided. for example, in the event that the incident sound field consists of sound emitted by a single speaker, the emitted sound having the short time spectrum x(f,t); then, under the assumption that no pre-processing is performed with relation to the ite microphone signal 60 and that the ite microphone 26 reproduces the actual hrtf perfectly then the following signals are provided: s iec ( f,t )=hrtf( f ) x ( f,t ) (12) s 1,2 btec ( f,t )= h 1,2 ( f ) x ( f,t ) (13) where h 1,2 (f) are the hearing aid related transfer functions of the two bte microphones 14 , 16 . after sufficient adaptation, the hearing aid impulse response convolved with the resulting adapted filters and summed will be equal the actual hrtf so that lim t→∞ g 1 ( f,t ) h 1 ( f )+ g 2 ( f,t ) h 2 ( f )=hrtf( f ) (14) if the speaker moves and thereby changes the actual hrtf, the adaptive cue filters 42 , 44 , i.e. the adaptive controller 56 by adjusting the filter coefficients, adapt towards the new minimum of the minimization problem (11). the time constants of the adaptation are set to appropriately respond to changes of the current sound environment. in the event that feedback occurs in the hearing aid, adaptation may be stopped, i.e. the filter coefficients may be prevented from changing, or the adaptation rate may be slowed down, in order to avoid that feedback is transferred from the audio signal of the at least one ite microphone to the output signal(s) of the at least one bte sound input transducer during presence of feedback. the filter coefficients of the adaptive cue filters 42 , 44 may be predetermined so that a set of filter coefficients is provided for a specific hrtf. the sets of filter coefficients, one set for each predetermined hrtf, may be determined using a manikin, such as kemar. the filter coefficients are determined for at number of direction of arrivals for the hearing aid as disclosed above; however under controlled conditions and allowing adaptation of long duration. in this way, an approximation to the individual hrtfs is provided that can be of sufficient accuracy for the hearing aid user to maintain sense of direction when wearing the hearing aid. during use, the set of filter coefficients is selected that reduces, and preferably eventually minimizes, the difference between the combined output signal, possibly pre-processed, of the at least one bte sound input transducer and the output signal, possibly pre-processed, of the at least one ite microphone. during use, the adaptive cue filter may be allowed to further adapt to the individual hrtf of the user in question. the adaptation may be stopped when the filter coefficients have become stable so that the at least one ite microphone is no longer used for the hrtf in question. the new hearing aid circuitry shown in fig. 7 may operate in the entire frequency range of the hearing aid 10 . the hearing aid 10 shown in fig. 7 may be a multi-channel hearing aid in which microphone audio signals 38 , 40 , 60 to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels. for a multi-channel hearing aid 10 , fig. 7 may illustrate the circuitry and signal processing in a single frequency channel. the circuitry and signal processing may be duplicated in a plurality of the frequency channels, e.g. in all of the frequency channels. for example, the signal processing illustrated in fig. 7 may be performed in a selected frequency band, e.g. selected during fitting of the hearing aid to a specific user at a dispenser's office. the selected frequency band may comprise one or more of the frequency channels, or all of the frequency channels. the selected frequency band may be fragmented, i.e. the selected frequency band need not comprise consecutive frequency channels. the plurality of frequency channels may include warped frequency channels, for example all of the frequency channels may be warped frequency channels. outside the selected frequency band, the ite microphone 26 may be connected conventionally as an input source to the processor 18 of the hearing aid 10 and may cooperate with the processor 18 of the hearing aid 10 in a well-known way. in this way, the ite microphone supplies the input to the hearing aid at frequencies where the hearing aid is capable of supplying the desired gain with this configuration. in the selected frequency band, wherein the hearing aid cannot supply the desired gain with this configuration, the microphones 14 , 16 of bte hearing aid housing are included in the signal processing as disclosed above. in this way, the gain can be increased while the spatial information of the sound environment as provided by the ite microphone is simultaneously maintained. fig. 8 is a block diagram illustrating a new hearing aid 10 similar to the hearing aid 10 shown in fig. 7 except for the fact that adaptive feedback cancellation circuitry has been added, including an adaptive feedback filter 70 with an input 72 connected to the output of the hearing aid processor 18 and with outputs 74 - 1 , 76 - 1 , 76 - 2 , each of which is connected to a respective subtractor 78 - 1 , 80 - 1 , 80 - 2 for subtraction of each output 74 - 1 , 76 - 1 , 76 - 2 from a respective microphone output 31 , 33 , 35 to provide a respective feedback compensated signal 82 - 1 , 84 - 1 , 84 - 2 as is well-known in the art. each feedback compensated signal 82 - 1 , 84 - 1 , 84 - 2 is fed to the corresponding pre-processor 32 , 34 , 36 , and also to the adaptive feedback filter 70 for control of the adaption of the adaptive feedback filter 70 . the adaptive feedback filter outputs 74 - 1 , 76 - 1 , 76 - 2 provide signals that constitute approximations of corresponding feedback signals travelling from the output transducer 22 to the respective microphone 14 , 16 , 26 as is well-known in the art. the outputs 76 - 1 , 76 - 2 approximating feedback signals of the bte microphones are further connected to the adaptive controller 56 . the adaptive controller 56 of fig. 8 controls adjustment of the filter coefficients of adaptive cue filters 42 , 44 by solving minimization problem (11) subject to the condition that or by solving minimization problem in order to preserve spatial cue and simultaneously take feedback into account. typically p=2, and/or w(f)=1. the new hearing aid circuitry shown in fig. 8 may operate in the entire frequency range of the hearing aid 10 . the hearing aid 10 shown in fig. 8 may be a multi-channel hearing aid in which microphone audio signals 38 , 40 , 60 to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels possibly apart from the adaptive feedback cancellation circuitry 70 , 72 , 74 - 1 , 74 - 2 , 76 - 1 , 76 - 2 , 78 - 1 , 78 - 2 , 80 - 1 , 80 - 2 , 82 - 1 , 82 - 2 , 84 - 1 , 84 - 2 that may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. for a multi-channel hearing aid 10 , the part of fig. 8 corresponding to the circuitry of fig. 7 may illustrate the circuitry and signal processing in a single frequency channel, while the adaptive circuitry that may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. the circuitry and signal processing may be duplicated in a plurality of the frequency channels, e.g. in all of the frequency channels. for example, the signal processing illustrated in fig. 8 may be performed in a selected frequency band, e.g. selected during fitting of the hearing aid to a specific user at a dispenser's office. the selected frequency band may comprise one or more of the frequency channels, or all of the frequency channels. the selected frequency band may be fragmented, i.e. the selected frequency band need not comprise consecutive frequency channels. the plurality of frequency channels may include warped frequency channels, for example all of the frequency channels may be warped frequency channels. outside the selected frequency band, the at least one ite microphone may be connected conventionally as an input source to the processor of the hearing aid and may cooperate with the processor of the hearing aid in a well-known way. in this way, the at least one ite microphone supplies the input to the hearing aid at frequencies where the hearing aid is capable of supplying the desired gain with this configuration. in the selected frequency band, wherein the hearing aid cannot supply the desired gain with this configuration, the microphones of bte hearing aid housing are included in the signal processing as disclosed above. in this way, the gain can be increased while simultaneously maintain the spatial information about the sound environment provided by the at least one ite microphone. fig. 9 is a block diagram illustrating a new hearing aid 10 similar to the hearing aid 10 shown in fig. 7 and operating in a way similar to the hearing aid 10 shown in fig. 7 , except for the fact that the circuit has been generalized to include an arbitrary number n of ite microphones 26 - 1 , 26 - 2 , . . . , 26 -n, and an arbitrary number m of bte microphones 14 - 1 , 14 - 2 , . . . , 14 -m. in fig. 7 , n=1 and m=2. in fig. 9 , n and m can be any non-negative integer. the output signals 31 - 1 , 31 - 2 , . . . , 31 -n from the n ite microphones 26 - 1 , 26 - 2 , . . . , 26 -n are delayed by delays 41 - 1 , 41 - 2 , . . . , 41 -n after pre-processing in pre-processors 32 - 1 , 32 - 2 , . . . , 32 -n to compensate for the delays of the output signals 33 - 1 , 33 - 2 , . . . , 33 -m from the m bte microphones 14 - 1 , 14 - 2 , . . . , 14 -m, caused by the adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m. the delays 41 - 1 , 41 - 2 , . . . , 41 -n may also be used for beamforming. the output signals 31 - 1 , 31 - 2 , . . . , 31 -n from the n ite microphones 26 - 1 , 26 - 2 , . . . , 26 -n are further combined in the signal combiner 64 , e.g. as a weighted sum, and the output 60 of the signal combiner 64 is fed to a subtractor 72 as in the circuit shown in fig. 7 . likewise, the output signals 33 - 1 , 33 - 2 , . . . , 33 -m from the m bte microphones are pre-processed in pre-processors 34 - 1 , 34 - 2 , . . . , 34 -m and filtered in the respective adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m and combined in the signal combiner 50 , e.g. as a weighted sum, and the output 52 of the signal combiner 50 is fed to the subtractor 62 and the hearing aid processor 18 as in the circuit of fig. 7 . the adaptive controller 56 controls the adaptation of the filter coefficients of adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m to reduce, and preferably eventually minimize, the difference 58 between the output of bte signal combiner 50 and ite signal combiner 64 , provided by subtractor 62 , e.g. by solving the minimization problem (2) already mentioned above: wherein s iec is the output signal 60 of signal combiner 64 , and g 1 (f,t), g 2 (f,t), . . . , g n (f,t) are the transfer functions of the respective adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m. typically p=2, and/or w(f)=1. possible weights in the signal combination performed by the signal combiner 58 are included in the transfer functions g 1 (f,t), g 2 (f,t), . . . , g n (f,t). these weights may be frequency dependent. in this way, the output signal 52 of the bte signal combiner 50 models the combined ite microphone audio signal 60 of the ite microphones 26 - 1 , 26 - 2 , . . . , 26 -n, and thus also substantially models the hrtfs of the user. the new hearing aid circuitry shown in fig. 9 may operate in the entire frequency range of the hearing aid 10 . the hearing aid 10 shown in fig. 9 may be a multi-channel hearing aid in which microphone audio signals 31 - 1 , 31 - 2 , . . . , 31 -n, 33 - 1 , 33 - 2 , . . . , 33 -m to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels. for a multi-channel hearing aid 10 , fig. 9 may illustrate the circuitry and signal processing in a single frequency channel. the circuitry and signal processing may be duplicated in a plurality of the frequency channels, e.g. in all of the frequency channels. for example, the signal processing illustrated in fig. 9 may be performed in a selected frequency band, e.g. selected during fitting of the hearing aid to a specific user at a dispenser's office. the selected frequency band may comprise one or more of the frequency channels, or all of the frequency channels. the selected frequency band may be fragmented, i.e. the selected frequency band need not comprise consecutive frequency channels. the plurality of frequency channels may include warped frequency channels, for example all of the frequency channels may be warped frequency channels. outside the selected frequency band, the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n may be connected conventionally as an input source to the processor 18 of the hearing aid 10 and may cooperate with the processor 18 of the hearing aid 10 in a well-known way. in this way, the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n supply the input to the hearing aid at frequencies where the hearing aid is capable of supplying the desired gain with this configuration. in the selected frequency band, wherein the hearing aid cannot supply the desired gain with this configuration, the microphones 14 - 1 , 14 - 2 , . . . , 14 -m of bte hearing aid housing are included in the signal processing as disclosed above. in this way, the gain can be increased while simultaneously maintain the spatial information about the sound environment provided by the at least one ite microphone. in the hearing aid 10 shown in fig. 10 , adaptive feedback cancellation has been added to the hearing aid shown in fig. 9 similar to the way illustrated in fig. 8 in comparison with fig. 7 , i.e. an adaptive feedback filter 70 is added with an input 72 connected to the output of the hearing aid processor 18 and outputs 74 - 1 , 74 - 2 , . . . , 74 -n, 76 - 1 . 76 - 2 , . . . , 76 -m connected to subtractors 78 - 1 , 78 - 2 , . . . , 78 -n, 80 - 1 , 80 - 2 , . . . , 80 -m for subtraction of each output from a respective microphone output to provide a feedback compensated signal 82 - 1 , 82 - 2 , . . . , 82 -n, 84 - 1 , 84 - 2 , . . . , 84 -m fed to the corresponding pre-processing circuits 32 - 1 , 32 - 2 , . . . , 32 -n, 34 - 1 , 34 - 2 , . . . , 34 -m and to the adaptive feedback filter 70 for control of the adaption of the adaptive feedback filter 70 . the adaptive feedback filter outputs 74 - 1 , 74 - 2 , . . . , 74 -n, 76 - 1 . 76 - 2 , . . . , 76 -m provide signals that constitute approximations of corresponding feedback signals travelling from the output transducer 22 to the respective microphones 26 - 1 , 26 - 2 , . . . , 26 -n, 14 - 1 , 14 - 2 , . . . , 14 -m as is well-known in the art. further, the outputs 76 - 1 , 76 - 2 , . . . , 76 -m approximating feedback signals of the bte microphones 14 - 1 , 14 - 2 , . . . , 14 -m are connected to the adaptive controller 56 that controls the filter coefficients of adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m. in accordance with, e.g. equation 1 subject to condition 1, or equation 5, in order to preserve spatial cue and simultaneously take feedback into account. the adaptive controller 56 controls the adaptation of the filter coefficients of adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m to reduce, and preferably eventually minimize, the difference 58 between the output 60 of the ite signal combiner 64 and the output 52 of bte signal combiner 50 , provided by subtractor 62 , e.g. by solving the minimization problem: subject to the condition that wherein s iec is the output signal 60 of signal combiner 64 , and g 1 (f,t), g 2 (f,t), . . . , g n (f,t) are the transfer functions of the respective adaptive cue filters 42 - 1 , 42 - 2 , . . . , 42 -m. typically p=2, and/or w(f)=1. possible weights in the signal combination performed by the signal combiner 58 are included in the transfer functions g 1 (f,t), g 2 (f,t), . . . , g n (f,t). these weights may be frequency dependent. in this way, the output signal 52 of the bte signal combiner 50 models the combined ite microphone audio signal 60 of the ite microphones 26 - 1 , 26 - 2 , . . . , 26 -n, and thus also substantially models the hrtfs of the user. the new hearing aid circuitry shown in fig. 10 may operate in the entire frequency range of the hearing aid 10 . like the hearing aids shown in figs. 7-9 , the hearing aid 10 shown in fig. 10 may be a multi-channel hearing aid in which microphone audio signals 31 - 1 , 31 - 2 , . . . , 31 -n, 33 - 1 , 33 - 2 , . . . , 33 -m to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels, possibly apart from the adaptive feedback cancellation circuitry 70 , 72 , 74 - 1 , 74 - 2 , . . . , 74 -n, 76 - 1 , 76 - 2 , . . . , 76 -m, 78 - 1 , 78 - 2 , . . . , 78 -n, 80 - 1 , 80 - 2 , . . . , 80 -m, 82 - 1 , 82 - 2 , . . . , 82 -n, 84 - 1 , 84 - 2 , . . . , 84 -m, 86 that may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. as in figs. 7-9 , fig. 10 may also illustrate the circuitry and signal processing in a single frequency channel of a multi-channel hearing aid 10 . the circuitry and signal processing may be duplicated in a plurality of the frequency channels, e.g. in all of the frequency channels apart from the adaptive circuitry that may still operate in the entire frequency range; or, may be divided into its own frequency channels, typically with fewer frequency channels than the remaining illustrated circuitry. for a multi-channel hearing aid 10 , the part of fig. 10 corresponding to the circuitry of fig. 9 may illustrate the circuitry and signal processing in a single frequency channel, while the adaptive circuitry may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. the illustrated circuitry and signal processing may be duplicated in a plurality of the frequency channels, e.g. in all of the frequency channels. for example, the signal processing illustrated in fig. 10 may be performed in a selected frequency band, e.g. selected during fitting of the hearing aid to a specific user at a dispenser's office. the selected frequency band may comprise one or more of the frequency channels, or all of the frequency channels. the selected frequency band may be fragmented, i.e. the selected frequency band need not comprise consecutive frequency channels. the plurality of frequency channels may include warped frequency channels, for example all of the frequency channels may be warped frequency channels. outside the selected frequency band, the at least one ite microphone may be connected conventionally as an input source to the processor 18 of the hearing aid and may cooperate with the processor 18 of the hearing aid in a well-known way. in this way, the at least one ite microphone 26 - 1 , 26 - 1 , . . . , 26 -n supply the input to the hearing aid at frequencies where the hearing aid is capable of supplying the desired gain with this configuration. in the selected frequency band, wherein the hearing aid cannot supply the desired gain with this configuration, the microphones of bte hearing aid housing are included in the signal processing as disclosed above. in this way, the gain can be increased while simultaneously maintain the spatial information about the sound environment provided by the at least one ite microphone. the hearing aid 10 shown in fig. 11 is similar to the hearing aid 10 shown in fig. 10 and operates in the same way, apart from the fact that, in fig. 11 , a signal combiner 66 has been inserted in front of the processor 18 . the added signal combiner 66 comprises first filters connected between the processor input and the output 60 of the signal combiner 64 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n, and second complementary filters connected between the processor input and the output 52 of the signal combiner 50 of the at least one bte microphone 14 - 1 , 14 - 2 , . . . , 14 -m, the filters passing and blocking, respectively, frequencies in complementary frequency bands so that the output 60 of the signal combiner 64 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n constitutes the main part of the input signal 68 supplied to the processor input in one or more first frequency bands, and the output 52 of the signal combiner 50 of the at least one bte microphone 14 - 1 , 14 - 2 , . . . , 14 -m constitutes the main part of the input signal 68 supplied to the processor input in one or more complementary second frequency bands. in this way, the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n may be used as the sole input source to the processor 18 in one or more frequency bands wherein the required gain for hearing loss compensation can be applied to the output signal 60 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n. outside these one or more frequency bands, the combined output signal 52 of the at least one bte sound input transducer 14 - 1 , 14 - 2 , . . . , 14 -m is applied to the processor 18 for provision of the required gain. the combination of the signals performed in signal combiner 66 could e.g. be based on different types of band pass filtering. the hearing aid 10 shown in fig. 11 may be a multi-channel hearing aid in which microphone audio signals 31 - 1 , 31 - 2 , . . . , 31 -n, 33 - 1 , 33 - 2 , . . . , 33 -m to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels possibly apart from the adaptive feedback cancellation circuitry 70 , 72 , 74 - 1 , 74 - 2 , . . . , 74 -n, 76 - 1 , 76 - 2 , . . . , 76 -m, 78 - 1 , 78 - 2 , . . . , 78 -n, 80 - 1 , 80 - 2 , . . . , 80 -m, 82 - 1 , 82 - 2 , . . . , 82 -n, 84 - 1 , 84 - 2 , . . . , 84 -m, 86 that may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. the signal combiner 66 may connect the audio signal 60 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n as the sole input source to the processor 18 in one or more frequency channels in which no feedback is expected, and the combined output signal 52 of the at least one bte sound input transducer 14 - 1 , 14 - 2 , . . . , 14 -m in frequency channels with risk of feedback. the hearing aid 10 shown in fig. 12 is similar to the hearing aid 10 shown in fig. 11 and operates in the same way, apart from the fact that, in fig. 12 , the signal combiner 66 is adaptive, e.g. so that the interconnections of the output 60 of the signal combiner 64 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n and the output 52 of the signal combiner 50 of the at least one bte microphone 14 - 1 , 14 - 2 , . . . , 14 -m can be changed during operation of the hearing aid 10 , e.g. in response to the status of the feedback loops, whereby, the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n may be used as the sole input source to the processor 18 in one or more frequency bands in which no feedback is currently present, whereas in one or more frequency bands in which feedback is evolving, the combined output signal 52 of the at least one bte sound input transducer 14 - 1 , 14 - 2 , . . . , 14 -m is applied to the processor 18 for provision of the required gain without feedback. the hearing aid 10 shown in fig. 12 may be a multi-channel hearing aid in which microphone audio signals 31 - 1 , 31 - 2 , . . . , 31 -n, 33 - 1 , 33 - 2 , . . . , 33 -m to be processed are divided into a plurality of frequency channels, and wherein signals are processed individually in each of the frequency channels possibly apart from the adaptive feedback cancellation circuitry 70 , 72 , 74 - 1 , 74 - 2 , . . . , 74 -n, 76 - 1 , 76 - 2 , . . . , 76 -m, 78 - 1 , 78 - 2 , . . . , 78 -n, 80 - 1 , 80 - 2 , . . . , 80 -m, 82 - 1 , 82 - 2 , . . . , 82 -n, 84 - 1 , 84 - 2 , . . . , 84 -m, 86 that may still operate in the entire frequency range; or, may be divided into other frequency channels, typically fewer frequency channels than the remaining illustrated circuitry. the signal combiner 66 may adaptively connect the audio signal 60 of the at least one ite microphone 26 - 1 , 26 - 2 , . . . , 26 -n as the sole input source to the processor 18 in one or more frequency channels in which no feedback instability is currently present, and the combined output signal 52 of the at least one bte sound input transducer 14 - 1 , 14 - 2 , . . . , 14 -m in frequency channels with current risk of feedback. although particular embodiments have been shown and described, it will be understood that it is not intended to limit the claimed inventions to the preferred embodiments, and it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the claimed inventions. the specification and drawings are, accordingly, to be regarded in an illustrative rather than restrictive sense. the claimed inventions are intended to cover alternatives, modifications, and equivalents.
|
126-259-917-805-380
|
JP
|
[
"CN",
"US",
"JP"
] |
G03G15/00,G03G21/14,G06K15/00,G03G21/00,B41J29/38,B41J29/46,H04N1/00
| 2010-03-25T00:00:00 |
2010
|
[
"G03",
"G06",
"B41",
"H04"
] |
image forming apparatus and method for image forming
|
an image forming apparatus includes: a monitor that monitors a state of communication performed in the image forming apparatus; and a controller that, when the monitor monitors that the state of the communication is abnormal, controls the communication based on an operation of the image forming apparatus in which a state has been changed within previously determined time including a time point at which the state of the communication has become abnormal.
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1. an image forming apparatus comprising: a data signal monitor that monitors a communication state of a data signal in the image forming apparatus; a controller that, when the data signal monitor detects that the communication state of the data signal is abnormal, delays communication of the data signal such that the communication of the data signal is not performed during a previously determined time including a time point at which the communication state of the data signal has become abnormal due to an operation of the image forming apparatus; and a memory that, when the data signal monitor detects that the communication state of the data signal is abnormal, stores the operation of the image forming apparatus in which the state has been changed, wherein when a number of times that the operation of the image forming apparatus in which the state has been changed is stored in the memory exceeds a previously determined threshold value, the controller delays the communication of the data signal during previously set time for the operation of the image forming apparatus in which the state has been changed, and wherein in a case when the number of times that the operation of the image forming apparatus in which the state has been changed is stored in the memory exceeds the previously determined threshold value, when time obtained by subtracting the previously set time for the operation of the image forming apparatus in which the state has been changed from previously set communication time for a previously determined data amount is shorter than time required for the communication for the previously determined data amount, the controller reduces the previously set time for the operation of the image forming apparatus in which the state has been changed. 2. the image forming apparatus according to claim 1 , wherein when the data signal monitor detects that the communication state of the data signal is abnormal, the controller delays image data transmission/reception based on the operation of the image forming apparatus within the previously determined time including the time point at which the communication state of the data signal has become abnormal. 3. the image forming apparatus according to claim 1 , wherein the communication state of the data signal is abnormal when noise superimposed on the data signal cannot be eliminated. 4. an image forming apparatus comprising: a monitor that monitors a state of communication performed in the image forming apparatus; a controller that, when the monitor monitors that the state of the communication is abnormal, controls the communication based on an operation of the image forming apparatus in which a state has been changed within previously determined time including a time point at which the state of the communication has become abnormal; and a memory that, when the monitor monitors that the state of the communication is abnormal, stores the operation of the image forming apparatus in which the state has been changed, wherein when the number of times stored in the memory exceeds a previously determined threshold value, the controller performs control not to perform the communication during previously set time for the operation of the image forming apparatus in which the state has been changed, and wherein in a case where the number of times stored in the memory exceeds the previously determined threshold value, when time obtained by subtracting the previously set time for the operation of the image forming apparatus in which the state has been changed from previously set communication time for a previously determined data amount is shorter than time required for the communication for the previously determined data amount, the controller reduces the previously set time for the operation of the image forming apparatus in which the state has been changed. 5. an image forming apparatus comprising: a noise monitor that monitors noise which occurs in the image forming apparatus; a controller that, when the noise monitor detects that the noise has occurred, delays communication of a data signal such that communication of the data signal is not performed during a previously determined time including a time point at which the noise has occurred due to an operation of the image forming apparatus; and a memory that, when the noise monitor detects that the noise has occurred, stores the operation of the image forming apparatus in which the noise has occurred, wherein when a number of times that the operation of the image forming apparatus in which the noise has occurred is stored in the memory exceeds a previously determined threshold value, the controller delays the communication of the data signal during previously set time for the operation of the image forming apparatus in which the noise has occurred, and wherein in a case when the number of times that the operation of the image forming apparatus in which the noise has occurred is stored in the memory exceeds the previously determined threshold value, when time obtained by subtracting the previously set time for the operation of the image forming apparatus in which the noise has occurred from previously set communication time for a previously determined data amount is shorter than time required for the communication for the previously determined data amount, the controller reduces the previously set time for the operation of the image forming apparatus in which the noise has occurred. 6. a non-transitory computer readable medium storing a program causing a computer to execute a process for image forming, the process comprising: for a computer of an image forming apparatus, monitoring a communication state of a data signal in the image forming apparatus; when it is detected that the communication state of the data signal is abnormal, delaying communication of the data signal such that the communication of the data signal is not performed during a previously determined time including a time point at which the communication state of the data signal has become abnormal due to an operation of the image forming apparatus; and when it is detected that the communication state of the data signal is abnormal, storing the operation of the image forming apparatus in which the state has been changed, wherein when a number of times that the operation of the image forming apparatus in which the state has been changed is stored exceeds a previously determined threshold value, the communication of the data signal is delayed during previously set time for the operation of the image forming apparatus in which the state has been changed, and wherein in a case when the number of times that the operation of the image forming apparatus in which the state has been changed exceeds the previously determined threshold value, when time obtained by subtracting the previously set time for the operation of the image forming apparatus in which the state has been changed from previously set communication time for a previously determined data amount is shorter than time required for the communication for the previously determined data amount, the previously set time for the operation of the image forming apparatus in which the state has been changed is reduced. 7. a method for image forming, the method comprising: monitoring a communication state of a data signal in an image forming apparatus; when it is detected that the communication state of the data signal is abnormal, delaying communication of the data signal such that the communication of the data signal is not performed during a previously determined time, stored in a memory, including a time point at which the communication state of the data signal has become abnormal due to an operation of the image forming apparatus; and when it is detected that the communication state of the data signal is abnormal, storing the operation of the image forming apparatus in which the state has been changed, wherein when a number of times that the operation of the image forming apparatus in which the state has been changed is stored exceeds a previously determined threshold value, the communication of the data signal is delayed during previously set time for the operation of the image forming apparatus in which the state has been changed, and wherein in a case when the number of times that the operation of the image forming apparatus in which the state has been changed exceeds the previously determined threshold value, when time obtained by subtracting the previously set time for the operation of the image forming apparatus in which the state has been changed from previously set communication time for a previously determined data amount is shorter than time required for the communication for the previously determined data amount, the previously set time for the operation of the image forming apparatus in which the state has been changed is reduced.
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cross-reference to related applications this application is based on and claims priority under 35 usc 119 from japanese patent application no. 2010-070173 filed mar. 25, 2010. background technical field the present invention relates to an image forming apparatus, a computer readable medium storing a program and a method for image forming. summary according to an aspect of the present invention, there is provided an image forming apparatus including: a monitor that monitors a state of communication performed in the image forming apparatus; and a controller that, when the monitor monitors that the state of the communication is abnormal, controls the communication based on an operation of the image forming apparatus in which a state has been changed within previously determined time including a time point at which the state of the communication has become abnormal. brief description of the drawings an exemplary embodiment of the present invention will be described in detail based on the following figures, wherein: fig. 1 is a cross-sectional view of an image forming apparatus according to an exemplary embodiment of the present invention; fig. 2 is a schematic cross-sectional view showing an image forming unit in fig. 1 in more detail; fig. 3 is a block diagram showing a configuration of a communication control program which operates in an apparatus main body controller in fig. 1 ; figs. 4a to 4c are examples of data signals indicating communication states; fig. 5 illustrates an example of periods indicating rotational positions of a photoreceptor drum; fig. 6 is a timing chart for explaining the communication control program in fig. 3 in more detail; fig. 7 is a timing chart showing control of communication between the apparatus main body controller and an image forming unit controller; fig. 8 is a flowchart showing an operation (s 10 ) of the communication control program in fig. 3 ; and fig. 9 is a block diagram showing a configuration of a second communication control program which operates in the apparatus main body controller in fig. 1 . detailed description hereinbelow, an exemplary embodiment of the present invention will be described in detail based on the drawings. note that the following description is merely an example of implementation of the present invention and the present invention is not limited to the example described below but may be arbitrarily changed in accordance with necessity. for example, an image forming apparatus according to the exemplary embodiment of the present invention is described below as a color printer; however, the image forming apparatus may be another device than the color printer (for example, a monochrome printer, a facsimile machine or a multi-function device). further, another device than the image forming apparatus (for example, a personal computer) may be used. fig. 1 is a cross-sectional view of an image forming apparatus according to the exemplary embodiment of the present invention. as shown in fig. 1 , an image forming apparatus 1 according to the exemplary embodiment of the present invention has an apparatus main body 10 as well as an operation panel 20 , a scanner 30 and a paper feeder 40 , which are attached to the apparatus main body 10 . further, the apparatus main body 10 has image forming units 12 y (yellow), 12 m (magenta), 12 c (cyan) and 12 k (black) provided for colors forming a color image. note that in the following drawings, “n” does not always indicate the same number, and substantially the same components have the same reference numerals. note that hereinbelow, when any one of plural components such as “image forming units 12 y, 12 m, 12 c and 12 k” is given without being specified, it may be simply abbreviated to e.g. an “image forming unit 12 ”. further, the apparatus main body 10 , the image forming unit 12 and the paper feeder 40 , respectively having a controller, operate under the control of the controller. note that although not shown, an apparatus main body controller 100 of the apparatus main body 10 , an image forming unit controller 120 of the image forming unit 12 and a paper feeder controller 400 of the paper feeder 40 are control circuit boards having a cpu, a memory, a storage medium, a bus connecting these elements, and the like. these control circuit boards are communicably interconnected via cables, connectors and the like. the apparatus main body 10 has the image forming unit 12 to form a toner image, an intermediate transfer belt 102 on which the toner image is transferred from the image forming unit 12 , a transfer roller 104 to transfer the toner image to paper in a position opposite to the image forming unit 12 , a fixing part 106 to fix the toner image transferred to the paper, and a paper conveyance passage 110 to convey the paper. the fixing part 106 is provided with a flash lamp 108 . the toner image is fixed with optical energy emitted from the flash lamp 108 . the paper conveyance passage 110 is provided with plural pairs of conveyance rollers 112 along the paper conveyance passage 110 . in the paper conveyance passage 110 , the printed surface of the paper on which print processing has been performed is faced down and discharged to the discharge tray 114 . the operation panel 20 receives a print processing command (for example to print-output image data) from a user, and transmits the received print processing command to the apparatus main body controller 100 . note that although not shown, the operation panel 20 is communicably connected to the apparatus main body controller 100 via a cable, a connector and the like. the scanner 30 reads a set original, and transmits the read content as image data to the apparatus main body controller 100 . note that although not shown, the scanner 30 is communicably connected to the apparatus main body controller 100 via a cable, a connector and the like. the paper feeder 40 has a paper feed tray 402 . the paper feed tray 402 is provided with a paper feed head 404 . upon reception of the print processing command with the apparatus main body controller 100 as a trigger, the paper feed head 404 is actuated, and paper is supplied from the paper feed tray 402 via a paper feed passage 406 to the apparatus main body 10 . as in the case of the paper conveyance passage 110 , the paper feed passage 406 is provided with plural pairs of conveyance rollers 112 along the paper feed passage 406 . note that although not shown, a part of the side surface of the paper feeder 40 on the side of the apparatus main body 10 is utilized as a guide surface to communicate the paper feed passage 406 to the paper conveyance passage 110 . fig. 2 is a schematic cross-sectional view showing the image forming unit 12 in fig. 1 in more detail. as shown in fig. 2 , the image forming unit 12 has a photoreceptor drum 122 , a charging device 124 , an exposure device 126 , a developing roller 128 and a pre-transfer charging unit 130 . the photoreceptor drum 122 has a photo conductive layer such as an opc (organic photo conductor) on its surface. the charging device 124 applies electric charge to the surface of the photoreceptor drum 122 to uniformly charge the surface of the charging device 124 . the exposure device 126 , having a light beam emission source such as a laser diode, emits a light beam on the charged surface of the photoreceptor drum 122 , thereby eliminates charge in the irradiated part and forms an electrostatic latent image corresponding to an output image. the developing roller 128 supplies toner corresponding to the output image to the photoreceptor drum 122 , thereby forms a toner image from the electrostatic latent image on the surface of the photoreceptor drum 122 . the pre-transfer charging unit 130 applies electric charge to the surface of the photoreceptor drum 122 , thereby uniformly charges the surface of the photoreceptor drum 122 prior to transfer by the transfer roller 104 . fig. 3 is a block diagram showing a configuration of a communication control program 50 which operates in the apparatus main body controller 100 in fig. 1 . the communication control program 50 is stored on the memory, the storage medium or the like, and read and executed by the cpu. as shown in fig. 3 , the communication control program 50 has a monitor 500 , a memory 502 , an inquiry part 504 , a determination part 506 and a communication controller 508 . the monitor 500 monitors states of communication between the apparatus main body controller 100 and the image forming unit controller 120 , the paper feeder controller 400 , the operation panel 20 and the scanner 30 connected to the apparatus main body controller 100 , and communication between the image forming unit controllers 120 . the communication states are monitored as e.g. data signals shown in figs. 4a to 4c . when the data signal in fig. 4a is monitored, the communication state is normal. when the data signal in fig. 4b is monitored, although noise is superimposed on the data signal, the noise can be eliminated by sampling or the like. accordingly, the communication state is normal. when the data signal in fig. 4c is monitored, since noise which cannot be eliminated without difficulty is superimposed on the data signal, the communication state is abnormal. however, even when the data signal in fig. 4c is monitored, there is a probability that a communication abnormality does not actually occur but an abnormality caused in the component of the image forming apparatus 1 influences the communication state. for example, failure of a motor which actuates the component of the image forming apparatus 1 increases load current, which causes serious induction noise upon starting of the motor, and the noise is superimposed on the data signal. in the memory 502 in fig. 3 , based on the operation state of each of the components of the image forming apparatus 1 , a timing at which the communication state becomes abnormal (hereinbelow, “abnormal timing”) and the number of times of occurrence of an abnormality in the communication state (hereinbelow, “abnormal times”), linked with each other, are stored. note that the information stored in the memory 502 may be deleted upon power-on or power-off of the image forming apparatus 1 , or may be deleted based on an instruction inputted by the user with respect to the operation panel 20 . further, the information may be deleted upon change of the component(s) of the image forming apparatus 1 . further, upon deletion of the information, all the abnormal times and abnormal timings may be deleted or only the abnormal times beyond a previously determined (hereinbelow, “predetermined”) threshold value and abnormal timings corresponding to these abnormal times may be deleted. upon monitoring of a communication state abnormality by the monitor 500 as a trigger, the inquiry part 504 inquires about the operation states of the respective components of the image forming apparatus 1 , and transmits the results of inquiry to the determination part 506 . the operation states of the respective components of the image forming apparatus 1 are indicated as e.g. on/off data signals from the respective components of the image forming apparatus 1 . note that it may be arranged such that the inquiry part 504 inquires about the temperature and the humidity in the image forming apparatus 1 detected by sensors (not shown) in addition to the operation states of the respective components of the image forming apparatus 1 , or it may be arranged such that the inquiry part 504 inquires about a rotational position of the photoreceptor drum 122 in fig. 2 . the rotational position of the photoreceptor drum 122 is indicated as, e.g., a period divided from the period of 1 rotation of the photoreceptor drum 122 (here, divided period 1 , divided period 2 , . . . divided period n−1 and divided period n) as shown in fig. 5 . the determination part 506 in fig. 3 determines an abnormal timing based on the operation state of each of the components of the image forming apparatus 1 obtained from the inquiry by the inquiry part 504 . for example, in a component of the image forming apparatus 1 , when an abnormality in its communication state is monitored and the operation state is changed at the same time, the time point at which the operation state in the component has been changed is determined as an abnormal timing. further, the determination part 506 stores the determined abnormal timing in the memory 502 and counts up the abnormal times corresponding to the determined abnormal timing. when the abnormal times counted by the determination part 506 exceeds a predetermined threshold value (that is, the abnormal times at the same abnormal timing exceeds the predetermined threshold value), the communication controller 508 controls a communication interface (not shown) provided in the apparatus main body controller 100 , the image forming unit controller 120 , the paper feeder controller 400 , the operation panel 20 , the scanner 30 and the like so as to control a communication timing. fig. 6 is a timing chart for explaining the communication control program 50 in fig. 3 in more detail. as shown in fig. 6 , the respective components of the image forming apparatus 1 (here, the photoreceptor drum 122 , the developing roller 128 , the pre-transfer charging unit 130 , the transfer roller 104 , the charging device 124 , the exposure device 126 and the paper conveyance passage 110 shown in fig. 2 ) operate, and the image forming unit controllers 120 k and 120 c communicate with each other. when the communication control program 50 is executed, and the monitor 500 in fig. 3 first monitors an abnormality in the communication between the image forming unit controllers 120 (( 1 ) in fig. 6 ), the inquiry part 504 in fig. 3 inquires about the operation states of the respective components of the image forming apparatus 1 . the determination part 506 in fig. 3 determines an abnormal timing, and stores the determined abnormal timing (here, timing of actuation of the transfer roller 104 as shown in ( 2 ) in fig. 6 ) and the abnormal times (here, once), linked with each other, into the memory 502 in fig. 3 . further, when the abnormal times in the communication between the image forming unit controllers 120 exceeds a predetermined number of times (e.g., five times), in the subsequent communication, the communication controller 508 in fig. 3 delays communication start time so as not to perform communication at the abnormal timing which influences communication state due to actuation of the transfer roller 104 . note that it may be arranged such that the communication controller 508 reduces the number of times of communication so as not to perform communication at the abnormal timing. more particularly, as shown in ( 3 ) in fig. 6 , control is performed so as to delay the communication start timing by time t 1 . it may be arranged such that the time t 1 is previously stored, linked with an abnormal timing, in the memory 502 or the like and read from the memory 502 , otherwise, it may be arranged such that the time t 1 is obtained by adjusting previously-stored time in correspondence with the temperature and the humidity in the image forming apparatus 1 and/or the rotational position of the photoreceptor drum 122 . time t 2 is previously set such that it is longer than time t 3 logically required for communication for a predetermined data amount (such that the time t 2 includes margin m). especially, when time t 4 obtained by subtracting the time t 1 from the time t 2 is shorter than the time t 3 , since a part of predetermined data cannot be communicated, the time t 1 is reduced such that the time t 4 is longer than the time t 3 or communication is also performed in the time t 1 . note that communication may be performed sequentially from data with the highest priority in consideration of a probability that data with low priority cannot be communicated. further, it may be arranged such that, in the subsequent communication, when the accumulated time of the time t 1 exceeds a predetermined threshold value, a warning is displayed on the operation panel 20 or the like. further, it may be arranged such that, a warning is displayed on the operation panel 20 or the like only when the accumulated time of the time t 1 exceeds the predetermined threshold value in not all the communications but in predetermined communication (for example, only communication between the image forming unit controllers 120 ). the above description has been made about communication between the image forming unit controllers 120 as an example, and further, communication between the apparatus main body controller 100 and the image forming unit controller 120 is similarly performed. for example, as shown in fig. 7 , when an abnormal timing is a time point of light emission in the flash lamp 108 in fig. 1 , the apparatus main body controller 100 controls the timing of video data transmission not to transmit the video data to the image forming unit controller 120 during the time of light emission in the flash lamp 108 . fig. 8 is a flowchart showing the operation (s 10 ) of the communication control program 50 in fig. 3 . as shown in fig. 8 , at step s 100 , it is determined whether or not an abnormality of communication state has been monitored by the monitor 500 in fig. 3 . when it is determined that the communication state has become abnormal, the process proceeds to step s 102 , otherwise, the determination is repeated until the communication state becomes abnormal. at step s 102 , the inquiry part 504 in fig. 3 inquires about the operation states of the respective components of the image forming apparatus 1 in fig. 1 . note that the inquiry part 504 may inquire about the temperature and the humidity in the image forming apparatus 1 and/or the rotational position of the photoreceptor drum 122 in fig. 2 , in addition to the operation states of the respective components of the image forming apparatus 1 . at step s 104 , the determination part 506 in fig. 3 determines an abnormal timing based on the operation states of the respective components of the image forming apparatus 1 inquired at step s 102 . at step s 106 , the determination part 506 stores the determined abnormal timing in the memory 502 in fig. 3 , and counts up the abnormal times corresponding to the determined abnormal timing. at step s 108 , the determination part 506 determines whether or not the abnormal times counted up at step s 106 exceeds a predetermined threshold value. when it is determined that the abnormal times exceeds the predetermined threshold value, the process proceeds to step s 110 , otherwise, returns to step s 100 . at step s 110 , the communication controller 508 in fig. 3 reads the time t 1 in which communication is not performed from the memory 502 or the like based on the abnormal timing determined at step s 104 . note that it may be arranged such that the read time t 1 is adjusted in correspondence with the temperature and the humidity in the image forming apparatus 1 and/or the rotational position of the photoreceptor drum 122 . at step s 112 , the communication controller 508 subtracts the time t 1 calculated at step s 110 from the previously-set time t 2 for a predetermined data amount, thereby calculates the time t 4 . at step s 114 , the communication controller 508 determines whether or not the time t 4 calculated at step s 112 is shorter than the time t 3 required for communication for the predetermined data amount. when it is determined that the time t 4 is shorter the time t 3 , the process proceeds to step s 116 , otherwise, proceeds to step s 118 . at step s 116 , the communication controller 508 adjusts the time t 1 calculated at step s 110 such that the time t 4 becomes longer than the time t 3 , or performs control to also perform communication in the time t 1 . at step s 118 , the communication controller 508 delays the communication start timing by the time t 1 or does not delay the communication start timing, so as not to perform the communication during the time t 1 read at step s 110 (or the time t 1 adjusted at step s 116 ). as described above, the states of communication between the apparatus main body controller 100 , and the image forming unit controller 120 , the paper feeder controller 400 , the operation panel 20 , and the scanner 30 connected to the apparatus main body controller 100 , and communication between the forming unit controllers 120 are monitored, and the communication is controlled based on a timing at which communication state becomes abnormal. however, when noise of the power source is detected, in accordance with the degree of noise, there is a strong probability that the noise influences the communication state. accordingly, it may be arranged such that the power source of the image forming apparatus 1 , power sources of the components of the image forming apparatus 1 , the signal ground and the frame ground and the like are monitored, and communication is controlled based on a timing of detection of noise at a predetermined or higher level. [modification] fig. 9 is a block diagram showing a configuration of a second communication control program 60 which operates in the above case in the apparatus main body controller 100 in fig. 1 . as shown in fig. 9 , the communication control program 60 has a monitor 600 , a memory 602 , the inquiry part 504 , a determination part 604 and the communication controller 508 . the monitor 600 monitors the power source of the image forming apparatus 1 , the power sources of the components of the image forming apparatus 1 , the signal ground and the frame ground. in the memory 602 , timings of noise detection (hereinbelow, “noise detection timing”) and the number of times of noise detection (hereinbelow, “noise detection times”), linked with each other, are stored based on the operation states of the respective components of the image forming apparatus 1 . upon monitoring of noise in the power source of the image forming apparatus 1 , the power sources of the components of the image forming apparatus 1 , the signal ground and the frame ground by the monitor 600 as a trigger, the inquiry part 504 inquires about the operation states of the respective components of the image forming apparatus 1 and transmits the obtained operation states to the determination part 604 . the determination part 604 determines a noise detection timing based on the operation states of the respective components of the image forming apparatus 1 inquired by the inquiry part 504 . further, the determination part 604 stores the determined noise detection timing in the memory 602 , and counts up the noise detection times corresponding to the determined noise detection timing. when the noise detection times counted up by the determination part 604 exceeds a predetermined threshold value (that is, the noise detection times at the same noise detection timing exceed the predetermined threshold value), the communication controller 508 controls the communication interface so as not to perform communication at the noise detection timing at which the noise at the predetermined or higher level influences the communication state. in this manner, the communication state (or noise) is monitored, and the communication is not performed at a timing at which the communication state easily becomes abnormal (or timing at which high degree of noise easily occurs). this arrangement reduces inconvenience that an abnormality in the component of the image forming apparatus 1 influences the communication state to cause abnormal communication state even when actually no communication abnormality occurs. thus time before the cause of the abnormality is identified can be reduced, and the operating ratio of the image forming apparatus 1 can be increased. the foregoing description of the exemplary embodiment of the present invention has been provided for the purposes of illustration and description. it is not intended to be exhaustive or to limit the invention to the precise forms disclosed. obviously, many modifications and variations will be apparent to practitioners skilled in the art. the exemplary embodiment was chosen and described in order to best explain the principles of the invention and its practical applications, thereby enabling others skilled in the art to understand the invention for various embodiments and with the various modifications as are suited to the particular use contemplated. it is intended that the scope of the invention be defined by the following claims and their equivalents.
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133-350-782-981-926
|
US
|
[
"US"
] |
G08C23/04,H01H9/02,H04B10/10
| 1997-06-30T00:00:00 |
1997
|
[
"G08",
"H01",
"H04"
] |
remote control keypad unit
|
a remote control device for operating an electronic device having an means. the remote control device is configured to be grasped for operation by both hands of a user and is comprised of a body having a lower part an upper part and a continuous sidewall extending between said lower and upper parts. one or more operation areas are positioned on the body and are equipped with a plurality of channel operation buttons, the channel operation buttons being arranged on the body and numbered to correspond with a user's fingers such that when the remote control is grasped in both of the user's hands, each of the user's fingers are comfortably positioned upon one of the plurality of operation buttons so as to facilitate control of the electronic device such that selection may be rapidly and conveniently changed by depressing the desired button with the finger which rests upon the operation button which corresponds to the desired selection. additional basic control buttons, such as volume control, are easily reached by the user's fingers while grasping the body or bodies. the remote control device also includes channel operation means capable of generating a code signal which corresponds to one or more of the channel operation buttons when one or more of the channel operation buttons are depressed. an infrared beam emitter or wired connection is also provided for producing a signal beam to engage the infrared beam receiver of the television set to change a channel.
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1. a remote control keypad unit for operating an electronic device having a receiver means, said remote control device configured to be grasped for operation by both hands of a user, comprising: a body having a lower part, an upper part and a sidewall extending between said lower and upper parts, said sidewall defining a first side and a second side; an operation area positioned on said body, said operation area equipped with a plurality of operation buttons, said operation buttons arranged on said body such that when said remote control is grasped in both of said user's hands, each of said user's fingers are positioned upon one of said plurality of operation buttons so as to facilitate control of the electronic device such that selections on the electronic device may be changed by depressing the desired button with the finger which rests upon the operation button which corresponds to the desired selection; operation means capable of generating a code signal which corresponds to one or more of said operation buttons when one or more of said operation buttons are depressed; and electrical connection means for transmitting said code signal to said electrical receiver means of the electronic device to change a selection. 2. the remote control keypad unit as recited in claim 1, wherein eight operation buttons are positioned on said lower part of said body and two operation buttons are positioned on said upper part of said body, said operation buttons positioned on said upper part of said body are configured for actuation by the thumbs of the user's hands, said operation buttons positioned on said lower part of said body of said remote control are arcuately arranged in two rows of four operation buttons and are configured to receive the pinky, ring, middle and index fingers of each of the hands of the user such that said remote control is naturally grasped in the user's hands for operation. 3. the remote control keypad unit as recited in claim 1, further comprising selection scrolling buttons and volume control buttons positioned on said sidewall. 4. the remote control keypad unit as recited in claim 3, wherein said selection scrolling buttons are positioned on said first side of said sidewall, said selection scrolling buttons being positioned for easy touch activation by one of the fingers of the user's hands. 5. the remote control keypad unit as recited in claim 3, wherein both said selection scrolling buttons and said volume control buttons are positioned on one of said first or said second side of said sidewall. 6. the remote control keypad unit as recited in claim 2, wherein said operation buttons are provided with symbolic selection indicators positioned thereon. 7. the remote control keypad unit as recited in claim 2, wherein said operation area further comprises symbolic selection indicators positioned proximate said operation buttons. 8. the remote control keypad unit as recited in claim 2, wherein each of said operation buttons are assigned a symbol to correspond to selection inputs to be entered by the fingers of the user's hands. 9. the remote control keypad unit as recited in claim 2, wherein said operation buttons positioned on said top part of said body are positioned on a raised member for comfort and to facilitate actuation of said operation buttons by the thumbs of said user's hands. 10. a remote control keypad unit for operating an electronic device having a receiver means, said remote control keypad unit comprising: a first and a second body, each of said bodies configured to be grasped for operation by a corresponding hand of both hands of a user, wherein a sidewall extends between a lower part and an upper part of each of said bodies, said sidewall defining a first side and a second side; an operation area positioned on said bodies, said operation area equipped with a plurality of operation buttons, said operation buttons arranged on said bodies such that when said remote control is grasped by said both hands of said user, at least one finger from each of said user's hands are positioned so as to rest on at least one corresponding operation button of said plurality of operation buttons, wherein said operation buttons are coupled to operation means capable of generating a plurality of code signals, each of said code signals corresponding to at least one of said operation buttons being depressed, and wherein said code signals are transmitted via a direct electrical connection means to said direct electrical receiver means of the electronic device. 11. the remote control keypad unit of claim 10, wherein said operation buttons are configured to facilitate control of said electronic device by changing a selection on said electronic device via said code signals, when at least one said buttons are depressed. 12. the remote control keypad unit of claim 10, wherein said operation area is positioned on at least one of said upper part, said lower part, said first side, and said second side. 13. the remote control keypad unit of claim 10, wherein said first and second bodies are configured as two separate units so that said user can grasp each of said bodies with said corresponding hand without constraining said hands to one position.
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field of the invention this invention relates to digital keypad controllers used for operating electronic devices and appliances, and in particular, to remote control keypad devices having tactile elements which facilitate the location of different keys on the keypad by the operator. background of the invention the prior art is replete with numerous different types of remote control keypads for controlling electronic devices. remote control digital keypads are commonly used to control numerous different types of electronic devices, such as television sets, stereos, video cassette recorders or cd recorders, computers, video games, as well as many different household electrical appliances. these control keypads are configured in a variety of shapes and sizes for ease of use by an operator in the home. most control keypads include a plurality of raised "buttons" which are marked with numeric, alphanumeric, and/or other symbolic indicia for entering channel or station numbers, or for initiating or controlling a certain task. prior art remote control keypads come in a variety of shapes and sizes for use by one or two hands. single hand remote control keypads include such devices as those disclosed in u.s. pat. no. 5,432,510 and u.s. pat. no. 4,791,408 which disclose remote control input keypads for single hand operation. these devices are ergonomically designed to fit in one hand for facilitating multiple key character input. these devices, however, are provided with only a small number of keys, each of which control numerous letters and numbers. as such, the user must memorize numerous button configurations and sequences in order to type the desired letter or number. other prior art remote control keypad units require the use of both hands, such as u.s. pat. no. 4,878,055 and u.s. pat. no. 4,745,397. these prior art devices are designed to be held in one hand while the second hand is used to depress one or more the numerous input control buttons or operation keys positioned on the unit's keypad. as these devices require the use of both hands, use in the dark is often difficult. additionally, if the user is using the remote control keypad unit for controlling a television and desires to change the channel, the user must divert his or her attention from the program being watched in order to view the numerical keypad, locate the desired button, and input the new desired channel. in u.s. pat. no. 5,426,449 there is disclosed a pyramid shaped ergonomic keyboard for use with a personal computer. this device requires the placement of both hands upon the keyboard for the input of letters and numbers. this device, however, is designed exclusively for computer use and comprises a detailed layout of various letters and numbers with which the user must familiarize his or herself. u.s. pat. no. 5,253,068 teaches a remote control unit for controlling a television and which is shaped like a pistol or handgun such that a television viewer holds the remote control unit like a gun and changes the channels on the television by pointing the gun-shaped remote control at the television and pulling the trigger to "shoot" the channel to change the program by directing an infrared light beam to a receiver on the television or on a vcr. the handgrip portion of the gun-shaped remote control is provided with switches and buttons for entering the channel numbers, raising and lowering the volume and turning on and off the television or vcr, in addition to a variety of other switches and buttons which control specialized features. also, this remote control may not comfortably fit in the hands of all users. additionally, many people have strong feelings against the use of guns and some households may thus desire not to use gun-shaped objects within their homes. u.s. pat. no. 5,408,275 directed to an apparatus and method for controlling a television receiver teaches a remote control which comprises a keyboard for entering channels, and a rotary encoder which controls the volume and on-screen displays. this remote control, however, requires precision in using the rotary encoder in order to obtain the desired volume, and in addition, requires the user to scroll through numerous on-screen displays which interrupts the user's viewing of the television program being watched. in u.s. pat. no. 5,436,625 there is disclosed a folding electronic device in the form of a folding remote controller for a television set. the remote controller comprises a folding case consisting of a first case and a second case connected to one another by a pivotal hinge. both the first and second case are provided with a plurality of input means and control buttons thereon for changing channels, controlling volume, color, contrast, etc. the hinge connection allows the first and second case to be folded upon one another to provide a compact unit when not in use. however, because of the compactness of this device when the first and second case are folded together, there is a likelihood that the device may be easily lost or displaced. additionally, the hinged connection of the first and second case provides a potential for easy breakage or separation thus rendering the remote control inoperable. u.s. pat. no. 3,906,369 discloses a function switch arrangement for a hand-held remote control unit. the remote control unit comprises a housing having a pair of spaced parallel handgrips. located forwardly of the handgrips and extending between them is a console having a function switch mounting surface with a v-shaped horizontal profile. an array of thumb actuated function switches is located on the console and arranged in upper and lower rows for easy access and control by the operator's thumbs. a pair of trigger switches, which effectuate proportional control by the functions initiated by the aforementioned thumb function switches, are mounted on the underside of the handgrips within range of operator's forefinger. a safety disabling switch is located beneath the function switch rows and extends transversely between the handgrip frame members so that it may also be activated by either of the operator's thumbs without disturbing the operator's grip on the unit. this device is large and bulky and is not directed for use in controlling television sets and electrical household appliances, but rather is designed for operating radio controlled airplanes and boats. u.s. pat. no. 4,655,621 teaches a combinatorial keyboard which encodes characters and spaces. this reference teaches a keyboard for a typewriter or computer which comprises two groups of keys for operation by the fingers of two hands of an operator. each group of keys comprises five home keys arranged in a first single continuous row for each hand, and means for decoding operation of the keys to provide signals representative of characters. this device, however, requires a variety of functions by each finger and is directed to producing letters and/or numbers upon a piece of paper or upon a computer monitor screen; it is not adapted for use as a remote control for changing channels on a television set. u.s. pat. no. 5,479,163 discloses a digital keypad for controlling electrical devices and which includes tactile keys circularly arranged on the controller in a clock face pattern and including a handle portion which is detachably connected perpendicularly to the horizontal controller key pad, and which includes a trigger for transmitting signals to the electrical device. the keys are marked with numeric indicia in sequential numeric order from 1 to 12, each switch being radially spaced 30-degrees apart. in use, the handle is grasped in one hand and the second hand is used to depress the keys arranged on the controller. after inputting the desired keys, the trigger on the handle is depressed to transmit the signal. the provision of the handle in this device, however, renders this device large and bulky. additionally, the user is still required to use one hand to grasp the handle while the second hand is used to locate and depress the keys on the controller keypad. another two-handed keypad device for controlling electronic devices is disclosed in u.s. pat. no. 5,551,693. this device comprises a controller unit having a pair of handles on each end which diverge toward the user for gripping within the user's hands. each handle of the controller unit is provided with control sections which include a plurality of key elements arranged on the top surface as well as other controls on the lower and side surfaces of the control sections of the handles. this device, however, is directed for use with electronic video games and is not provided with numeric or letter keys, but is rather provided with directional controls only. accordingly, there is a need for a numeric, alphanumeric, and/or other symbolic remote control keypad unit for controlling electronic devices with simplicity and ease and which can be operated in a rapid manner which does not require excess finger strokes and which does not tire the user's eyes during operation of the device in which the finger is specialized to a specific button or switch, and which does not require the user to divert his or her eyes from the viewing screen to look for the buttons. objects and summary of the invention it is thus a general object of the present invention to provide a control keypad unit for controlling electronic devices which is simple to manufacture and easy to operate. a more specific object of the present invention is to provide a remote control keypad unit having numeric, alphanumeric, and/or other symbolic keys for controlling television sets, video cassette recorders, video games, stereo systems and other electronic devices. it is another object of the present invention to provide a remote control keypad unit which facilitates rapid location of specific symbols on the keypad. it is another object of the present invention to provide a remote control keypad unit which is configured to permit placement of a user's fingers upon strategically arranged keys on the unit such that the user is capable of changing channels or stations without the fingers ever leaving the keys. another object of the present invention is to provide a remote control keypad having specific symbolic buttons assigned for each finger of the user's hands. it is another object of the present invention to number the user's fingers in a manner similar to the way in which people are taught to count on their fingers during childhood. it is a further object of the present invention to provide a remote control keypad unit which permits a user to rapidly switch to a specifically desired channel, station, or other selection without having to roll-up or down channels, stations, or other selections. it is an additional object of the present invention to provide a remote control keypad unit which sends an electronic signal through a wire connection, or in another embodiment an infrared beam, which engages a receiver on a television set, videocassette recorder, stereo system, video game or other electronic devices. it is still an additional object of the present invention to provide a remote control keypad unit which fits comfortably within a user's hands and which is configured to permit placement of a user's fingers upon strategically arranged keys on the unit such that the user is capable of changing channels, stations, or other selections, in the dark or without diverting his or her eyes from the television screen. it is an additional object of the present invention to provide a remote control key pad unit which is designed to permit a user to "surf" the television channels by rapidly scanning numerous channels without diverting his or her eyes from the television screen. these and other objects of the invention are realized by providing a remote control unit comprising a housing configured to be grasped within both hands of a user for activating and changing stations or channels on television sets, videocassette recorders, stereo systems and other electronic devices. the housing includes an upper surface and a lower surface upon which numeric and/or alphanumeric keys or buttons are arranged in a manner such that when the housing is grasped within both hands of a user, the user's fingers naturally lay upon the buttons. additionally, channel operation buttons for the ten fingers are ergonomically arranged so that the appropriate numbered finger is arranged with its corresponding numbered switch. to facilitate this, the housing places the numbered buttons 0-9 in unique positions such that each one of the basic numbers are assigned, and thus readily located, at the fingertip of a specific finger. the finger located at each channel operation button corresponds to the numbered finger in the way we normally count the basic numbers on our fingers. for example, with the user's palms facing downward and starting at the pinky on the left hand, the fingers are numbered 1-5 on the left hand, and continuing with 6-10 (or "0") from the thumb to the pinky on the right hand. this manner of assigning numbers to a user's fingers utilizes the natural and ingrained manner in which people have been taught to count during their childhood, and thereby incurs the realization of the inherent advantages of speed, efficiency and convenience in using the fingers to easily and efficiently operate the remote control unit of the present invention. in order to make the remote control relatively compact and to conform to the natural position of the user's hands, four channel operation buttons corresponding to four of the fingers of each hand (minus the thumbs), should be positioned on the lower surface of the housing. the two thumbs operate two channel operation buttons positioned on the upper surface of the housing. when the user's hands grasp the remote control unit and the user's fingers are placed upon the corresponding numbered buttons, the user is able to change channels or stations simply by pressing the button or buttons which their fingers are contacting. as such, the user can easily and rapidly change channels or stations in the dark and/or without diverting their eyes from the television or without having to look at the controller. additionally, since the user need only push the button upon which his or her fingers lie, the remote control unit is easily used in the dark or can be used by those with poor eyesight. the remote control unit of the present invention eliminates the present "hunt and peck" method of locating a channel on a remote control unit held in one hand and pressing the desired button or buttons with a finger of the second hand. by placing one's fingers upon the corresponding numbered keys arranged on the remote control unit, a television viewer or stereo listener may instantly change directly to the desired channel without having to "hunt and peck". as such, excessive finger movement is eliminated, time for changing channels is decreased, and those with stiff or arthritic fingers can use the remote control unit with ease. additionally, the placement of a user's fingers upon correspondingly numbered keys arranged on the remote control unit greatly facilitates what has become commonly known as "surfing" the television channels. the efficiency and speed afforded by the design of the remote control unit of the present invention is also advantageous as the numbers of television channels offered increases. the remote control unit of the present invention may also be provided with additional controls and buttons, such as an "on/off" button, volume control and channel scroll, positioned upon the remote control which may be easily reached by the slight movement of a finger of one or both hands. the above description sets forth rather broadly the more important features of the present invention in order that the detailed description thereof that follows may be understood, and in order that the present contributions to the art may be better appreciated. other objects and features of the present invention will become apparent from the following detailed description considered in conjunction with the accompanying drawings. it is to be understood, however, that the drawings are designed solely for the purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims. detailed description of the drawings in the drawings in which like reference characters denote similar elements throughout the several views: fig. 1 illustrates a side elevational view of the remote control according to one embodiment of the present invention; fig. 2 illustrates a top view of the remote control illustrated in fig. 1 according to the present invention; fig. 3 illustrates a bottom view of the remote control illustrated in fig. 1 according to the present invention; fig. 4 illustrates a side elevational view of a second embodiment of the remote control according to the present invention; fig. 5 illustrates a top view of the second embodiment of the remote control illustrated in fig. 4; fig. 6 illustrates a bottom view of the second embodiment of the remote control illustrated in fig. 4; fig. 7 illustrates a top view of the second embodiment of the remote control illustrated in fig. 4 grasped by and retained in both hands of a user for operation; fig. 8 illustrates a bottom view of the second embodiment of the remote control illustrated in fig. 4 grasped by and retained in both hands of a user for operation; fig. 9 illustrates a pair of hands illustrated with the palms facing downward and illustrating each finger as corresponding to a specific number for operation of the remote control according to the present invention; fig. 10 illustrates a third embodiment of the remote control according to the present invention; fig. 11 illustrates a perspective view of the third embodiment of the remote control as illustrated in fig. 10 grasped by and retained in a user's hands for operation; fig. 12a illustrates an elevational view of an alternative embodiment of the remote control according to the present invention and grasped by and retained within both hands of a user; fig. 12b illustrates an elevational view of an alternative embodiment of the remote control according to the present invention in which the remote control is comprised of two separate units fitting into each hand; fig. 13 illustrates an elevational view of an additional alternative embodiment of the remote control according to the present invention and grasped by and retained within both hands of a user; and fig. 14 illustrates a side elevational view of an additional alternative embodiment of the remote according to the present invention and configured such that the volume control and channel scrolling buttons are positioned on one sidewall so that a user may change the volume or scroll channel by grasping the remote only with the right hand. detailed description of the presently preferred embodiment referring now to the drawings for a more detailed description of the present invention and more particularly to figs. 1-4 thereof, a wireless remote control keypad unit 10 is shown and described. remote control 10 has a housing or body 11 defined by a lower part 12, an upper part 14 and a continuous sidewalls 16 positioned between upper part 12 and lower part 14. a keypad or plurality of channel operation buttons 18, 20, 22, 24, 26, 28, 30, and 32 are arranged on lower part 12 in an operation control area 17 as illustrated in figs. 2, 5 and 7. channel operation buttons 34 and 36 are arranged on upper part 14 of remote control 10 in a second operation control area 33 as illustrated in fig. 2. located on or proximate each channel operation button 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36 is a number, such as indicated as x in fig. 2 and y in fig. 3, which alone or in a combination of two or more numbers, corresponds to a channel on a television or stereo when depressed by a user. a plurality of lights, such as leds and other indicators (not shown) may also be disposed on remote control 10. remote control 10 may also include a beam emitter 38 embedded into a front surface 40 which is generally pointed or directed towards the television, stereo or other electronic device which the remote control 10 is controlling or activating. additional operation buttons for such things as channel scrolling 42 and volume control 44 may be positioned on sidewalls 16a, 16b as illustrated in the various embodiments in figs. 1-9. as illustrated in figs. 2, 5, and 7, upper part 14 is also provided with an "on/off" or power button 46 for activating and shutting down the electronic device being controlled. other control buttons, such as 50 illustrated in fig. 7, may be positioned on remote control 10 for controlling any of a variety of functions such as for controlling mutation of sound, color contrast, brightness or for fine tuning sound. built within remote control 10 are selection operation means which include key switches, various circuits, mode selector switches, storage battery, etc. connected to the channel operation buttons, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, the selection scrolling operation buttons 42, and the volume buttons 44. when any one or more of the operation buttons is depressed, a code signal, which is advantageously an infrared beam, corresponding to the operation button or buttons is emitted through beam emitter 38, or in another instance a wire, and received by a coded signal receiver on the television, stereo or other electronic device being operated. fig. 3 illustrates a removable battery casing 48 on lower part 12 of remote control 10 for replenishing a battery or batteries when their power has been depleted. the invention is not limited in the location of the battery casing 48 which may be located anywhere on remote control 10. additionally, the invention is not limited to the shape or size of the housing 11 such that the housing may be altered in shape to reflect the shape and size of an individual user's hand. for example, remote control 10 may be provided in a few basic sizes to accommodate the different size hands of users. additionally, stick-on pads (not shown) to enlarge sides 16a, 16b of remote control 10 may be provided to afford a longer grasp. additionally, remote control 10 may be provided with a standard numeric pad (not shown) could also be provided on top side 14 of remote control 10 in the area ahead of raised member 52 (as shown in fig. 2), in the event that the user does not want to grasp remote control 10 with both hands. remote control 10 is configured to be operated by both hands of a user. each of the embodiments of remote control 10 as illustrated in figs. 1, 2, 5 and 11 are ergonomically designed to be easily and comfortably grasped within both hands of the user such that remote control 10 fits comfortably within the user's hands for effortless operation. selection operation buttons 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36 are advantageously positioned such that when remote control 10 is grasped or cupped within the user's hands as illustrated in figs. 8, 9 and 12, the fingers of each of the user's hands rests comfortably upon one of the selection operation buttons 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36 arranged on lower part 12 and upper part 14 of remote control 10. the selection operation buttons may be recessed relative to the housing or raised depending on the specific requirements of the user. additionally, selection operation buttons 18, 22, 26 and 30 are arranged in an arc or semi circle so that when the used's right hand grasps the remote control 10, the user's finger's are ergonomically arranged on the lower part 12 of the remote control 10. similarly, selection operation buttons 20, 24, 28 and 32 are arranged in an arc or semi circle so that when the user's left hand grasps the remote control 10, the user's finger's are ergonomically arranged on the lower part 12 of the remote control 10. as is evident, by placing the numeric switches on an arc which reflects the natural shape of the hand, each number finger is conveniently placed to activate its corresponding number switch. in order to facilitate the rapid changing of channels, stations, or other selections such that a user may simply depress one or more channel operation buttons 18, 20, 22, 24, 26, 28, 30, 32, 34, and 36 without having to look at the channel operation buttons or remove his or her eyes from the program being watched, channel operation buttons are numbered so as to correspond to the fingers of each of the user's hands. for example, in figs. 3, 4, 6, 7, 8 and 9 the channel numbers assigned to each channel operation button correspond to the numbers assigned to the fingers of the user's hands numbered with the palms facing downward as shown in fig. 9. as indicated in fig. 9, the fingers of the user's left hand are numbered from 1 to 5 from the pinky, ring finger, middle finger, index finger to the thumb. the numbering of the user's fingers continues consecutively from 6 to 0 (the "0" connotes the number "10") starting from the user's thumb on the right hand, the index finger, the middle finger, the ring finger and to the user's pinky or small finger. using this numbering of the user's fingers, when remote control 10 as illustrated in figs. 3, 4, 6, 7, 8 and 11 is grasped in the user's hands as shown in figs. 7 and 8, each finger as numbered in fig. 9 lies on its corresponding selection operation button. for example, the pinky finger of the left hand numbered "l1" as indicated in fig. 9, lies against selection operation button 20 which controls numeric digit 1, as seen in fig. 8. likewise, the pinky finger of the user's right hand which is assigned the number "r0" in fig. 9 lies against channel selection operation button 18 which controls numeric digit 0, as seen in fig. 8 when remote control 10 is grasped in the user's hands. as illustrated in fig. 7, the user's left and right thumb fingers, which are assigned numbers l5 and r6 respectively in fig. 9, are positioned against operation buttons 34 and 36 respectively which control numeric digit 5 and 6 respectively. as illustrated in figs. 1 and 2, channel control buttons 34 and 36 may be raised from upper part 14 of remote control 10 and disposed upon raised member 52 to allow comfortable placement of the user's thumbs against channel control buttons 34 and 36. this arrangement of the user's fingers to control the channel number the identically numbered channel via the selection operation buttons on remote control 10 permits rapid changing of channels or stations in the dark and without requiring the user to look at the numbered selection operation buttons, thus eliminating the familiar "hunt and peck" method of holding the remote control in one hand, viewing and searching for the desired numbered channel button on the keypad and depressing the desired channel button with a finger of the second hand. for example, if the user desires to rapidly turn to channel "74", all that the user need to press is the user's right index finger "r7" to activate selection operation button 30 and the user's left index finger "l4" to activate selection operation button 32. if the user desires to switch to channel "14", the user then presses selection operation buttons 20 and 32 with the user's fingers l1 and l4. when remote control 10 is grasped in the user's hands as illustrated in figs. 7 and 8, channel scrolling buttons 42 and volume control buttons 44 on sidewalls 16a, 16b are easily controlled by the user's index fingers, numbered l4 and r7 in fig. 9. when remote control 10 is grasped in the user's hands for normal selection operation, the user's index fingers, numbered l4 and r7 in fig. 9, lie on selection operation buttons 32 and 30 respectively to control channels 4 and 7 respectively. when the user desires to scroll up or down channels or to increase or decrease the volume, the user simply removes the one or both of the index fingers from selection operation buttons 30 and/or 32 and moves to the channel scrolling buttons 42 and/or volume control buttons 44 on sidewalls 16a, 16b. after depressing channel scrolling buttons 42 and/or raising or lowering the volume via volume control buttons 42, the user returns his or her index fingers, numbered 4 and 7 in fig. 9, back to their natural position on selection operation buttons 32 and 30 respectively on lower part 12 of remote control 10. by assigning the channel numbers to correspond with the user's numbered fingers, it becomes ingrained in the user's brain that each finger controls a particular selection operation button which corresponds to the number of the finger. this takes advantage of natural way in which people have been taught to count during childhood and inherently facilitates the rapid location of a specific channel number by the simple depression of a selection operation button corresponding to a particular numbered finger. it is understood that although the above discussed arrangement of the selection operation buttons and the numbering of the fingers is the preferred embodiment of the present invention, the invention is not limited in this respect and the assignment of the channel numbers to each of the selection operation buttons is not limited to the arrangement as illustrated in the figures, such that different selection operation buttons may be numerically arranged differently with the numbering of the user's fingers than numbered accordingly so as to correspond with the channel numbers assigned to the selection operation buttons. furthermore, the configuration of remote control 10 is not limited to the embodiments illustrated in figs. 1-8, and other configurations of remote control 10 exist such as indicated in figs. 10-13, which are easily grasped and retained within both hands of the user for effortless operation. in accordance with the differing designs and configurations of remote control 10 as illustrated in the figures, the arrangement of the channel control buttons may likewise be arranged in a variety of configurations for comfort and to facilitate positioning of the fingers on the channel control buttons. for instance, as a result of the inclined configuration of lower part 12 in the embodiments illustrated in figs. 1, 3, 10 and 11, selection operation buttons, 18, 20, 22, 24, 26, 28, 30 and 32 are positioned in a curved configuration to facilitate finger placement. in the flat embodiment of remote control 10 illustrated in figs. 4-6, selection operation buttons, 18, 20, 22, 24, 26, 28, 30 and 32 on lower part 12 are arranged in a substantially straight line. in the embodiments illustrated in fig. 12a and 12b, the selection operation buttons (not shown) are positioned on an interior surface of remote control 10 so as to correspond to the positioning of the user's fingers when the user grasps the remote control. fig. 12b illustrates an alternative to the embodiment shown in fig. 12a. the remote control shown in fig. 12b is comprised of two separate handheld units 10. in turn, the user's hands would not be constrained to one position, as shown by the embodiment in fig. 12a. in fig. 13, remote control 10 is grasped with both thumbs of the user's hands positioned on lower part 12 and the remaining fingers of both hands positioned on upper part 14. the selection operation buttons (not shown) of the embodiment illustrated in fig. 13 are accordingly positioned to correspond to the positioning of the user's fingers when remote control is grasped and retained in the user's hands. remote control 10 may also be configured to permit the user to change the volume or scroll up or down the channels by grasping remote control 10 with only one hand, which would be convenient if the user wanted to activate these functions only. using the right hand as an example, fig. 14 illustrates remote control 10 having channel scrolling buttons 42 and volume control buttons 44 positioned together on sidewall 16a. in this configuration, a user who does not wish to change the channel by grasping remote control with both hands, but desires only to scroll the channels upward or downward, or who desires to change the volume, etc. may simply grasp remote control in the right hand and depress channel scrolling buttons 42 and/or volume control buttons 44 with the right index finger, r7, as numbered in fig. 9. it is understood that remote control 10 may be so designed for left-handed operation of channel scrolling buttons 42 and/or volume control buttons 44 by positioning these buttons on sidewall 16b. thus, while there have been shown and described and pointed out fundamental novel features of the invention as applied to preferred embodiments thereof, it will be understood that various omissions and substitutions and changes in the form and details of the disclosed invention may be made by those skilled in the art without departing from the spirit of the invention. it is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto. it is to be understood that the drawings are not necessarily drawn to scale, but that they are merely conceptual in nature.
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133-898-991-530-885
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US
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[
"US"
] |
G01N33/551,G01N33/543,G01N33/53,C12M1/34,G01N30/00,G01N33/566
| 2010-02-25T00:00:00 |
2010
|
[
"G01",
"C12"
] |
hybrid target analyte responsive polymer sensor with optical amplification
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disclosed is a product that includes an optical sensor; a target-responsive hydrogel matrix on a surface of the optical sensor (where the hydrogel matrix comprises one or more target-specific receptors and one or more target analogs), and one or more high refractive index nanoparticles within the hydrogel matrix, where a detectable change occurs in a refractive index of the hydrogel matrix when contacted with one or more target molecules. sterile packages and detection devices containing the product, and methods of detecting a target molecule using the product, are also disclosed.
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1. a product comprising: an optical sensor; a target-responsive hydrogel matrix on a surface of the optical sensor, wherein the hydrogel matrix comprises one or more target-specific receptors and one or more target analogs; and one or more high refractive index nanoparticles within the hydrogel matrix; wherein a detectable change occurs in a refractive index of the hydrogel matrix when contacted with one or more target molecules. 2. the product according to claim 1 , wherein the optical sensor is a porous material. 3. the product according to claim 1 , wherein the porous material is a porous semiconductor material comprising p-doped silicon, n-doped silicon, intrinsic or undoped silicon, intrinsic or undoped germanium, doped germanium, a semiconductor material based on a group ii material, a material based on group iii-v materials, a semiconductor material based on a group vi material, or combinations thereof. 4. the product according to claim 3 , wherein the porous semiconductor material is doped with one or more of b, al, ga, in, p, as, sb, and ge. 5. the product according to claim 3 , wherein the porous semiconductor material is silicon. 6. the product according to claim 2 , wherein the porous material is selected from the group consisting of single layer materials, double layer architectures, mirrors, microcavities, rugate filters, and stacked combinations of these. 7. the product according to claim 6 , wherein the porous material comprises a stack of upper and lower layers including strata of alternating porosity of distinct or graded refractive index, and optionally including a central layer interposed between the upper and lower layers. 8. the product according to claim 2 , wherein the porous material is nanoporous, microporous, or macroporous. 9. the product according to claim 2 , wherein the porous material is formed from silicon wafers or silicon films on a support. 10. the product according to claim 1 , wherein the hydrogel matrix is selected from the group consisting of synthetic hydrogels, natural hydrogels, and mixtures thereof. 11. the product according to claim 10 , wherein the hydrogel matrix is selected from the group consisting of polyacrylamide hydrogels, polyvinyl hydrogels, polylactic acid hydrogels, polyglycolic acid hydrogels, polyethylene glycol hydrogels, agarose hydrogels, collagen hydrogels, acrylic hydrogels, acrylated quaternary ammonium monomeric hydrogels, polyurethane hydrogels, organic/inorganic hybrid hydrogels, cross-linked keratin hydrogels, polyethylene amines, chitosan, and combinations thereof. 12. the product according to claim 10 , wherein the hydrogel matrix comprises one or more polymers having side groups that can be used to tether bioactive reagents. 13. the product according to claim 1 , wherein the hydrogel matrix comprises one or more agents selected from the group consisting of antimicrobial agents, bacteriostatic agents, antiviral agents, and antifungal agents. 14. the product according to claim 1 , wherein the one or more receptors and the one or more target analogs form one or more reversible crosslinks within the hydrogel matrix, wherein binding between at least one of the target molecules and at least one of the receptors breaks at least one of the reversible crosslinks, resulting in swelling of the hydrogel matrix and a change in the refractive index of the hydrogel matrix. 15. the product according to claim 14 , wherein the one or more high refractive index nanoparticles are nonspecifically encapsulated in the hydrogel matrix, and wherein said swelling of the hydrogel matrix results in release of at least one of the nanoparticles from the hydrogel matrix, whereby a change in the refractive index of the hydrogel matrix occurs. 16. the product according to claim 14 , wherein the one or more receptors and/or the one or more target analogs are coupled to the one or more nanoparticles, the one or more receptors, the one or more target analogs, and the one or more nanoparticles collectively forming the one or more reversible crosslinks within the hydrogel matrix, wherein binding between at least one of the target molecules and at least one of the receptors further results in displacement and release of at least one of the nanoparticles from the hydrogel matrix, whereby a change in the refractive index of the hydrogel matrix occurs. 17. the product according to claim 1 , wherein the one or more receptors or the one or more target analogs are coupled to the hydrogel matrix and the other of the one or more receptors and the one or more target analogs are coupled to the one or more nanoparticles, whereby the one or more nanoparticles are reversibly bound to the hydrogel matrix, wherein binding between at least one of the target molecules and at least one of the receptors results in displacement and release of at least one of the nanoparticles from the hydrogel matrix, whereby a change in the refractive index of the hydrogel matrix occurs. 18. the product according to claim 1 , wherein the one or more receptors are monovalent. 19. the product according to claim 1 , wherein the one or more receptors are multivalent. 20. the product according to claim 1 , wherein the one or more receptors are selected from the group consisting of non-polymeric small chemical molecule complexes, peptides, polypeptides, proteins, peptide-mimetic compounds, antibody complexes, oligonucleotides, enzymes, and ribozymes. 21. the product according to claim 20 , wherein the one or more receptors are selected from the group consisting of receptors for cell surface molecules, lipid a receptors, antibodies or fragments thereof, peptide monobodies, lipopolysaccharide-binding polypeptides, peptidoglycan-binding polypeptides, carbohydrate-binding polypeptides, phosphate-binding polypeptides, nucleic acid-binding polypeptides, and polypeptides that bind an organic warfare agent. 22. the product according to claim 1 , wherein the target molecule is selected from the group consisting of antigens, antibodies, proteins, glycoproteins, peptidoglycans, carbohydrates, lipoproteins, lipoteichoic acid, lipid a, phosphates, nucleic acids, pathogens, host markers of infection, organic warfare agents, organic compounds, drugs of abuse, opiates, pain killers, antimicrobial peptides, immune function markers, cancer markers, and disease markers. 23. the product according to claim 1 , wherein the one or more high refractive index nanoparticles are selected from the group consisting of inp, pbs, pbse, cdse, zns, cdse core zns shell, cdte, cds, si, fexoy, tio2, alxoy, znos, sic, and tic. 24. the product according to claim 1 , wherein the one or more high refractive index nanoparticles have a refractive index greater than 1.5, at least 1.7, greater than 2.0, at least 2.5, or at least 3.6. 25. the product according to claim 1 , wherein the one or more high refractive index nanoparticles have a diameter of about 5 to about 50 nm. 26. the product according to claim 2 , wherein the one or more high refractive index nanoparticles are small enough to diffuse out of the porous material. 27. the product according to claim 1 , wherein the detectable change in the refractive index occurs at a target molecule concentration of between picograms per milliliter and milligrams per milliliter. 28. the product according to claim 27 , wherein the detectable change in the refractive index occurs at a target molecule concentration of picograms per milliliter. 29. the product according to claim 27 , wherein the detectable change in the refractive index occurs at a target molecule concentration of nanograms per milliliter. 30. the product according to claim 1 , wherein the detectable change in the refractive index occurs in the visible range. 31. the product according to claim 1 , wherein the detectable change in the refractive index of the hydrogel matrix is amplified by the presence of the high refractive index nanoparticles. 32. the product according to claim 1 further comprising: a vapor barrier applied to at least one side of the hydrogel matrix. 33. the product according to claim 1 further comprising: a release layer contacting at least one side of the hydrogel matrix. 34. a sterile package containing a sterile product according to claim 1 . 35. a detection device comprising: a product according to claim 1 , and a source of illumination positioned to illuminate the product. 36. the detection device according to claim 35 further comprising a detector positioned to capture light reflected from the product and to detect changes in the refractive index of the hydrogel matrix. 37. the detection device according to claim 36 , wherein the detector is a spectral analyzer of a human eye. 38. a method of detecting a target molecule comprising: exposing a product according to claim 1 to a sample under conditions effective to allow binding of a target molecule in the sample to the one or more receptors; and determining whether a change in refractive index of the hydrogel matrix occurs following said exposing, whereby a change in refractive index indicates the presence of the target molecule in the sample. 39. the method according claim 38 , wherein said determining comprises: measuring a first refractive index before said exposing; measuring a second refractive index after said exposing; and comparing the first and second refractive indices. 40. the method according to claim 39 , wherein said measuring is carried out using a light source and a spectral analyzer. 41. the method according to claim 39 , wherein said measuring is carried out using a light source and a spectral analyzer. 42. the method according to claim 38 , wherein the sample is blood, water, a suspension of solids in an aqueous solution, or a tissue homogenate. 43. the method according to claim 42 , wherein the solids suspended in the aqueous solution are food particles, soil particles, or a cell suspension from a clinical isolate. 44. the method according to claim 38 further comprising: quantifying the amount of target molecule(s) present in the sample based on the degree of change in refractive index that occurs.
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this application claims the benefit of u.s. provisional patent application ser. no. 61/308,242, filed feb. 25, 2010, which is hereby incorporated by reference in its entirety. the invention was made with government support under grant no. 5k25ai060884 awarded by national institutes of health/national institute of allergy and infectious diseases and grant nos. t32da007232 and f31da025398 awarded by national institutes of health/national institute on drug abuse. the u.s. government has certain rights. field of the invention the present invention relates generally to hybrid target analyte responsive polymer sensors that include high refractive index nanoparticles, as well as methods of making and using these sensors. background of the invention the increasing need for rapid and portable biosensor technology is evidenced by the growing worldwide markets for environmental field testing (ft) (g ershon j. s hugar et al ., e nvironmental f ield t esting and a nalysis r eady r eference h andbook (2001)) and point-of-care (poc) biomedical diagnostics markets (kalorama information, “world markets for point of care diagnostics,” 13 (2009)), the latter with obvious applications in home health testing (e.g. cholesterol, pregnancy), drugs of abuse screening (e.g. sporting venues, clinic, sobriety check points), and pathogen surveillance for military, homeland security and public health testing. a successful ft/poc platform technology will, in addition to speed, sensitivity and accuracy, be inexpensive and not require extensive training or sophisticated instrumentation for readout. it would utilize a signal transduction strategy that readily extends to the detection of a wide range of targets for which the concentration level that triggers a positive response is tunable for a screening assay and has a wide dynamic range and high target specificity for a quantitative assay. immunochromatographic test strips comprise many of the commercially-available rapid diagnostics. signal transduction is based on lateral flow technology that couples a target antibody to a colorimetric agent such as gold nanoparticles which are drawn over capture and control zones by capillary action. lateral flow devices produce signals detectable by eye but suffer sensitivity and reliability issues and studies indicate that, while simple and rapid, they produce less than acceptable results for wide clinical acceptance (ferris & martin, j. fam. pract. 34:593-97 (1992); hook et al., jama 272:867-70 (1994); kluytmans et al., j. clin. microbiol. 31:3204-10 (1993)). in recent years innovation in ft/poc technology development has focused on label free sensors exploiting the unique optical and electrical properties of nanomaterials (wang et al., mater. today 8(5):20-31 (2005); jain, clin. chim. acta 358(1/2):37-54 (2005)). one such material, electrochemically synthesized porous silicon (psi) (bonanno & delouise, anal. chem. 82:714-22 (2010), holds great promise for ft/poc sensor development. psi is prepared by anodic electrochemical dissolution of a single crystal silicon wafer in an electrolyte containing hydrofluoric acid (hf) (jane et al., trends biotech. 27:230-39 (2009); sailor, acs nano 1(4):248-52 (2007); delouise & miller, proc. spie 5357:111-25 (2004); vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001)). etch parameters can be tuned to achieve a high degree of control over pore diameter (10-150 nm) and porosity (20-90%) which are essential properties for fabrication of photonic structures for biosensing applications as they dictate the optical and signal transduction properties and device sensitivity. there are many advantages of psi technology for ft/poc sensing applications including inexpensive fabrication, precise control of pore morphology (pore diameter and porosity), intrinsic filtering properties (molecular size selection), high surface area (>100 m 2 /g), versatile surface chemistry, capacity for label-free colorimetric readout, and compatibility with high throughput array and microfluidic technologies (bonanno & delouise, anal chem. 82:714-22 (2010); sailor, acs nano 1(4):248-52 (2007); jane et al., trends biotech. 27(4):230-39 (2009); bonanno & delouise, biosens. bioelect. 23:444-48 (2007)). many proof of principle psi sensors have been demonstrated for detecting proteins (ouyang et al., anal. chem. 79(4):1502-06 (2007); delouise & miller, mater. res. soc. symp. proc. 782:a5.3.1 (2004)), oligonucleotides (rong et al., biosens. bioelect. 23(10):1572-76 (2008); di francia et al., biosens. bioelect. 21(4):661-65 (2005); steinem et al., tetrahedron 60:11259-67 (2004)), enzymes (kilian et al., acs nano 1(4):355-61 (2007); delouise & miller, anal. chem. 77(10):3222-30 (2005); delouise & miller, anal. chem. 77(7):1950-56 (2005); orosco et al., adv. mater. 18(11):1393-96 (2006)), small molecules (bonanno & delouise, anal. chem. 82:714-22 (2010); lin et al., biosensor sci. 278(5339):840 (1997)), and gases (pancheri et al., sens. actuators b 89:237 (2003)). however, little effort has focused on the translation of psi devices for ft/poc clinical use. the bio sensor signal transduction principle is based on measurement of refractive index (η) changes. the η of a psi layer depends on porosity which can be varied precisely between η=3.6 (bulk silicon, 0% porosity), to η=1 (air, 100% porosity). optical devices (mirrors, microcavities, and rugate filters) are fabricated by etching multilayer structures with alternating porosity (jane et al., trends biotech. 27:230-39 (2009)). these structures function as label-free optical sensors by reporting changes in η (porosity) that result when target binds immobilized receptors. target binding causes a change in porosity and consequently a change in refractive index (η) that is monitored as a shift in the color of reflected light (i.e., wavelength shift, δλr) from the sensor. the magnitude of δλr is a function of the thickness (amount) of the bound material and its refractive index. target binding decreases porosity, which increases 11, causing a red shift in the optical spectrum. the magnitude of the optical shift has been shown to be a linear function of pore filling (delouise & miller, proc. spie 5357:111-25 (2004)). wavelength shift sensitivity (wss) is a figure of merit specific to each sensor and is measured by displacing air in the pores with liquids of varying refractive index. the wss value is the slope of the plot of wavelength shift magnitude vs. η. for typical sensors, the wss values range between 200-400 nm/riu (delouise & miller, mater. res. soc'y symp. proc. 782:a5.3.1 (2003); delouise & miller, anal. chem. 77(10):3222-30 (2005); delouise & miller, proc. spie 5357:111-25 (2004)), which translates to detecting a ˜10 −3 to 10 −4 change in refractive index. this enables target detection sensitivity ranging from mg/ml (bonanno & delouise, biosens. bioelect. 23:444-48 (2007) to μg/ml (dancil et al., j. am. chem. soc'y 121:7925-30 (1999)) or pg/mm 2 (delouise & miller, anal. chem. 77(10):3222-30 (2005); lin et al., science 278:840-43 (1997)) or nm (kilian et al., acs nano 1(4):355-61 (2007)) depending upon the receptor/target system and the assay protocol used (sailor, acs nano 1(4):248-52 (2007); jane et al., trends biotech. 27(4):230-39 (2009)). a much higher limit of detection is desired (picomolar or ng/ml) but this has not yet been achieved with psi technology. novel optical signal amplification strategies to increase detection sensitivity and to achieve colorimetric read out by eye would be advantageous. devising a strategy to achieve these goals must take into consideration the unique characteristics of the psi transducer. first, because signal transduction occurs within the porous matrix, the sensor architecture and assay protocol must be designed to overcome the effects of pore blocking, steric crowding, and baseline drift. baseline drift in the psi optical response can result from either corrosion of the sensor or from nonspecific adsorption of substances present in complex biological samples (dancil et al., j. am. chem. soc'y 121:7925-30 (1999); lees et al., langmuir 19(23):9812-17 (2003); canham et al., physica status solidi ( a ) 182:521 (2000)). methods to prevent baseline drift are well developed and involve passivating the psi surface with si—o or si—c bond formation (thermal oxidation or hydrosilylation) and utilizing appropriate blocking chemistries and washing protocols (buriak & allen, j. am. chem. soc'y 120:1339-40 (1998); kilian et al., chem. commun. 14(6):630-40 (2009); boukherroub et al., j. electrochem. soc'y 149:59-63 (2002); canham et al., adv. mater. 11:1505-09 (1999)). pore blocking and steric crowding effects are also well understood and can be overcome by tuning the pore diameter and optimizing the surface receptor concentration (delouise & miller, mater. res. soc'y symp. proc. 782:a5.3.1 (2003); bonanno & delouise, langmuir 23:5817-23 (2007)). the latter, unfortunately, may limit the ability to take advantage of the enormous internal surface area of psi to immobilize a high receptor concentration. strategies to attain optical signal amplification for improving the limit of detection and colorimetric readout by eye are less developed and constitute an active area of research in the psi sensor field (kilian et al., acs nano 1(4):355-61 (2007); orosco et al., adv. mater. 18(11):1393-96 (2006); bonanno & delouise, adv. funct'l mater. 20(4):573-78 (2010)). in traditional bioassay design, signal amplification is commonly achieved using fluorescent or enzymatic secondary reporters (elisa, pcr). the coupling of enzymatic and/or catalytic reactions to biosensor signal generation is a growing trend (jane et al., trends biotech. 27(4):230-39 (2009); wang & lin, trends analyt. chem. 27 (7):619-26 (2008); jensen & torabi, j. optical soc'y am. b: opt. phys. 3(6):857-63 (1986)). while effective, these methods add significant cost and assay time that label-free technologies seek to overcome for poc applications. sailor and coworkers have recently demonstrated clever extrapolations of enzymatic signal generation to enhance detection sensitivity of proteases in psi sensors (orosco et al., adv. mater. 18(11):1393-96 (2006)). in this work a protein layer is coated over a psi sensor. protease activity was then detected by measuring optical red shifts (increase in refractive index) due to small peptide fragments (˜7 mm) of the digested protein layer infiltrating the psi pores. this was followed by the work of gooding and coworkers (kilian et al., acs nano 1(4):355-61 (2007)) who embedded protein within the psi matrix and optically detected protease activity (37 nm) by monitoring a blue shift (decreases in refractive index) resulting from protein cleavage and peptide diffusion out of the sensor matrix. these approaches are unfortunately limited to detection of a generic class of enzymes. to overcome these limitations, voelcker and coworkers have pioneered a label-free optical signal amplification strategy based on inducing psi corrosion (steinem et al., tetrahedron 60:11259-67 (2004); voelcker et al., chem bio chem. 9:1776-86 (2008)). formation of a duplex during dna detection was found to trigger oxidative corrosion of the psi substrate causing an irreversible increase in porosity and pore size and a profound decrease in refractive index (steinem et al., tetrahedron 60:11259-67 (2004)). detection of dna at 0.1 amol/mm 2 was achieved by this method. this serendipitous effect was later rationally extended by systematically identifying a transition metal complex that could catalyze psi oxidation. a nickel(ii)cyclam derivative was developed as a catalyst label and integrated into a detection assay to achieve amplified detection of biomolecules at submicromolar concentrations (voelcker et al., chem bio chem. 9:1776-86 (2008)). while this approach is still under development, the irreversible oxidative corrosion of the transducer may prove difficult to control and versatility in target has yet to be demonstrated. while constituting significant advancements, the above mentioned amplification strategies do not directly exploit the fact that the psi is a volume (porosity) sensitive transducer. additionally, clinical and poc diagnostic devices require the specific detection of biological and/or chemical targets at low concentration, in an inexpensive, convenient, reliable, and rapid manner. many innovative approaches have been reported to address this complex problem yet a need still exists for practical technology solutions. responsive hydrogels that undergo morphological changes resulting from external stimuli have displayed great promise in chemical sensing (holtz & asher, nature 389:829-32 (1997)) and medical diagnostics (lapeyre et al., biomacromolecules 7:3356-63 (2006); kim et al., angew. chem. int'l ed. 45:1446-49 (2006); miyata et al., nature 399:766-69 (1999)) as well as drug delivery (kiser et al., nature 394:459-62 (1998)), tissue engineering (lutolf et al., proc. nat'l acad. sci. usa 100:5413-18 (2003)), and microfluidic applications (yu et al., appl. phys. lett. 78:2589-91 (2001)). variation of polymer composition, structure, and incorporation of specific functional groups have been exploited to develop hydrogels that respond to an array of biochemical targets including antigen (yu et al., appl. phys. lett. 78:2589-91 (2001)), dna (murakami & maeda, biomacromolecules 6:2927-29 (2005)), toxins (frisk et al., chem. mater. 19:5842-44 (2007)), drugs (ehrbar et al., nat. mater. 7:800-04 (2008)), and enzymes (thornton et al., chem. commun . ( camb ) 47:5913-15 (2005)). integration of these smart polymers into specifically engineered sensing systems constitutes an active area of research. miniaturization of hydrogel dimensions facilitates reduced response times relative to bulk gel kinetics as required particularly for poc diagnostic testing (lei et al., langmuir 20:8947-51 (2004)). notable success in development of smart hydrogel microlenses into multiplexed stimuli-sensor arrays has been achieved with response time of seconds (kim et al., biomacromolecules 8:1157-61 (2007); dong et al., nature 442:551-54 (2006)). however, reliance on optical instrumentation to monitor the responses from these microscale devices (change in refractive index or lens radius of curvature) is a drawback for poc applications. a more attractive approach for poc applications is to integrate smart hydrogels with colloidal crystal arrays (holtz & asher, nature 389:829-32 (1997); lapeyre et al., biomacromolecules 7:3356-63 (2006)) or photonic bandgap materials (segal et al., adv. funct'l mater. 17:1153-62 (2007)). these composite materials potentially enable direct optical detection of hydrogel morphological changes with rapid steady state response times of seconds to minutes. porous silicon (psi) is a photonic material that is ideally suited for this application due to its inexpensive fabrication, robust optical transduction, and ease in translation for high-throughput analysis (chan et al., j. am. chem. soc'y 123:11797-98 (2001); lin et al., science 278:840-43 (1997); bonanno & delouise, biosens. bioelectron. 23:444-48 (2007); cunin et al., nat. mater. 1:39-41 (2002)). the unique capability of the psi transducer to report refractive index (η) change that occur within the porous matrix can be exploited to detect target molecules binding directly to the psi surface or optical changes that occur to a target-responsive gel incorporated into the porous matrix. chemical and biological sensors have been developed to specifically capture target molecules onto the porous surface area to analyze complex samples in high-throughput and multiplexed assays (chan et al., j. am. chem. soc'y 123:11797-98 (2001); lin et al., science 278:840-43 (1997); bonanno & delouise, biosens. bioelectron. 23:444-48 (2007); cunin et al., nat. mater. 1:39-41 (2002)). in addition, visual color readout has been achieved in the detection of protease activity (orosco et al., adv. mater. 18:1393-96 (2006); gao et al., anal. chem. 80:1468-73 (2008)). protease digestion of a protein layer coated on top of a psi photonic crystal caused cleavage products to infiltrate the pores producing a large η change that was observed by eye as a color change. these studies highlight the potential for developing psi photonic sensors for poc diagnostic applications. the capability to easily tune the optical spectrum of the psi-based 1-d photonic crystal during fabrication facilitates a more deterministic color change combination for portable poc sensing applications. for example, design of a green-to-red color change may be more readily interpreted than a sensor that results in a red-to-deeper-red or blue-to-green color change. hydrogel-supported psi sensors have also been investigated (segal et al., adv. funct'l mater. 17:1153-62 (2007); delouise et al., adv. mater. 17:2199-203 (2005); bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008); bonanno & delouise, proc. spie 7167:71670f (2009)). results show that the sensor maintains the capability to detect small changes in η (10 −3 -10 −4 ) that result from diffusion of small analytes (delouise et al., adv. mater. 17:2199-203 (2005)). composite hydrogel-psi sensors are also able to detect gel structural changes induced in response to stimuli (temperature and ph) (segal et al., adv. funct'l mater. 17:1153-62 (2007)) or that result from changes in gel composition (bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008); bonanno & delouise, proc. spie 7167:71670f (2009)). however, incorporation of a bio or chemo responsive hydrogel into a photonic psi sensor with a tunable target response remains to be demonstrated. the present invention is directed to overcoming these and other deficiencies in the art. summary of the invention a first aspect of the present invention relates to a product comprising: an optical sensor; a target-responsive polymer matrix on a surface of the optical sensor, wherein the polymer matrix comprises one or more target-specific receptors and one or more target analogs; and one or more high refractive index nanoparticles within the polymer matrix; wherein a detectable change occurs in a refractive index of the polymer matrix when contacted with one or more target molecules. a second aspect of the present invention relates to a method of detecting a target molecule comprising exposing a product described herein to a sample under conditions effective to allow binding of a target molecule in the sample to the one or more receptors; and determining whether a change in refractive index of the polymer matrix occurs following said exposing, whereby a change in refractive index indicates the presence of the target molecule in the sample. the products of the invention provide a favorable aqueous environment for molecular-level interactions to occur (zhang, nat. mater. 3(1):7-8 (2004), which is hereby incorporated by reference in its entirety), and increase the number of receptor sites over what can be immobilized onto a planar surface (charles et al., biosens. bioelect. 20(4):753-64 (2004), which is hereby incorporated by reference in its entirety) by dispersing them throughout the psi sensor volume. this also overcomes problems of receptor steric crowding limitations that arise in surface immobilization (bonanno & delouise, langmuir 23:5817-23 (2007), which is hereby incorporated by reference in its entirety). the products of the invention are ideally suited for detection of small molecular weight targets which pose difficulties to detect directly using label-free optical transducers because of the small refractive index changes they induce upon capture (wang et al., electrochem. commun. 9(2):343-47 (2007), which is hereby incorporated by reference in its entirety). because target specificity is determined foremost by the bioactive cross-linker and its differential binding affinity towards target and target analog, this constitutes a versatile sensor platform capable of detecting a wide range of bio/chemical targets. brief description of the drawings figs. 1a-c are schematic illustrations of a representative trap-gel-psi sensor ( figs. 1a-1b ), and a magnified sensor showing cross-link dissociation, gel swelling, and eventual out diffusion in the presence of target ( fig. 1c ). fig. 2 is a schematic illustration of exemplary protocols for cross-link formation. fig. 3 is a graph of the relative wavelength shift (nm) for processing of hybrid optical sensor constructs illustrating the optical signal enhancement afforded by incorporation of 0.29 wt % high refractive index quantum dot™ nanoparticles in a 5 wt % polyacrylamide hydrogel. on=overnight; tcep=tris[2-carboxyethyl]phosphine. figs. 4a-d relate to the temporal optical detection of tcep-responsive s—s-copaam hydrogel dissolution by wet psi sensor reflectance spectrometry measurements taken with varying three design parameters: s—s-copaam hydrogel cross-linking density varied by adjusting mol % napmaam (0-37.27 mol %) ( fig. 4a ); varied outside concentration of tcep (500 μl of 0-100 mm) ( fig. 4b ); and varied psi pore diameter and architecture (19-106 nm diameter single layer pores, all having thickness of 1.68 μm; and bragg mirrors with alternating 19/43 and 73/106 nm diameter pores having thicknesses of 3.2 and 2.8 μm, respectively) ( fig. 4c ). fig. 4d is a graph of the normalized wavelength shift at 4 hours relative to the average pore diameter. dissolution was dependent on the average pore diameter of the psi substrate. d=diameter; p=porosity; sl=single layer. figs. 5a-b relate to ellman colorimetric assay detection of sulfhydryl groups. fig. 5a is a standard curve created to identify absorbance intensity values at 405 nm for varying amounts of free sulfhydryl groups. each mol of cysteamine contains 1 mol of free sulfhydryl groups. fig. 5b is a graph of the amount of sulfhydryl groups present in sulfhydryl functional copolymer solutions (4.14 mol % napmaam) of 5 and 10 wt % in water monitored by ellman's assay. figs. 6a-f are a schematic of a chemical procedure for synthesizing a disulfide cross-linked hydrogel, a type of chemical-responsive hydrogel. various molar ratios of aam and napmaam monomers are diluted in water ( fig. 6a ). free radical polymerization of monomers form co-polymer chains with reactive primary amine groups ( fig. 6b ). reaction with n-succinimidyl-s-acetylthiopropionate (satp) ( fig. 6c ) and deprotection with hydroxylamine ( fig. 6d ) yields sulfhydryl functional copolymer chains in solution ( fig. 6e ). formation of disulfide bonds results in cross-linked hydrogel (s—s-copaam) ( fig. 6f ). fig. 7 shows pictures of bulk s—s-copaam hydrogels with varying mol % napmaam and their subsequent dissolution upon exposure to varying amounts of tcep with mixing. a more rigid hydrogel structure can be observed for higher cross-linking density (higher mol % napmaam). also, more tcep is needed to completely dissolve hydrogels with higher cross-linking density, as would be predicted by theory. figs. 8a-c relate to optical characterization of hydrogel and its infiltration into a psi sensor template. fig. 8a is a graph of the refractive indices of bulk s—s-copaam hydrogels with varying mol % napmaam measured on a bench-top abbe refractometer. the negative control (0 mol % napmaam) did not form hydrogel, but the bulk refractive index of the polymer solution was measured. fig. 8b shows the raw reflectance spectra measured using an avantes spectrometer, illustrating wavelength shifts associated with the addition of mercaptosilane (mpts), filling of the psi pores with water, and the swollen s—s-copaam hydrogel after 2 day soak in water. fig. 8c is a graph of the optical wavelength shift response of psi sensors when s—s-copaam hydrogels with varying mol % napmaam fill the pore volume, comparing the results experimentally determined with simulation results. figs. 9a-b relate to the visual color readout of hybrid hydrogel-psi sensors upon drying. fig. 9a shows side views of 10 mol % napmaam s—s-copaam hydrogels (bulk or cross-linked into a psi sensor) before and after exposure to 1 ml of 50 mm tcep for 15 minutes, rinsing with water, and air drying for 5 minutes. fig. 9b is a series of photographs (top down views) of 4.14 mol % napmaam s—s-copaam hydrogels cross-linked into psi bragg mirrors after incubation in 1 ml of varying concentrations of tcep solution on a shaker for 15 minutes, subsequent rinsing with water, and air-drying for 5 minutes. color shift from red to green is evident. fig. 10 is a schematic illustration of optical detection using a hybrid chemical-responsive hydrogel-porous si sensor. addition of target analyte, tcep, breaks disulfide cross-links in the hydrogel (s—s-copaam) causing a decrease in refractive index that is optically detected by blue wavelength shifts in the reflectance spectrum. addition of sufficient tcep results in gel dissolution and large enough shifts in reflected light to visually observe color change by eye. fig. 11 is a schematic drawing depicting the formation of hydrogels made using polyacrylamide/n-(3-aminopropyl)-methacrylamide random copolymers. fig. 12 is an illustration of morphine-3-glucuronide (m3g). figs. 13a-d are photographs showing the formation of target responsive gels synthesized by incorporation of m3g (target analog) on the polymer chain backbone and addition of anti-morphine ab and protein g to form cross links. trypan blue was added to aid in the visualization of the gel. gels withstood cycles of dehydration and rehydration. addition of free m3g caused gel dissociation after 15 minutes. similar results have been achieved with morphine in place of m3g. fig. 14 shows a hybrid photonic sensor with visual readout capability. an opiate responsive t-gel and ar-ab control gels were cross-linked directly in a macropsi sensor. after exposure to m3g target, only the t-gel sensor produced a color response upon drying. figs. 15a-c demonstrate that spin coating can be used to cast gel precursor solution on a psi sensor. fig. 15a is an sem image of thick gel on a psi sensor (scale bar 2 μm). fig. 15b is a graph of gel thickness spin coated on a silicon wafer as a function of spin speed. fig. 15c is a graph of the wavelength shift as a function of spin speed for gel precursor spin coated onto psi sensors. after gel formation the optical wavelength shift measured equaled expectations, validating complete pore infiltration. detailed description of the invention the present invention relates to products that include an optical sensor, a polymer matrix on a surface of the optical sensor, and one or more high refractive index nanoparticles within the polymer matrix. in use, the optical sensor can be used to detect changes in a refractive index of the polymer matrix in the presence of a target molecule. as discussed more fully below, the high refractive index nanoparticles have the effect of enhancing the refractive index change that is detected, thereby rendering the optical sensor much more sensitive to subtle changes in the polymer matrix caused by presence of the target, even allowing a signal change detectable by the naked eye. referring to fig. 1a , one embodiment of the product 10 is shown to include a polymer matrix 12 with an optical sensor 14 fully embedded in the polymer matrix. on one side of the polymer matrix is a vapor barrier 16 . the vapor barrier can be retained on the polymer matrix using either a mechanical connection of the matrix to the barrier or a chemical bonding. on an opposite side of the polymer matrix is a release layer 18 . the release layer 18 is intended to be removed from the polymer matrix during use, allowing the polymer matrix to be exposed for combining with a sample to be screened. in this embodiment, the matrix covers all exposed surfaces of the optical sensor. referring to fig. 1b , another embodiment of the product 20 is shown to include a polymer matrix 22 with an optical sensor 14 partially embedded in the polymer matrix. on one side of the polymer matrix (and optical sensor) is a vapor barrier 16 . the vapor barrier can be retained on the polymer matrix as described above. on an opposite side of the polymer matrix is a release layer 18 . the release layer 18 is intended to be removed from the polymer matrix during use, allowing the polymer matrix to be exposed for combining with a sample to be screened. in this embodiment, the matrix covers only a portion of the surfaces of the optical sensor. the optical sensor can have any suitable design or construction that is compatible for the target molecule detection in the matrix environment. exemplary optical sensor constructions include, without limitation, single layer materials, double layer architectures, mirrors, microcavities, rugate filters, and stacked combinations of these features. these include simple porous structures of the type disclosed in u.s. pat. no. 6,248,539 to ghadiri et al., which is hereby incorporated by reference in its entirety, as well as microcavity structures of the type disclosed in vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001); u.s. patent application publ. no. 2006/0276047 to ouyang et al.; u.s. pat. no. 7,226,733 to chan et al.; and delouise & miller, proc. spie 5357:111 (2004), each of which is hereby incorporated by reference in its entirety. these sensor constructions utilize porous materials, which in the present invention facilitates matrix infiltration of the pores. the pores (or cavities) in the porous sensor are typically sized in terms of their nominal “diameter” notwithstanding the fact that they are somewhat irregular in shape and may vary in diameter. pore diameters ranging from about 2 nm to about 10 μm are particularly desired, with diameters of about 10 to about 100 nm being preferred for visible light, about 2 to about 50 nm diameters being preferred for ultraviolet light, and 100 to 2000 nm being preferred for infrared light. thus, in certain embodiments the sensor construction may be characterized generally as mesoporous: having pores between about 2 to about 50 nm), nanoporous (having pores less than about 2 nm), or macroporous (having pores greater than about 50 nm). the nominal pore diameter should also be selected based upon the size of the target molecule(s) to be detected, and the dimensions of the high refractive index nanoparticles. the porous materials used to fabricate the sensor constructions are preferably semiconductor materials. semiconductor substrates which can be used to form the sensor can be composed of a single semiconductor material, a combination of semiconductor materials which are unmixed, or a mixture of semiconductor materials. semiconductor substrates which can be used to form the porous semiconductor material according to the present invention include, without limitation, silicon and silicon alloys. the semiconductor substrate is amenable to galvanic etching processes, which can be used to form the pores. these semiconductor materials can include, for example, group iv materials, including intrinsic or undoped silicon, p-doped (e.g., (ch 3 ) 2 zn, (c 2 hs) 2 zn, (c 2 h 5 ) 2 be, (ch 3 ) 2 cd, (c 2 h 2 ) 2 mg, b, al, ga, in) silicon, n-doped (e.g., h 2 se, h 2 s, ch 3 sn, (c 2 h 5 ) 3 s, sih 4 , si 2 h 6 , p, as, sb) silicon, intrinsic or undoped germanium, and doped germanium; mixtures of these materials; semiconductor materials based on group ii materials; semiconductor materials based on group iii-v materials (e.g., an, gan, inn, in x ga, in x as, al x gai x as, gaas, inp, inas, insb, gap, gasb, al oxides, and combinations thereof); and semiconductor materials based on group vi materials. the porous semiconductor materials can be fabricated according to any known procedures, e.g., those disclosed in vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001); u.s. patent application publ. no. 2006/0276047 to ouyang et al.; u.s. pat. no. 7,226,733 to chan et al.; delouise & miller, proc. spie 5357:111 (2004); and u.s. patent application publ. no. 2007/0007241 to delouise et al., each of which is hereby incorporated by reference in its entirety. basically, single layer devices can be fabricated by applying a constant current for a fixed period of time to achieve a substantially uniform porosity. multilayer devices can be fabricated by cycling between different current densities for desired time periods to produce different porosity layers. the electrochemical fabrication process can be controlled to produce a wide range of pore diameters and pore channel morphologies (dendritic to highly anisotropic). single and multilayer porous semiconductor structures are useful for substance delivery, and multilayer devices are particularly useful for optical sensing applications. the optical properties of the layer(s) may be designed for regulating the time release characteristics of the porous semiconductor material. the optical sensor can be any suitable thickness depending upon the intended use, but preferably less than about 25 microns, more preferably between about 2 to about 15 microns. typically, the thickness will vary inversely according to the desired porosity (i.e., higher porosity structures will be thicker than lower porosity structures) as well as according to the wavelength of light to be detected (i.e., structures which are used with shorter wavelength light can be thinner than structures which are used with longer wavelength light). the optical sensor can optionally be removed from its underlying solid substrate using an electropolishing step (see u.s. patent application publ. no. 2007/0184222 to delouise and miller, which is hereby incorporated by reference in its entirety) prior to embedding in the matrix. as a consequence, the porous semiconductor material that forms the optical sensor can made flexible, allowing the product to be applied to a curved surface. alternatively, the optical sensor can be formed on a solid support (e.g., on a silicon wafer substrate or a glass substrate). in at least one embodiment, the solid support forms a vapor barrier described above. in at least on embodiment, the porous semiconductor material is a microactivity biosensor of the type disclosed in u.s. pat. no. 7,226,733 to chan et al., which is hereby incorporated by reference in its entirety. the polymer matrix includes strands of one or more polymers (or co-polymers) that are reversibly cross-linked together by a cross-linking agent. as discussed more fully below, the cross-linking agent has an affinity for the target molecule, whereby the presence of target will break cross-links causing the matrix to swell. while swelling will produce a corresponding η change that can be optically detected with a reader, in preferred embodiments the majority of cross-links will dissociate and polymer chains will wash out of the sensor in the presence of a threshold concentration of the target molecule, thereby producing a visible color change that can be viewed by the naked eye when the sensor is dried. the polymer matrix may also optionally include one or more permanent cross-links (i.e., not broken in the presence of target). permanent cross-links may be formed using suitable methods, which will be apparent to the skilled artisan. the polymer used to form the matrix can be any suitable polymer material. matrix polymers, effective in this invention include but are not limited to: nylons, including without limitation nylon 6,6 and nylon 6,10; polyurethanes, polyacrylonitrile, polyvinyl alcohol, polylactic acid, polyethylene-co-vinyl acetate, polycarbonate, poly(iminocarbonate)s, polymethacrylates, poly(alkyl methacrylic acid)s, polyacrylates, poly(alkyl acrylic acid)s, poly(n,n′-diethylaminoethyl methacrylate), poly(n,n′-dialkylaminoalkyl acrylamides), poly(ethylene oxide)/peo, polyethylene amines, polyethylene terephthalate, polystyrene, polyvinyl chloride, poly vinyl phenol, polyacrylamide, poly(n-alkyl acrylamide)s, polyglycolic acids, poly lactic-co-glycolic acids, polycaprolactone, poly(-hydroxyethyl methacrylate) (polyhema), poly(vinylidene fluoride), poly(vinylidene chloride), poly(ethylene glycol)/peg, polyvinyl pyrrolidone, polyethylene, polypropylene, poly(-hydroxybutyrate), poly(ortho esters), polyanhydrides, poly(ether-ester) azopolymers, poly(dimethyl siloxane), poly(phosphazene)s, other copolymers of the above homopolymers (e.g., poly(methacrylic acid-co-ethylene glycol), and others. matrix polymers may also comprise natural polymers, such as agarose, collagen, keratin, silk, silk-like protein polymers, elastin, elastin-like protein polymers, poly(amino acids), cellulose acetate, hyaluronic acid, chitosan, fibronectin, and others. combination fibers comprising mixtures of different synthetic and/or natural polymers can also be prepared. polymer combinations help to optimize solubility and mechanical properties of the fibers. in one embodiment, the polymer matrix comprises a hydrogel polymer, comprising synthetic hydrogels, natural hydrogels, and mixtures thereof. a hydrogel matrix is particularly well suited for the present invention, because the properties of the hydrogel material can be tailored to maintain environmental conditions (e.g., hydration, ph, and ionic strength) while enabling binding and recognition to occur in a more “solution-like” environment. any of a variety of known hydrogels can be adapted for use in the products of the present invention. exemplary hydrogels include, without limitation, those found in commercial or investigative products available from johnson & johnson (e.g., nu-gel® wound dressing, nu-gel® collagen wound gel), coloplast, 3m (e.g. 3m™ tegaderm™ absorbent clear acrylic dressing), and prototype composites supplied by conmed (e.g., clearsite® tm transparent membrane), as well as hydrogels formed using any of the above-identified natural or synthetic polymers and those disclosed in peppas et al., biomed. engin. 2:9-29 (2000); u.s. pat. no. 6,855,743 to gvozdic (polyvinyl alcohol hydrogels); u.s. pat. no. 6,800,278 to perrault et al. (e.g., acrylated quaternary ammonium monomelic hydrogels); u.s. pat. no. 6,861,067 to mcghee et al. (polyurethane hydrogels); u.s. pat. no. 6,710,104 to haraguchi (organic/inorganic hybrid hydrogels); u.s. pat. no. 6,468,383 to kundel (e.g., hydrogel laminates formed by crosslinking of one or more hydrophilic polymers); u.s. pat. no. 6,238,691 to huang (polyurethane hydrogels with, optionally, antimicrobial and/or bacteriostatic agents); and u.s. pat. no. 5,932,552 to blanchard et al. (hydrogels formed of cross-linked keratin), each of which is hereby incorporated by reference in its entirety. as will be apparent to one of skill in the art, the hydrogels may also include additional agents useful for the application of choice including, for example, antimicrobial agents, bacteriostatic agents, antiviral agents, and antifungal agents. in the present invention, the polymer matrices preferably include a side group (e.g., amines, carboxylic acids, thiols) that is suitable for tethering a reagent useful for polymer cross-linking by way of example, amine-containing polyacrylamide (napmaam/aam) chains can be prepared by radical copolymerization of acrylamide (aam, sigma) with aminopropyl-methacrylamide (napmaam, polysciences) monomers using sodium formate (hcoona, sigma) to control chain length. using known synthesis schemes (bonanno & delouise, proc. spie 7167:11 (2009), which is hereby incorporated by reference in its entirety), it is possible to synthesize copolymer chains that vary in molecular weight (m w 10-100 kda) and the number of amine reactive sites per chain (2-20 mol %). in this embodiment, polymer chains with m w <150 kda are utilized to afford a sufficiently porous gel environment. the cross-linking agent can be any suitable agent capable of reversibly binding to one or more of the polymer strands with the matrix. in one embodiment, the cross-linking agent is formed using one or more receptors and one or more target analogs. the receptors reversibly bind to the target analogs, albeit with a lower affinity than the target molecule. thus, in the presence of the target molecule, the target analog is displaced, breaking the cross-link between polymer strands. breaking the reversible cross-links results in swelling of the polymer matrix and a change in the refractive index of the polymer matrix. in one embodiment, the one or more high refractive index nanoparticles are nonspecifically encapsulated in the polymer matrix. in this embodiment, swelling of the polymer matrix in the presence of the target results in release of at least one of the nanoparticles from the polymer matrix, whereby a change in the refractive index of the polymer matrix occurs. in other embodiments, the one or more high refractive index nanoparticles are specifically retained in the polymer matrix (via one of the cross-linking reagents and/or via direct attachment to the polymer matrix). alternatively, both non-specific and specific retention of the nanoparticles can be utilized. combining non-specific and specific nanoparticle retention in the same optical sensor may be useful for tuning the magnitude of the amplification that occurs at different target concentrations. in certain embodiments, one or more receptors and/or one or more target analogs are also coupled to the one or more nanoparticles. in this embodiment, the one or more receptors, the one or more target analogs, and the one or more nanoparticles collectively form one or more reversible crosslinks within the polymer matrix. binding of one of the target molecules to one of the receptors results in displacement and release of at least one of the nanoparticles from the polymer matrix, whereby a change in the refractive index of the matrix occurs. in a further embodiment, one or more receptors or one or more target analogs are coupled to the polymer matrix and the other of the one or more receptors and the one or more target analogs is coupled to the one or more nanoparticles, whereby the one or more nanoparticles are reversibly bound to the polymer matrix. binding of one of the target molecules to one of the receptors results in displacement and release of at least one of the nanoparticles from the polymer matrix, whereby a change in the refractive index of the matrix occurs. in these various embodiments, the one or more receptors can be monovalent, i.e., capable of binding only a single target analog or target at a time. alternatively, the one or more receptors can be multivalent, i.e., capable of binding to more than one target analog or target at a time. the one or more receptors can be any molecule that can be used to form a labile bond. exemplary classes of receptor molecules include, without limitation, non-polymeric small chemical molecule complexes (e.g., bis (which forms non-reversible crosslinks), bac (which forms reversible crosslinks)), peptides, polypeptides, proteins, peptide-mimetic compounds, antibody complexes (e.g., whole antibodies, antibody fragments, recombinant single chain variable fragment antibodies (scfv)), oligonucleotides (e.g., nucleic acid molecules, sdna, rna), nucleic acid aptamers, enzymes, and ribozymes. specific sub-classes include receptors for cell surface molecules, lipid a receptors, antibodies or fragments thereof, peptide monobodies, lipopolysaccharide-binding polypeptides, peptidoglycan-binding polypeptides, carbohydrate-binding polypeptides, phosphate-binding polypeptides, nucleic acid-binding polypeptides, polypeptides that bind an organic warfare agent, and polypeptides that bind to specific protein or polypeptide targets. the target analogs can be any agent that structurally and/or functionally mimics the target, but has a lower affinity for the receptor than the target. thus, target analogs can be derivatives of the target. in some instances, specific attachment of a target molecule to a polymer chain and/or cross-linking agent alters a the receptor's binding affinity for the target molecule. in such cases, the target molecule itself may be used as the target analog, provided the receptor has a lower binding affinity for the specifically-attached target molecule than for unbound target. target molecules that can be detected in accordance with the present invention include, without limitation, antigens, antibodies, proteins, glycoproteins, peptidoglycans, carbohydrates, lipoproteins, lipoteichoic acid, lipid a, phosphates, nucleic acids, pathogens, host markers of infection, organic warfare agents, organic compounds, drugs of abuse, opiates, pain killers, explosives, biomolecules (e.g., metabolites), antimicrobial peptides, immune function markers, cancer markers, and disease markers. in one embodiment, the detectable change in refractive index occurs at a target molecule concentration of between picograms per milliliter and milligrams per milliliter. in another embodiment, the detectable change in refractive index occurs at a target molecule concentration in the nanomolar to micromolar range. exemplary target molecule/target analogs include, without limitation, a first oligonucleotide and a second oligonucleotide that contains one or more mismatches with respect to a receptor oligonucleotide; drug compounds (including aptamers for recreational drug molecules (see u.s. patent application publ. no. 2003/0224435 to seiwert, which is hereby incorporated by reference in its entirety) such as morphine and structural analogs of morphine such as morphine-3-glucuronide (m3g), which has a lower affinity for certain morphine binding antibodies; avidin or streptavidin/antibodies that bind to biotin with lower affinity that either avidin or streptavidin; antibodies for detection of environmental pollutants (polychlorinated biphenyls, polyaromatic hydrocarbons), neurotransmitters (acetylcholine), peptide hormones, microbial pathogens, etc. one exemplary system, illustrated in fig. 2 (protocol 1), includes polymer strands that can be covalently linked with a target analog, and then cross linked with a receptor specific for the target analog. receptor cross-links specific for the target analog can be displaced in the presence of target, because the receptor has greater affinity to the target than to the target analog. another exemplary system, illustrated in fig. 2 (protocol 2), includes polymer strands that can be covalently linked with a target analog, and then cross linked with a pair of receptors specific for the target analog along with a secondary ligand (e.g., protein g (two antibody binding sites) or protein a (four antibody binding sites)). this effectively spaces the polymer chains further apart and promotes greater porosity to the polymer. as with the protocol 1 system, receptor cross-links specific for the target analog can be displaced in the presence of target. a related system, illustrated in fig. 2 (protocol 3), includes polymer strands that can be covalently linked with a target analog, and then cross linked with a pre-assembled linker that includes two or more receptors specific for the target analog along with a secondary ligand (e.g., protein g (two antibody binding sites) or protein a (four antibody binding sites)). as with the protocol 1 and 2 systems, receptor cross-links specific for the target analog can be displaced in the presence of the target. yet another system, illustrated in fig. 2 (protocol 4), includes two sets of polymer strands for co-polymer matrix formation. one set of strands is functionalized for covalent bond formation with a target analog, and a second set of strands is functionalized with a receptor specific for the target analog. cross-linking of the strands is directly between the two agents (receptor and target analog). receptor-target analog cross-links can be displaced in the presence of target. a related system, illustrated in fig. 2 (protocol 5), also includes two sets of polymer strands for co-polymer matrix formation. as with protocol 4, one set of strands is functionalized for covalent bond formation with a target analog, and a second set of strands is functionalized with a receptor specific for the target analog. in this embodiment, both direct cross-linking as in protocol 4 and secondary ligand (e.g., protein g/a)-assisted cross-linking is utilized. receptor cross-links specific for the target analog can be displaced in the presence of target. the protocols illustrated in fig. 2 can be modified to detect any target of interest using suitable target-specific receptors and target analogs as described herein. the one or more high refractive index nanoparticles can be incorporated into the polymer matrix in each of the exemplary protocols in a variety of ways, including: (a) specific attachment to one or more of the polymer chains, (b) specific attachment to one or more of the receptors, (c) specific attachment to one or more of the target analogs, (d) specific attachment to the secondary ligand, (e) nonspecific encapsulation, and (f) combinations of (a)-(e). specific attachment in (a)-(d) may be carried out by any number of methods, including covalent attachment to the respective agent and/or indirect attachment via, e.g., a second receptor-ligand interaction in which the second receptor is specific for the high refractive index nanoparticle (for example, the nanoparticle or the agent to which it is specifically attached is functionalized with biotin and the other is functionalized with streptavidin). regardless of the mode for introducing the high refractive index nanoparticles into the matrix, the nanoparticles are preferably loaded into the gel at about 0.01 to about 50 wt %, more preferably about 0.1 to about 10 wt %. the one or more high refractive index nanoparticles can be formed of any suitable material. in one embodiment, the refractive index of the nanoparticles is greater than 1.5. in another embodiment, the refractive index of the nanoparticles is at least 1.7. in another embodiment, the refractive index of the nanoparticles is greater than 2.0. in another embodiment, the refractive index of the nanoparticles is at least 2.5. in a further embodiment, the refractive index of the nanoparticles is at least 3.6. the nanoparticles can be any size between about 1 nm and about 1000 nm, preferably between about 2 nm and about 750 nm. in preferred embodiments, the nanoparticles have a diameter that is small enough to diffuse out of the pores of the optical sensor. by way of example, the nanoparticles are preferably between about 5 and about 100 nm, more preferably between about 5 and about 50 nm. exemplary high refractive index nanoparticles include, without limitation, inp, pbs, pbse, cdse, zns, cdse core zns shell, cdte, cds, si, fexoy, tio2, alxoy, znos, sic, tic, and other oxides and carbides and core/shell types. coating of the optical sensor surface with a well-controlled polymer thickness can be carried out by spin coating the optical sensor with a polymer solution. inducing cross-link formation can be performed before, during, or after spin-coating. preferably, in the final product, any polymer matrix remaining on an exterior surface of the porous matrix is less than 50 microns thick, more preferably less than about 100 nanometers thick. in a preferred embodiment, the pores of the porous matrix are substantially filled with the polymer matrix, while the exterior surface of the product is substantially free of the polymer matrix. the product, once formed, is intended to be used with a sample to be tested. the sample can be actively introduced to the polymer matrix. in certain embodiments, the product can be applied at a wound site or on uninterrupted skin or tissue so that the sample is passively absorbed into the polymer matrix. regardless, the fabrication procedures are intended to be conducted in a sterile environment so as to prevent contamination. moreover, the sterile product, once prepared, is intended to be packaged in a sterile packaging to allow for distribution and handling prior to end use. sterile packaging procedures are known in the art. another aspect of the present invention is a method of making a product of the invention. this method involves preparing an optical sensor and at least partially embedding the optical sensor in a hydrogel matrix. typically, one or more polymer solutions is poured or spin coated onto the optical sensor, thereby infiltrating the pores, and cross-linking is allowed to take place. because cross-linking generally takes several days, suitable cross-linking agents may be added to the polymer solution(s) before, during, or after the one or more polymer solutions are poured or spin-coated onto the matrix, provided cross-linking primarily takes place within the optical sensor. the cross-linking can be carried out as described above. the high refractive index nanoparticles may likewise be added before, during, or after the one or more polymer solutions are poured or spin-coated onto the optical sensor. in at least one embodiment, one or more high refractive index nanoparticles are encapsulated within the polymer matrix by: dissolving the polymer precursor(s) into a solution containing the high refractive index nanoparticles, adding the cross-linking agents, and then pouring or spin-coating the resulting polymer solution over the optical sensor. in at least another embodiment, the high refractive index nanoparticles are covalently bound to one or more cross-linking agents before being added to the polymer solution(s). in at least another embodiment, the high refractive index nanoparticles are covalently bound to one or more polymers before the polymer solution(s) are poured or spin-coated onto the optical sensor. combinations of the three preceding embodiments are also contemplated. although in certain embodiments the products are intended to be used with ambient light or a direct light source to produce a change in refractive index that is detectable by eye (e.g., from red to green), in other embodiments changes in the refractive index that are too subtle to be measured by eye can be measured using a detection device that includes, in addition to the product, a source of illumination and a detector positioned to capture light reflected from the product and to detect changes in the refractive index of the hydrogel matrix. exemplary detectors include, without limitation, collecting lenses, monochrometers, and spectrometers. a computer with an appropriate microprocessor can be coupled to the detector to receive data from the device and analyze the data to compare the optical response (reflected light, transmitted light, and/or photoluminescence) before and after exposure of the device to a target molecule. many widely available detectors afford the detection of optical shifts of about 0.001 nm or greater. a further aspect of the present invention relates to a method of detecting a target molecule in a sample. basically, a product of the present invention is exposed to a sample under conditions effective to allow binding of a target molecule in the sample to the one or more receptors, thereby displacing the target analogs. after such exposure, it is determined whether the biological sensor emits an optical response (reflected light, transmitted light, and/or photoluminescence) emission pattern which has shifted due to the change in refractive index. if a detectable change is not detected, then the target molecule is not present in the sample (or is present below the limit of detection). however, if a detectable change is detected, then the target molecule is present in the sample. to determine whether a shift has occurred, a first (baseline) optical response (reflected light, transmitted light, and/or photoluminescence) emission pattern is measured prior to exposure to a sample. after exposure to the sample, a second optical response emission pattern is measured and the first and second emission patterns are compared. a shift as little as about 0.001 nm can indicate the presence of the target in the sample. however, to facilitate large shifts that are more easily detected, following exposure any swelled polymer matrix and high refractive index nanoparticles can be washed from the optical detector. after washing, the second measurement can be made. for detection by naked eye, the baseline measurement can be simply noting the color of the optical sensor before sample exposure. as noted above, the optical sensor (and product containing the same) can be used to detect the presence of a target (e.g., pathogen) in a sample. samples which can be examined include blood, water, urine, sweat, a suspension of solids (e.g., food particles, soil particles, etc.) in an aqueous solution, or a cell suspension from a clinical isolate (such as a tissue homogenate from a mammalian patient). for example, the product may be used to detect a pathogen in a sample. other exemplary uses include, without limitation, pregnancy tests and diabetes test strips. as will be apparent to one of ordinary skill the art, one or more therapeutic agents may optionally be retained within the polymer matrix as described in u.s. patent application publ. no. 2007/0184222 to delouise and miller, which is hereby incorporated by reference in its entirety, such that the therapeutic agents are released from the product when the cross-links break in the presence of the target. in such embodiments, the amplified change in refractive index can serve as an optical (e.g., visual) confirmation of therapeutic agent delivery. the cross-link architecture can be designed to release varying concentrations of the therapeutic agent at varying target concentrations. yet another aspect of the present invention is a method of detecting a pathogen and/or infection at a wound site. this method involves providing a product according to the present invention in which the polymer matrix contains one or more cross-linking agents specific for a target molecule (of the pathogen or host marker of infection to be detected). in the presence of the target molecule, the polymer matrix will destabilize and swell, allowing the high refractive index nanoparticles and polymer matrix to wash away from the optical sensor. as a result, the refractive index of optical sensor changes, causing a detectable shift in the optical properties of the optical sensor. detection of the pathogen/infection can be made without removing the optical sensor/product from the wound site, in which case a light source and spectrometer may need to be used to detect any change in the refractive index. alternatively, detection of the pathogen/infection can be made following removal of the optical sensor/product from the wound site, and after washing any swollen or destabilized polymer and high refractive index nanoparticles from the optical sensor surface. examples the following examples are provided to illustrate embodiments of the present invention but are by no means intended to limit its scope. example 1 psi transducer substrate preparation and characterization the methods employed to produce the macroporous silicon sensors used in examples 1-6 have been described in detail elsewhere (kilian et al., acs nano 1(4):355-61 (2007); delouise & miller, anal. chem. 77(10):3222-30 (2005), each of which is hereby incorporated by reference in its entirety). briefly, psi mirror structures were fabricated from n+ <100> silicon wafers (sb doped, 0.01-0.08 ω-cm) using a room temperature electrochemical etch process. the aqueous electrolyte contained basf pluronic l31 (0.1%) surfactant and hydrofluoric acid (5% hf). the mirror structure used in examples 1-6 was fabricated with alternating current densities of 40 and 70 ma/cm 2 to yield 16 alternating layers of 71 and 84% porosity with a total thickness of ˜2.9 μm measured by sem. the psi samples were thermally oxidized in dry o 2 at 900° c. to enhance stability of the psi and to create hydrophilic pore channels. these devices exhibit a wavelength shift sensitivity (wss) of the 205 nm/riu determined by infiltrating liquids with varying η into the porous matrix and measuring the magnitude of the wavelength shift. wss is the slope of a plot of wavelength shift vs. η. example 2 preparation glutathione coated quantum dots commercial cdse/zns core/shell octadecylamine (oda)-capped quantum dots™ (qds) (620 nm emission, nn-labs, #cz620) in toluene were used in examples 3-4. glutathione-capped qds (gsh-qds) were synthesized in-house via a ligand exchange procedure. efficient ligand exchange requires working with solvent systems in which ligands are readily soluble. it was observed that oda ligand exchange does not work efficiently in toluene. therefore, qds were first transferred to tetrahydrofuran (thf). a 200 μl aliquot of stock qds was added to a methanol:acetone (1:1) solution and separated by centrifugation at 14,000 rpm for 5 minutes. toluene was decanted and qds were resuspended in 200 μl of tetrahydrofuran (thf). gsh was added to methanol and the ph of the solution adjusted to ph=11 with tetramethylammonium hydroxide pentahydrate ((ch 3 ) 4 noh.5h 2 o). the gsh methanol solution (20 mg/ml, 1 ml) was slowly added to the thf qd solution (0.25 μm, 200 μl) of cdse/zns qds at room temperature. the mixture was stirred at 60° c. for 2 hours and precipitated with the addition of ether by centrifugation at 14,000 rmp for 5 minutes. the supernatant was discarded and the qd sample was redispersed in deionized water. the solution was filtered through a 300 kda membrane filter (microsep centrifugal filter, pall life sciences) for purification. excess gsh was removed by the dialysis against deionized water using micro dispodialyzer 5000 mwco (harvard apparatus). surface charge (zeta potential) and hydrodynamic radius were measured using malvern instruments nanosizer. results are reported in table 1 below. table 1optical properties of qd nanoparticles.quantumzeta potentialhydrodynamicsampleyield (%)(mv)diameter (nm)oda-qds56n/an/agsh-qds40.7−23.820.9 example 3 preparation of hydrogel-psi hybrid sensors for examples 3-4, an acrylamide (aam) polymer crosslinked with n,n′-methylenebisacrylamide (bis) and n,n bis-acryloyl cystamine (bac) formulated with a molar ratio of 195:4:1 aam:bac:bis was used. the measured polymer density is 1.020 g/ml. bac contains a disulfide linkage that cleaves under suitable reducing conditions to cause swelling of the polyacrylamide (pa) gel. in this example, 50 mm tris[2-carboxyethyl]phosphine (tcep) reducing agent was used. all monomers (aam, bac, bis) were diluted in an aqueous 25 v/v % ethanol stock solution. the monomer stock solution contained 0.05 g aam, 0.00376 g bac, 0.000556 g bis, 135.78 μl ethanol, and 407.35 μl water, to yield a 10 wt % monomer stock solution. n,n,n′n′-(tetramethylethylenediamine) (temed) was added to the monomer stock solution at 2.1 wt % (1.46 μl). to prepare hybrid psi devices, 15 μl of monomer stock solution was added to either 15 μl of water for control or 15 μl of a 17.8 μm gsh-qd solution prepared as described in example 2 to yield a final 5 wt % hydrogel. the qd loading was estimated to be 0.29 wt %. the gel/qd solution was ultrasonicated for 1 minute. ammonium persulfate (aps) initiator (2 μl of 2 wt %) was used as a free radical generator to initiate polymerization. aps (2 μl) was added to the monomer solutions and mixed quickly with a pipette. within ˜30 seconds, ˜10 μl of the solutions were pipetted into a custom glass fixture that restricts oxygen presence and controls thickness of the gel height above the psi sensor to be the thickness of teflon tape (˜100 μm). the remaining polymer with aps initiator (˜20 μl) was left in the eppendorf tube and kept closed to restrict oxygen to create bulk hydrogels for η measurements made using a bench-top abbe refractometer (bausch & lomb). all gels were left for overnight to cross-link at room temperature in the dark. example 4 optical detection with hybrid-psi sensors the optical reflectance spectra were measured using an advantes 3648-usb2 spectrophotometer with an optical resolution of 0.06 nm pixel −1 . an incident beam of white light (spot size ˜1.3 mm 2 ) was illuminated at normal incidence. all plots containing error bars represent the standard deviation of each data point taken with a minimum of n=2 for interday experiment trials and 3 measurement locations per sensor. reflectivity spectra were first recorded following thermal oxidization of the psi sensors. next, the wavelength shift for water filling pores was measured as a reference for each location on chip. chips were dried with n 2 gas and the hydrogel was cast into the sensor as explained in example 3. the cross-linked gels were soaked overnight in 5 ml water at room temperature to allow for equilibrium swelling and possible qd out-diffusion. the hybrid-psi sensors were then held within a custom fixture under 10 ml of pbs and the wavelength shifts were measured in 3 identical locations. finally, 500 μl of 50 mm tcep reducing agent was added to hybrid sensor/gels and temporal blue wavelength shift response was monitored for 2 hours at a single location. the hybrid-psi sensors were then rinsed with di water 3 times to remove tcep (η=1.3368) from the sensor and resulting wavelength shifts remeasured in 3 identical locations. the magnitude of wavelength shifts reported are in reference to water filling the pores. optical shifts for casting the control and qd (˜8.9 μm, 0.29 wt %) loaded hydrogels into the psi sensor matrix and following over night (o/n) water soak and exposure to tcep reducing agent (2 hours) are listed in table 2 and displayed in fig. 3 . the wavelengths shifts recorded immediately after casting the hydrogel and following o/n soak water are in reference to pure water filling the pores. results show the sensor hybrid containing the gel loaded with the high refractive index qd produced a statically significant 2× larger shift (5.47 nm) than the control (2.8 nm). following an o/n soak in water, both gels produced an optical blue shift equating to ˜20% decrease of the magnitude relative to the initial shift resulting from gel infiltration. since the % change in the magnitude of the blue shift following o/n water soak for the qd loaded gel is equivalent to the control, the origin of the decrease is consistent with osmotic equilibrium hydrogel swelling and out-diffusion of polymer monomers and not loss of encapsulated qd (chatterjee et al., j. aerospace eng. 16:55-64 (2003), which is hereby incorporated by reference in its entirety). this data suggests that a 5 wt % polyacrylamide gel with 0.76 wt % cross-linker is sufficient to encapsulate anionic qd (−24 mv surface charge) with hydrodynamic radius of ˜21 nm as predicted from stellwagen, electrophoresis 19(10):1542-47 (1998), which is hereby incorporated by reference in its entirety, and holmes & stellwagen, electrophoresis 12:612-19 (1991), which is hereby incorporated by reference in its entirety. table 2optical red shifts (nm) following processingof hybrid optical sensors.+tcep (2 hr) +hydrogelsoak o/n in waterwater rinseavgstdevavgstdevavgstdevcntrl2.800.162.300.781.2070.328qd~8.9 um5.470.454.510.561.8140.418 these samples were then treated with tcep disulfide reducing agent to break the bac cross links, which were formulated at a 4:1 bac:bis mole ratio. significant swelling is anticipated but the gel cannot completely dissolve due to the persistence of bis cross links. each hybrid gel sensor was soaked in 500 μl 50 mm tcep for 2 hours and then rinsed with water. optical shifts recorded following tcep treatment revealed significant blue shifts for both gels with the qd gel exhibiting a larger % decrease due to loss of the high refractive index nanoparticles (np). the residual red shifts following tcep treatment for both gel samples were similar (not statistically different, p=0.05), which suggests efficient qd release. this data demonstrates that high refractive index np can be used for optical amplification. using a bench-top abbe refractometer, the refractive index of the 5 wt % polyacrylamide control hydrogel was measured to be η=1.3459. the refractive index of the qd loaded hydrogel was measured to be η=1.3488. it was estimated, assuming a qd loading level of 0.29% and a qd η ˜2.5 (imai et al., eu. polymer j. 45(3):630-38 (2009), which is hereby incorporated by reference in its entirety), that the refractive index of the bulk qd gel should be η=1.3493, which is only slightly higher (δ=0.0005) than what was experimentally measured. from knowledge of the sensor wss (205 nm/riu), the anticipated sensor red shift (δλ r ) for gels in the porous sensor relative to water (η=1.3333) can be predicted. the control gel red shift was measured to be 2.30 nm after overnight water soak (see table 2), as expected. for the same gel loaded with qd, the measured red shift after overnight water soak was 4.51 nm (see table 2), which is a ˜23% higher refractive index change. this demonstrates that high refractive index nanoparticles may be used to amplify the optical signal. discussion of examples 1-4 the development of nanoporous silicon sensor design employing an optical amplification strategy was sought, to leverage the fact that psi is a volume (porosity) sensitive transducer. the approach was to integrate a target responsive hydrogel (trap-gel) into the porous matrix of a psi optical sensor (bonanno & delouise, adv. funct. mater. 20(4):573-78 (2010) (see examples 5-16, infra); bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008); bonanno & delouise, proc. spie 7167:71670f (2009), each of which is hereby incorporated by reference in its entirety). probe molecule analogues are covalently linked to the backbone of the hydrogel. chains can be crosslinked by, for example, multivalent antibodies. target competes for binding to the antibody causing crosslinks to break and consequent polymer swelling and chain dissolution. this strategy extends probe analogue throughout the 3-d internal volume of the pore volume improving upon techniques that limit probe immobilization to the internal rigid surface area (2-d) of psi. target induced material property changes (swell and mass loss) and the corresponding refractive index changes are significantly large for optical detection without signal amplification. proof of principle of this sensor design concept employing polyacrylamide and amine-functionalized polyacrylamide/n-(3-aminopropyl)-methacrylamide (paam-na) hydrogels have been demonstrated (bonanno & delouise, adv. funct'l mater. 20(4):573-78 (2010) (see examples 5-16, infra); bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008); bonanno & delouise, proc. spie 7167:71670f (2009), each of which is hereby incorporated by reference in its entirety). to improve signal to noise, extend the lower limit of detection, and enable colorimetric read out by eye, an optical amplification strategy was developed by incorporating high refractive index nanoparticles (np) into the hydrogel. np have been incorporated into polymer films, as high as 50 wt %, to make highly transparent high ri films for various optical applications (imai et al., eu. polymer j. 45(3):630-38 (2009); lü et al., j. mater. chem. 13:2189-95 (2003), each of which is hereby incorporated by reference in its entirety). studies show that the polymer ri scales linearly with np wt % loading (zimmermann et al., j. mater. res. 8(7):1742-48 (1993), which is hereby incorporated by reference in its entirety). in this sensor design, np can be incorporated in different ways to tune the hydrogel target optical response. for example, np can be nonspecifically encapsulated or surface functionalized to bind probe analogue directly on the polymer chain or to participate in forming chain cross-links target binding will induce swelling that allows np to diffuse out. the data described in examples 1-4 validate the viability of a np optical signal amplification scheme employing hybrid porous silicon (psi) sensors. the development of target responsive hydrogels integrated with psi optical transducers was investigated. these hybrid-psi sensors can be designed to provide a tunable material response to target concentration ranging from swelling to complete chain dissolution. the corresponding refractive index changes are significant and readily detected by the psi transducer. to increase signal to noise, lower the limit of detection, and provide a visual read out capability, the incorporation of high refractive index nanoparticles (np) into the hydrogel for optical signal amplification was investigated. these nps can be nonspecifically encapsulated, or functionalized with bio active ligands to bind polymer chains or participate in cross linking examples 1-4 demonstrate encapsulation of high refractive index qd nanoparticles into a 5wt % polyacrylamide hydrogel crosslinked with n,n′-methylenebisacrylamide (bis) and n,n bis-acryloyl cystamine (bac). a qd loading (˜0.29 wt %) produced a 2× larger optical shift compared to the control. dissolution of disulphide crosslinks using tcep reducing agent induced gel swelling and efficient qd release. it is believed that this hybrid sensor proof of concept demonstrates a versatile technology platform capable of detecting a wide range of bio/chemical targets. target analogs can be linked to the polymer backbone and cross-links can be achieved with target responsive multivalent receptors, such as antibodies, using known attachment chemistry. the optical signal amplification scheme will enable a lower limit of detection sensitivity not yet demonstrated with psi technology and, as demonstrated herein, colorimetric readout visible to the naked eye. example 5 copolymer synthesis procedures to copolymerize aam with napmaam were adopted from seiffert and oppermann, macromolec. chem. phys. 208:1744-52 (2007), which is hereby incorporated by reference in its entirety, and details are reported in bonanno & delouise, proc. spie 7167:71670f (2009), which is hereby incorporated by reference in its entirety. in brief, aam (mp biomedical, mw=71.08 g mol −1 ), napmaam (polysciences inc., mw=178.7 g mol −1 ), and sodium formate (hcoona, alfa aesar, mw=68.01 g mol −1 ) were added to deionized water (30° c., 15 minutes) and stirred under nitrogen. the total monomer concentration was fixed (4.6 mm in 10 ml water) and the exact monomer formulations are listed in table 3. chain transfer agent, hcoona, was added to control the linear polymer chain length (fevola et al., j. polym. sci. a 41:560-68 (2008), which is hereby incorporated by reference in its entirety). free radical polymerization was initiated with n,n,n′n′-(tetramethylethylenediamine) (0.25 mol %, 1.7 μl, sigma, mw=116.2 g mol −1 ) and ammonium persulfate (0.1 mol %, 70 μl of a 2wt % aqueous solution, sigma). precipitation in methanol (2 wt % hydrochloric acid) resulted in crude product that was filtered, washed in methanol, resolubilized in deionized water, and dialyzed against water (2 days at 4° c.) with stirring (spectra/por®, mwco=3500 g mol −1 ). remaining solvent was removed via rotary evaporation and high vacuum for 24 hours. characterization of the various copolymer products was completed by 1 h nmr spectroscopy and size exclusion chromatography (sec) as described in bonanno & delouise, proc. spie 7167:71670f (2009), which is hereby incorporated by reference in its entirety. table 3reaction mixtures and copolymer product characterization.composition of reaction mixture [a]characterization of resulting copolymer productsfraction offraction ofnapmaamnapmaamadded[aam][napmaam][hcoona]in copolymermn [c]mw [c]polydispersityrg [d][f, mol %][mmol][mmol][mmol][f, mol %] [b][g mol −1 ][g mol −1 ]mw/mn[nm]04.60005—————24.5080.09254.1417400631333.6321.5104.1400.460517.8224900956003.8426.5253.4501.150537.27332781439854.3337.4[a] copolymerization of aam with napmaam with varying mole fractions of napmaam (f) and fixed amount of sodium formate (hcoona) added to monomer reaction mixture in 10 ml volume deionized water.[b] f was determined using 1 h nmr (400 mhz in d 2 o) (bonanno & delouise, proc. spie 7167: 71670f (2009), which is hereby incorporated by reference in its entirety).[c] copolymer number average molecular weight (mn) and weight average molecular weight (mw) were determined using size exclusion chromatography (sec).[d] the radius of gyration (rg) was calculated using dynamic light scattering. rg is the root-mean-square distance of the elements in the chain from its center of gravity and describes the mean radius of the random coil polymer chains. example 6 sulfhydryl functionalization of copolymer copolymer was dissolved in phosphate buffered saline buffer (pbs, ph 7.4, 10 wt %). satp (thermo scientific, 2 μl of 1.533 m, mw=245.25 g mol −1 ) diluted in dimethylformamide was added to 50 μl of copolymer solution (2 hours at room temperature). unbound satp was removed with dialysis (harvard apparatus, dispo equilibrium dialyzer, mwco=5000 g mol −1 ) overnight at room temperature against 1000 excess volume of pbs. hydroxylamine-hcl in pbs (5 μl of 1 m, ph 7.1) was added to 50 μl satp-bound copolymer solution (mixed 1 hour at room temperature) to deprotect the acetylated sulfhydryl (sh) groups. ellman's assay (riddles et al., anal. biochem. 94:75-81 (1979), which is hereby incorporated by reference in its entirety) was performed to quantify sh attachment to copolymer chains with varying mol % napmaam (table 4). dimethylsulfoxide (dmso) was added as an oxidizing agent (2 μl) to sulfhydryl functionalized copolymer solutions (50 μl of 10 wt %) to promote disulfide bond formation. table 4characterization of aam/napmaam copolymers and sulfhydryl functionalized copolymers.fraction offraction ofcalculatedquantitiy of attachedratio of sulfhydrylnapmaam innapmaam incopolymerquantity ofsulfhydryl groupsconcentrationreaction solution,copolymer [a] ,mn [b]napmaamto copolymer [c]present to availablef [mol %]f [mol %][g/mol][nmoles][nmoles]napmaam moieties24.14174001.197.536.331017.82249003.5826.507.412537.27332785.6034.306.13[a] mol % napmaam was determined using 1 h nmr (bonanno & delouise, proc. spie 7167: 71670f (2009), which is hereby incorporated by reference in its entirety).[b] copolymer number average molecular weight (mn) and weight average molecular weight (mw) were determined using size exclusion chromatography (sec).[c] quantity of attached sulfhydryl groups was determined using colorimetric ellman's assay. example 7 psi sensor preparation the methods employed to produce psi films have been described in detail in bonanno & delouise, biosens. bioelectron. 23:444-48 (2007), which is hereby incorporated by reference in its entirety. briefly, mesoporous psi bragg mirrors were fabricated from p+ <100> silicon wafers (b doped, 0.006-0.009 ω-cm) using an electrochemical etch process at room temperature. etching was completed in electrolyte containing ethanol (70%) and hydrofluoric acid (hf, 15%). the bragg mirror consisted of 16 alternating layers of porosity (79 and 87%, d=19 and 43 nm, respectively) with a total thickness (˜3.2 μm) measured by sem. the wavelength shift sensitivity (wss=308.6 nm/riu) was determined using infiltration of liquids with known η values. the other psi architectures studied in figs. 4a-d were fabricated using similar electrochemical etching techniques and their resulting pore characteristics are listed in table 5. macroporous psi (d>50nm) was etched into n+ <100> silicon wafers (sb doped, 0.01-0.08 ω-cm) in electrolyte containing pluronic l31 (0.1%) and hf (5%). after thermal oxidation (900° c., 3 minutes) all psi sensors were silanized with (mercaptopropyl)trimethoxysilane (2 wt %, gelest) in ethanol (50%) for 15 minutes, rinsed with ethanol, rinsed with water, dried with nitrogen gas, and kept at 100° c. for 20 minutes to cross-link the silane and evaporate any remaining solvent. table 5characterization of psi sensor architectures.characterization of porous structureetching conditionsaverageliquidcurrentporegravimetricinfiltrationdopingdensityetch timedepthdiameter [a]porositywss [c]porositytypearchitecture[ma cm -2 ][s][μm][nm][%] [b][δλ/δriu][%] [d]psingle layer30143.81.681979287.1—psingle layer6094.41.684387393.9—nsingle layer40120.01.687378218.1—nsingle layer70108.01.6810692328.2—pmirror30/604.01/3.03 × 163.2019/4379/87308.664.2/73.5nmirror40/703.75/2.75 × 162.8873/10678/92231.5—[a] image j software analysis of top down sem images were used to calculate the average pore diameter within a distribution.[b] gravimetric measurements calculate % porosity based on mass measurements as described in equation 1. the si chip mass is measured prior to (m1) and post etching of a porous si layer for 300 seconds (m2). the porous si layer is dissolved away in basic koh and the final mass (m3) is measured.[c] wavelength shift sensitivity (wss) is measured by measuring the wavelength shift associated with filling the pores with fluids of known η. plotting wavelength shift versus change in η results in a linear plot with slope indicating the wss (δλ/δη).[d] bruggeman approximation theory is utilized in matlab to simulate porous si sensor response. input values of porous layer depth are held constant and the porosity values are calibrated to attain the same response as observed in experimental measuring of wss for filling pores with solutions of known η. the porosity values attained in simulation represent the open porosity available for liquid infiltration as described in segal et al., adv . funct ' l mater . 17:1153-62 (2007), which is hereby incorporated by reference in its entirety, and are often lower than those measured by gravimetric measurements. example 8 preparation of s—s-copaam-psi hybrid sensor the sulfhydryl functionalized copolymer solutions prepared as described in examples 5-6 were immediately applied to the mercaptosilane treated psi sensors in a custom glass fixture within a humidified chamber to minimize thickness of polymer on top of the psi sensor (700 μm). disulfide bond formation (cross-linking of the hydrogel) was allowed to continue at room temperature in the humidified chamber for 6 days, as ellman's assay (riddles et al., anal. biochem. 94:75-81 (1979), which is hereby incorporated by reference in its entirety) results indicated complete disulfide formation occurs within 5 days ( figs. 5a-b ) (see example 10, infra). the resulting hybrid s—s-copaam-psi sensors were soaked in deionized water (10 ml) for 2 days on a shaker plate (water replaced after 1 day) to allow equilibrium swelling and release of uncross-linked copolymer chains. example 9 optical detection of reflectance spectra the hybrid s—s-copaam-psi sensors were held within a custom fixture and exposed to a normal incident beam of white light (spot size ˜1.3 mm 2 ). reflectance spectra normal to the surface were measured using an advantes 3648-usb2 spectrophotometer (optical resolution of 0.06 nm pixel −1 ). the custom fixture holds the psi sensor in a well containing various solutions and is covered by glass to diminish solution evaporation. all error bars in plots represent the standard deviation of each data point taken with a minimum of n=2 for interday experiment trials and 3 measurement locations per sensor. example 10 ellman's reagent to quantify free sulfhydryl concentration in solution ellman's reagent, 5,5′-dithio-bis-(2-nitrobenzoic acid) (dtnb), is a versatile water-soluble compound used to quantitate free sulfhydryl (sh) groups in solution (riddles et al., anal. biochem. 94:75-81 (1979), which is hereby incorporated by reference in its entirety). a measurable yellow-colored product results when this chemical reacts with sh groups. a calibration curve was created by adding 30 μl of varying concentrations of cysteamine to 95 μl of 0.1 mm dtnb aqueous solution (ph 7.1) and measuring the absorbance at 405 nm ( fig. 5a ). sh attachment to various copolymer formulations (0-37.27 mol % napmaam) after satp chemistry was performed was determined by comparing absorbance measurements to the calibration curve. as disulfide bonds form between sh functional copolymer chains the number of free sh groups decreases. this reduction of sh concentration was temporally monitored to determine how long complete disulfide cross-linking of the s—s-copaam hydrogel network takes ( fig. 5b ). copolymer solution (30 μl, 4.14 mol % napaam) was added. the [sh] decreases and saturates by 5 days for the copolymer solution. all s—s-copaam hydrogels were therefore allowed to cross-link for 6 days in a humidified chamber before subsequent use. example 11 synthesis of disulfide cross-linked hydrogel (s—s-copaam) chemical formation of s—s-copaam is shown in figs. 6a-f . free radical polymerization of acrylamide (aam) and n-(3-aminopropyl)-methacrylamide (napmaam) monomers formed copolymer chains with a controlled concentration of nucleophilic amine moieties ( figs. 6a-b ) (bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008); bonanno & delouise, proc. spie 7167:71670f (2009); seiffert & oppermann, macromolec. chem. phys. 208:1744-52 (2007), each of which is hereby incorporated by reference in its entirety). reaction with n-succinimidyl-s-acetylthiopropionate (satp) adds protected sulfhydryl groups to the copolymer chains. the nhs-ester present in the satp molecule reacts with primary amines to form stable amide bonds ( fig. 6c ). the sulfhydryl groups were subsequently deprotected by hydroxylamine ( figs. 6d-e ) and cross-links between copolymer chains resulted upon formation of disulfide bonds ( fig. 6f ) producing a hydrogel network. addition of tcep reducing agent cleaves the cross-links inducing hydrogel dissolution. characterization by 1 h nmr spectroscopy proved that increasing the molar ratio of napmaam to aam in the pre-polymer solution resulted in sequentially more amine moieties in the copolymer chains (table 3) (bonanno & delouise, proc. spie 7167:71670f (2009), which is hereby incorporated by reference in its entirety). reaction chemistry for cross-linking is specific to the amine moieties. therefore, varying the mol % napmaam in the copolymer backbone controls the cross-linking ability of the copolymer chains. as cross-linking density increases, swelling is restricted and the η of the resulting hydrogel increases. visual increases in rigidity of the formed hydrogels were also observed as the mol % napmaam was increased (4.14, 17.82, and 37.27%, ( fig. 7 )). the negative control (0 mol % napmaam copolymer) did not form a hydrogel but remained in solution phase as expected. a bench-top abbe refractometer (bausch and lomb) was used to measure the η of each bulk hydrogel sample produced. samples were first incubated in deionized water for 2 days on a shaker plate to allow for equilibrium swelling and uncross-linked copolymer chains to diffuse out. a direct linear relationship between mol % napmaam and η values was observed ( fig. 8a ). the optical response of the psi bragg mirror was used to analyze hydrogel infiltration into the porous matrix. sulfhydryl functional copolymers in solution (10 wt %) were added to psi bragg mirrors that were functionalized with 3-(mercaptopropyl)trimethoxysilane (mercaptosilane) as described in detail in examples 5-8. the mercaptosilane coating enables the copolymer chains to cross-link via disulfide bonds to the psi substrate. chemically tethering the hydrogel to the psi produces reproducible optical responses that vary systematically with hydrogel composition (bonanno & delouise, proc. spie 7167:71670f (2009), which is hereby incorporated by reference in its entirety). changes in η of the psi sensor resulting from addition of mercaptosilane and hydrogel (after soaked in water for 2 days) can be seen as wavelength shifts in the spectral peak in fig. 8b . the wavelength shift for water (η=1.333) filling the pores is also shown as a reference spectrum to illustrate the additional shift attributed to cross-linked polymer fibers of the hydrogel. wavelength shift magnitude resulting for s—s-copaam hydrogels with varying mol % napmaam cross-linked in the psi bragg mirror are shown in fig. 8c . as mol % napmaam is increased a red wavelength shift is observed, which is consistent with an increase in η of the resulting hydrogel confined in the psi. as expected, a 0 mol % napmaam negative control polymer solution (100% aam, 10 wt %, η=1.3455) produced no detectable wavelength shift beyond that observed for water (η=1.333) filling the pores. here, polymer chains lack reactive amine moieties for sulfhydryl conversion and thus uncross-linked chains washed away during the 2 day soak period. the wavelength shift for each hydrogel filling the psi sensor was theoretically predicted using bruggeman effective-medium approximation (vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001), which is hereby incorporated by reference in its entirety. pores were simulated to be filled 100% with materials of η equal to what was measured on the bulk hydrogels (4.14, 17.82, 37.27 mol % napmaam) using a bench-top abbe refractometer and η water =1.333 was used for 0 mol % napmaam control ( fig. 8c ). simulation parameter values of thickness and open porosity of the psi layers (table 5) were determined by scanning electron microscopy (sem, thickness only), gravimetry, and optical measurements as previously described in segal et al., adv. funct'l mater. 17:1153-62 (2007), which is hereby incorporated by reference in its entirety. simulation and experimental results correlate within 1 standard deviation for each polymer tested ( fig. 8c ). this optical measurement data demonstrates that the cross-linked hydrogel fills the 3-d psi matrix. stability of the fully hydrated hybrid sensors (in 1 ml water) was optically monitored for 48 hours. no observable wavelength shift was detected for any of the samples (0, 4.14, 17,82, 37.27 mol % napmaam), indicating that the state of the composite hydrogel-psi material is stable over this period. initial testing indicates that dry storage (1 month) of the hybrid hydrogel-psi devices and rehydration before use facilitated reproducible results. this is consistent with previous work of hydrogel-supported psi sensors (delouise et al., adv. mater. 17:2199-203 (2005), which is hereby incorporated by reference in its entirety). example 12 investigation of system factors that govern sensor temporal response alternate forms of disulfide cross-linked hydrogels have previously been used as a proof-of-concept for integrating chemical-responsive hydrogels into microfluidic sensor systems (sridharamurthy et al., meas. sci. technol. 18:201-07 (2007); chatterjee et al., aerosp. engrg. 16:55-64 (2003), each of which is hereby incorporated by reference in its entirety). in each case, a disulfide containing cross-linker (cystaminebisacrylamide, bac) was used to form polyacrylamide hydrogels inside microchannels (diameter, d˜hundreds of nm). addition of reducing agents under flow conditions caused gel dissolution. three important design parameters were highlighted: 1) outside concentration of target molecule, 2) original volume of the hydrogel, 3) cross-linking density of the hydrogel (chatterjee et al., aerosp. engrg. 16:55-64 (2003), which is hereby incorporated by reference in its entirety). important differences in the present design include: different hydrogel structure (disulfide cross-linking of preformed copolymer chains), confinement of hydrogel into smaller psi pores (d˜tens of nm) that have one inlet/outlet, and static (no flow) conditions. the aforementioned design parameters were investigated individually as they pertain to the present sensor system (see figs. 4a-d ). after tcep analyte diffuses into the hydrogel-filled psi matrix a small positive wavelength shift can be observed, correlating to the increased η of the tcep solution (table 6). within seconds the hydrogel begins to dissolve causing a wavelength blue shift as uncross-linked copolymer chains diffuse out of the psi matrix. all wavelength shift data in figs. 4a-d are displayed in reference (0 on x-axis) to the reflectance peak position with water filling the psi matrix. as demonstrated in examples 1-4, incorporation of nanoparticles into the polymer matrix would enhance the wavelength shift. table 6refractive iindex of tcep solutions measured on a bench-top abbe refractometer (bausch & lomb, series 512).tcep solutionconcentration [mm]refractive index, η01.333011.3331101.3349501.33681001.3502 example 13 effect of hydrogel structure on observed dissolution response cross-linking density is shown to greatly affect hydrogel dissolution in fig. 4a . measurements were taken in a 1 ml bath of 50 mm tcep for all cases. the negative control (0 mol % napmaam) displays a wavelength red shift of 0.98 nm. this value correlates well with simulation for the increase in η of the tcep solution (η=1.3368) entering the pores compared to water (η water =1.333). no additional shift due to polymer is observed, because no amine moieties exist in the polymer backbone to allow sulfhydryl attachment or subsequent cross-linking moreover, no temporal response shows that the psi sensor is stable in the tcep solution over the test interval. samples that formed hydrogel networks (4.14-37.27 mol % napmaam, fig. 4a ) displayed an increased rate of wavelength blue shift response to tcep with lowering cross-linking density. this demonstrates that less cross-linked hydrogels break apart and diffuse out of the psi matrix more quickly. with higher cross-linking density, more entanglement of copolymer chains is probable and more disulfide bonds must break to free the chains. for the highest cross-linked sample (37.27 mol % napmaam) only a small decrease in wavelength shift was observed even after 4-hour incubation in >100 mol excess of tcep (5e-5 mol). quantification of sulfhydryl groups on the pre-copolymer chains (5.49e-8 mol) was performed with an ellman assay (table 4) (riddles et al., anal. biochem. 94:75-81 (1979), which is hereby incorporated by reference in its entirety). this result is consistent with literature that reports similarly high concentrations of reducing agents (0.1-1 m) were needed to dissolve disulfide cross-linked hydrogels (0.273-0.682 mol % bac cross-linker) over similar time periods (sridharamurthy et al., meas. sci. technol. 18:201-07 (2007); chatterjee et al., aerosp. engrg. 16:55-64 (2003), each of which is hereby incorporated by reference in its entirety). one key difference observed with the present sensor system is that the wavelength shift never returns to zero (water filling the pores) even after overnight soaking in 0.1 m tcep and subsequent rinsing with water. this indicates that residual polymer remains in the psi, which is discussed in example 15. example 14 dissolution response dependence on the concentration of applied target analyte the sensor system response was shown to also depend greatly on the concentration of tcep ( fig. 4b ). measurements were taken on 4.14 mol % napmaam hydrogels cross-linked into psi bragg mirrors mounted inside a 500 μl bath with varying tcep concentrations (0-100 mm). the negative control (water only) showed no response whereas a wavelength blue shift was observed for all concentrations of tcep tested (1-100 mm). the magnitude and rate of the response increased with tcep bath concentration for 1-50 mm solutions. both 50 mm and 100 mm tcep solutions resulted in similar response, indicating that dissolution of the hydrogel is the limiting factor. as tcep is noted for its fast diffusion and reactivity, chain disentanglement has previously been highlighted as the rate-limiting step for disulfide cross-linked hydrogel dissolution (chatterjee et al., aerosp. engrg. 16:55-64 (2003), which is hereby incorporated by reference in its entirety). the experiments described in examples 5-10 were performed in static solutions and future work may investigate how mixing improves dissolution kinetics. example 15 psi transducer architecture effects on confined hydrogel dissolution examples 5-16 particularly investigated how confinement of the hydrogel inside the psi volume affected dissolution. results by segal et al. show that pore size and porosity strongly influenced the extent and rate of the optical response reporting the phase transition behavior of a thermoresponsive hydrogel (poly(n-isopropylacrylamide) confined within a single layer porous sio 2 template (segal et al., adv. funct'l mater. 17:1153-62 (2007), which is hereby incorporated by reference in its entirety). therefore, the effects of pore diameter (d) and porosity (p) in single layer psi films as well as bragg mirror architectures comprised of alternating high and low porosity (large and small pore diameter) layers ( fig. 4c ) (vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001), which is hereby incorporated by reference in its entirety) were investigated. tcep concentration (500 μl, 50 mm) and hydrogel cross-linking (4.14 mol % napmaam) were kept constant. data in fig. 4c and fig. 4d are normalized to the initial wavelength shift value attained with hydrogel filling the pores for each sensor investigated. this allowed for easier comparison between different psi architectures as they display different wavelength shift sensitivity to changes inn (table 5) (vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001), which is hereby incorporated by reference in its entirety). the influence of psi sensor architecture on the incorporated hydrogel dissolution is evident in fig. 4c . dissolution includes three sequential phases: disentanglement of copolymer, dissolution of copolymer chains, and convective mass transport out of the psi matrix (chatterjee et al., aerosp. engrg. 16:55-64 (2003), which is hereby incorporated by reference in its entirety). the overall dissolution rate is determined by the slowest phase. the rate and saturating magnitude of the optical response decreased as pore diameter (d) was decreased in the single layers. this indicates that smaller pores restrict dissolution. in both cases, mirrors created from alternating porous layers (d=19/43 and 73/106 nm) displayed slower rates and smaller magnitudes of response than single layers of the same pore sizes. it is believed that irregular geometries existing at the interface between layers contributes to hindered disentanglement and/or diffusion. porosity does not seem to have as large of an effect on dissolution as pore size displays. this is evident by the fact that similar porosity single layers with different pore sizes exhibit different behavior ( fig. 4c ). a single time point at 4 hours of incubation in tcep is displayed for each of the investigated psi architectures ( fig. 4d ). a strong inverse linear dependence between average pore diameter and dissolution in single layer psi sensors is shown. again, it can also be seen that mirrors illustrate slightly higher amounts of polymer remaining (residual wavelength shift) in the psi matrix than single layers with similar average pore diameter. example 16 colorimetric detection of target analyte in solution visual detection of tcep by the unaided eye was achieved with the exemplary hydrogel-psi sensor system by color readout ( figs. 9a-b ). pictures of bulk s—s-copaam hydrogel (4.14 mol % napmaam) are contrasted to pictures of the same s—s-copaam cross-linked into a psi bragg mirror (d=19/43 nm) prior and post exposure to tcep ( fig. 9a ). a visual color change from red to green in the psi sensor is evident after a 15 minute soak in tcep (500 μl, 50 mm) on a shaker plate, subsequent rinsing with water, and 5 minute air-drying on the bench-top. in contrast to the wet measurements shown in figs. 4a-d , the dry measurements taken here resulted in a large wavelength blue shift (>100 nm) of the peak reflected light. this corresponds to sufficient dissolution of hydrogel from the psi matrix to prevent retention of water inside the internal pore volume resulting in the loss of water from the psi matrix in addition to copolymer. a dilution series of tcep concentration (0-100 mm) shows that the initiation of color change is dependent on applied tcep concentration ( fig. 9b ). for exposure to tcep>10 mm a complete visual color change from red to green is evident. see also fig. 10 . discussion of examples 5-16 examples 5-16 describe a hydrogel synthesis strategy based on amine functionalization of the otherwise chemically inert polyacrylamide. the amine groups allow incorporation of versatile reaction chemistries enabling the control of cross-links between copolymer chains based on complimentary target-probe systems. examples 5-8 demonstrate the incorporation of a model chemical-responsive hydrogel into a 1-d photonic psi sensor to achieve tunable direct optical detection. disulfide chemistry was incorporated to control cross-linking of this hydrogel system within a psi bragg mirror sensor. changes in η of a disulfide cross-linked hydrogel (s—s-copaam) incorporated into a psi bragg mirror were monitored upon exposure to a target reducing agent analyte (tris(2-carboxyethyl)phosphine (tcep)). fabrication of a psi bragg mirror involved anodic electrochemical etching of a p-type, boron-doped si wafer (vinegoni et al., “porous silicon microcavities,” in 2 s ilicon -b ased m aterials and d evices 122-88 (hari nalwa ed., 2001), which is hereby incorporated by reference in its entirety). control of the applied current was used to create alternating layers of high and low porosity to dictate the frequency of a distinct peak in the white-light reflectivity spectrum. tcep-induced dissolution of the s—s-copaam hydrogel resulted in decreasing η. large η changes resulted in visual color response that could be observed by the unaided eye. direct optical monitoring of a characteristic peak in the white light reflectivity spectrum of the incorporated psi bragg mirror facilitates real-time detection of the hydrogel dissolution in response to target analyte (reducing agent) over a time scale of minutes. the dissolution characteristics of the s—s-copaam hydrogel were shown to depend on hydrogel cross-linking density and the applied target analyte concentration. additionally, effects due to responsive hydrogel confinement in a porous template were shown to depend on pore size and architecture of the psi transducer substrate. this hybrid design exhibits characteristics optimal for poc chemical and/or biological sensing due to its inexpensive fabrication, straightforward optical detection, and capability for visual color readout without any secondary label amplification. the disulfide linked hydrogel system described in examples 5-16 serves as a further proof-of-concept for integrating chemical-responsive hydrogels into nano-structured psi sensors. one advantage of this sensing system is the capability for direct visual color readout (1 hour assay time and 5 minute drying time) in addition to the capability for more precise temporal monitoring with reflectance spectrometry. while examples 5-16 specifically report on optical detection of the dissolution response of a disulfide cross-linked hydrogel in response to tcep, which is well known, the disulfide crosslinking of this copolymer system is unique and the optical detection of dissolution based on refractive index changes of the nano-confined responsive hydrogel is demonstrated herein. the effects of nano-scale confinement of hydrogel dissolution properties are also demonstrated. this hybrid material system remains low-cost and proves to be easily translatable for poc sensing. it is expected that biologically relevant probe-target interactions can be incorporated onto the amine-functionalized copolymer backbone described in examples 5-16 to create crosslinked hydrogel networks, and that introduction of nanoparticles into the matrix will further enhance the sensitivity of these devices. example 17 gel formation polyacrylamide/n-(3-aminopropyl)-methacrylamide random copolymers that varied in amine mole fraction (0-25%) have previously been synthesized and characterized (nmr, size exclusion gel chromatography, custom protocols developed in the lab) (bonanno & delouise, proc. spie 7167:11 (2009), which is hereby incorporated by reference in its entirety). sodium formate chain transfer agent was used to control polymer chain length and reactions were terminated at low conversion. typical number average molecular weights (m n ) range between 15-20 kda and polydispersities of 2-3. the amines provide functional sites to attach bioactive groups to induce cross-links. hydrogels ( fig. 11 ) were formed using (a) glutaraldehyde to directly cross-link the amines (bonanno & delouise, proc. spie 7167:11 (2009), which is hereby incorporated by reference in its entirety), (b) disulphides (through modification of amines to sulfhydryls) (bonanno & delouise, adv. funct. mater. 20:1-6 (2010); bonanno & delouise, adv. funct'l mater. 20(4):573-78 (2010) (see examples 5-16, supra), each of which is hereby incorporated by reference in its entirety;), and (c) biotin-streptavidin (sa) interactions. in the glutaraldehyde studies, it was determined that a minimum of 4 wt % solids was needed to observe gel formation. in the sa system, the copolymer (17.5 mol % napmaam by 1h nmr) was biotinylated with amine reactive sulfo-nhs-lc-biotin (pierce). studies were conducted to determine the sa concentration needed to form hydrogels. sa was added to a copolymer solution by varying the molar ratio of sa:amines between 1.4 to 0.1 resulting in a 5 wt % solution. sa is a multivalent cross-linker with four biotin binding sites. in this series the number of sa biotin binding sites to biotin (assuming all amines were biotinylated) varied from 24:5, 3:1, 2:1, 1:1, 4:10. gel formation required that sa binds biotin on at least two different chains, forming crosslinks. it was observed that samples with biotin binding sites:biotin ratio of 3:1, 2:1, and 1:1 formed gels, while the higher and lower ratio samples did not noticeably increase in viscosity. presumably at low sa concentration the cross-link density was too low and at high concentration sa molecules did not bind biotin on different chains. in addition to the above, hydrogel formation was investigated in systems more pertinent to construction of the commercially useful optical sensors. specifically, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (edc) was utilized to couple the glucuronide side chain of m3g ( fig. 12 ) to the amines on the co-polymer chains (8.1 mol % napmaam) using a 2 molar excess of m3g to amines. m3g attachment was confirmed by nmr and size exclusion chromatography. coupling efficiency has not yet been rigorously determined, but an average increase in m n of ˜6000 following m3g attachment was measured. after dialysis, cross-linking the purified m3g-functionalized copolymer was attempted by direct addition of α-m ab solution with a stoichiometric 1:2 antibody to amine molar ratio (assuming 100% m3g coupling efficiency). the reaction proceeded at room temperature for 4 hours on a shaker plate, and was subsequently moved into 4° c. for a longer incubation period. after 7 days no visible sign of gel formation was noted. to this solution was added protein g (sigma, mw=21,600 g mol −1 ) in a 1:2 molar ratio of protein g:antibody because there are 2 antibody f c binding sites per protein g. successful formation of stiff hydrogels resulted within hours ( fig. 13a ) (see fig. 2 (protocol 2)). these gels withstood cycles of dehydration and rehydration ( figs. 13a-b ). the fully hydrated gels had sufficient mechanical integrity (unquantified) that prevented uptake into a pipet. preincubation of protein g with free antibody (1:2 molar ratio) also resulted in gel formation when added to m3g functionalized polymer chains (see fig. 2 (protocol 3)) provided that the total solids exceeded 4 wt %. these findings indicate the possible importance of cross-linker length and avidity. as a first attempt to determine whether protein g assisted gels were responsive to target, a high concentration of m3g (8.67 mm) in pbs solution was introduced. after application of the m3g, the solution was mixed with a pipette for 1 minute and the gel was observed to remain in a solid state ( fig. 13c ). after incubation in a humidified chamber for 15 minutes, mixing again with a pipette resulting in dissolution of the gel to a viscous solution, as evidenced by the presence of bubbles that could be easily taken up by a pipette ( fig. 13d ). this indicates that biomolecular responsive t-gels can be synthesized. example 18 hybrid sensor formation polyacrylamide, glutaraldehyde, disulphide, and m3g-based gels were successfully crosslinked directly into psi sensors and studies proved the optical sensor could detect small changes in η due to gel swelling and wt % gel solids (bonanno & delouise, proc. spie 7167:71670f (2009); bonanno & delouise, adv. funct. mater. 20(4):573-78 (2010) (see examples 5-16, supra); bonanno & delouise, mater. res. soc'y symp. proc. 1133:aa01-05 (2008), each of which is hereby incorporated by reference in its entirety). disulphide gels were responsive to presence of chemical reducing agent (tris(2-carboxyethyl)phosphine hydrochloride,tcep) and within 15 minutes dissolved to produce a visual color change when the sensor was dried. it was shown that the tcep concentration required to dissociate the gels was positively correlated with cross-link density (bonanno & delouise, adv. funct. mater. 20:1-6 (2010); bonanno & delouise, adv. funct'l mater. 20(4):573-78 (2010) (see examples 5-16, supra), each of which is hereby incorporated by reference in its entirety). proof of principle studies were also successful at cross-linking the m3g responsive t-gels described in example 17 directly into psi sensors ( fig. 14 ). in this example, a control gel was formed by adding rabbit igg and protein g to m3g coupled polymer chains. the control gel did not swell or appear as optically clear as the t-gel, and exposure to free m3g caused gel dissolution of the αm-ab gel only. after drying, the psi sensor changed color (orange to yellow) due to dissolution of the polymer chains causing a large ti change (˜100 nm), whereas the control chip remained orange as the porous matrix remained filled with dehydrated polymer. the specific color change reported is customizable and determined by design of the optical sensor. example 19 integrate t-gel with psi optical sensor t-gels will be crosslinked directly into macropsi sensors (pore diameter 50-150 nm) fabricated as previously described (delouise & miller, proc. spie 5357:111-25 (2004); ouyang et al., anal. chem. 79(4):1502-06 (2007); ouyang et al., appl. phys. lett. 88:163108 (2006); ouyang et al., proc. spie 5511:71-80 (2004), each of which is hereby incorporated by reference in its entirety). application of the t-gel to the psi sensor will be performed via spin coating to precisely control and minimize the thickness of the gel layer above the sensor matrix ( fig. 15a ). this is optimal for two reasons. first, target must diffuse through this gel layer before entering the sensor matrix where the signal is transduced. at low target concentrations, a thick gel layer on top of the sensor will inhibit target detection and may give rise to false negatives. second, a thick layer will also delay target diffusion into the porous sensor, which will translate to slower sensor response times. spin coating (ur chemistry dept) was used to cast thin gel precursor solutions on silicon wafers. after gel formation and equilibrium swelling, ellipsometry was used and it was observed, as expected, that spin speed and gel thickness are inversely related ( fig. 15b ). it was proven that gels cast onto sensor cross-link throughout the porous matrix by comparing the magnitude of the wavelength shift measured with theoretical estimates calculated by filling the porous matrix with a substance equal to the bulk gel refractive index ( fig. 15c ). these same spin coating techniques will therefore be used to optimize psi optical sensor function. example 20 transfer of organic soluble quantum dots into water ligand exchange procedures to transfer organic soluble qd into water using dihydrolipoic acid (dhla) and cysteamine were developed as described in table 7 (dhla) and table 8 (cysteamine). table 7transfer of topo/zns coated cdse qds into water with dhla.(1)added 50 μl of freshly prepared dihydrolipoic acid (dhla) and1 ml meoh, mixed.(2)the ph of the solution was adjusted to 11 with tetramethylammoniumhydroxide pentahydrate ((ch 3 ) 4 noh•5h 2 o).(3)0.5 ml (0.65 mg) topo-capped cdse/zns core/shell qds was addedto the solution.(4)the solution was heated at 60° c. with magnetic stirring for 3 hours.(5)the solution was then cooled down to room temperature.(6)the qds were precipitated with excess anhydrous ether, centrifugedat 6000 rpm for 10 minutes, and the supernatant was decanted toremove the organic solvent.(7)the precipitate was dried up using nitrogen.(8)the precipitate was then resolved in deionized water.(9)finally, the sample was dialyzed overnight, and stored in the dark. table 8transfer of topo/zns coated cdseqds into water with cysteamine.(1)0.5 ml (0.65 mg) topo-capped cdse/zns core/shell qds wasremoved toluene under vacuum.(2)0.5 ml thf was added, mixed.(3)50 mg cysteamine hydrochloride was added to a flask, and heatedat 80° c.(4)after melting, qds in thf was dropped to the flask and heatedat 80° c. for 2 hours.(5)the sample was dried up using nitrogen gas.(6)deionized water was added to resolve the sample.(7)finally, the sample was dialyzed overnight, and stored in the dark. the resulting water-soluble qds can be incorporated into a polymer hydrogel as described herein. although the invention has been described in detail for the purpose of illustration, it is understood that such detail is solely for that purpose, and variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention which is defined by the following claims.
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134-377-624-419-571
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US
|
[
"US"
] |
A61B5/055,A61B5/352,A61B6/00,A61B6/03,H05G1/62
| 2002-02-22T00:00:00 |
2002
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[
"A61",
"H05"
] |
method for three dimensional cine eba/cta imaging
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certain embodiments of the present invention provide a method for three-dimensional cine eba/cta imaging. the method includes monitoring a cardiac cycle of a patient and selecting a trigger point along the cardiac cycle. when the cardiac cycle of the patient reaches the trigger point, a computed tomography (ct) scan of the patient is initiated. at least two ct scans of the patient are performed during a time period over two or more cardiac cycles. a cine angiography image is constructed from the at least two ct scans.
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1 . a method for obtaining cine angiography images with a computed tomography (ct) scanner, comprising: monitoring a cardiac cycle of a patient; selecting a trigger point along said cardiac cycle; when said cardiac cycle of the patient reaches said trigger point, initiating a ct scan of the patient; performing at least two ct scans of the patient during a time period over two or more cardiac cycles; and constructing a cine angiography image from said at least two ct scans. 2 . the method of claim 1 , wherein said performing step obtains said at least two ct scans during a single cardiac cycle. 3 . the method of claim 1 , wherein said performing step obtains said at least two ct scans consecutively and beginning at different points within said time period. 4 . the method of claim 1 , wherein said performing step performs a complete ct scan in no more than 100 milliseconds. 5 . the method of claim 1 , further comprising sweeping an electron beam across a target ring to perform said at least two ct scans. 6 . the method of claim 1 , utilizing an x-ray fan beam to obtain said at least two ct scans. 7 . the method of claim 1 , further comprising combining a series of three dimensional images into a three dimensional cine loop based on said at least two ct scans. 8 . the method of claim 1 , further comprising displaying a series of moving three dimensional images based on said at least two ct scans. 9 . the method of claim 1 , wherein said initiating step includes prospective gating based on said cardiac cycle of the patient. 10 . the method of claim 1 , further comprising moving the patient with respect to the ct scanner between or during ct scans. 11 . the method of claim 1 , further comprising moving the patient with respect to the ct scanner during each of said at least two ct scans to obtain spiral scans. 12 . the method of claim 1 , wherein said performing step obtains multiple parallel ct slices from separate parallel rows of detectors in the ct scanner. 13 . the method of claim 1 , wherein said performing step obtains one image for each ct scan. 14 . a method for obtaining cine loop images with a computed tomography (ct) scanner, comprising: monitoring a cardiac cycle of a patient; selecting a trigger point along said cardiac cycle; when said cardiac cycle of the patient reaches said trigger point, initiating a ct scan of the patient; sweeping an electron beam along a target to generate an x-ray fan beam to perform at least two ct scans; and constructing a cine angiography image from said at least two ct scans. 15 . the method of claim 14 , wherein said sweeping step obtains said at least two ct scans during a single cardiac cycle. 16 . the method of claim 14 , wherein said sweeping step obtains said at least two ct scans consecutively and beginning at different points within a time period of two or more cardiac cycles. 17 . the method of claim 14 , wherein said sweeping step performs a complete ct scan in no more than 100 milliseconds. 18 . the method of claim 14 , further comprising combining a series of three dimensional images into a three dimensional cine loop based on said at least two ct scans. 19 . the method of claim 14 , further comprising displaying a series of moving three dimensional images based on said at least two ct scans. 20 . the method of claim 14 , wherein said initiating step includes prospective gating based on said cardiac cycle of the patient. 21 . the method of claim 14 , further comprising moving the patient with respect to the ct scanner between or during ct scans. 22 . the method of claim 14 , further comprising moving the patient with respect to the ct scanner during each of said at least two ct scans to obtain spiral scans. 23 . the method of claim 14 , wherein said sweeping step obtains multiple parallel ct slices from separate parallel rows of detectors in the ct scanner. 24 . the method of claim 14 , further comprising performing at least two ct scans of the patient during a time period over two or more cardiac cycles. 25 . a method for generating cine angiography images, comprising: monitoring a cardiac cycle of a patient; selecting a trigger point along said cardiac cycle; when said cardiac cycle of the patient reaches said trigger point, initiating a computed tomography (ct) scan of the patient; performing at least two ct scans of the patient during a cardiac cycle; constructing a cine angiography image from said at least two ct scans; and moving the patient with respect to a ct scanner between or during ct scans. 26 . the method of claim 25 , wherein said performing step obtains said at least two ct scans during a single cardiac cycle. 27 . the method of claim 25 , wherein said performing step obtains said at least two ct scans consecutively and beginning at different points within a time period of two or more cardiac cycles. 28 . the method of claim 25 , wherein said performing step performs a complete ct scan in no more than 100 milliseconds. 29 . the method of claim 25 , further comprising combining a series of three dimensional images into a three dimensional cine loop based on said at least two ct scans. 30 . the method of claim 25 , further comprising displaying a series of moving three dimensional images based on said at least two ct scans. 31 . the method of claim 25 , wherein said initiating step includes prospective gating based on said cardiac cycle of the patient. 32 . the method of claim 25 , further comprising moving the patient with respect to the ct scanner during each of said at least two ct scans to obtain spiral scans. 33 . the method of claim 25 , wherein said performing step obtains multiple parallel ct slices from separate parallel rows of detectors in the ct scanner.
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cross reference to related applications the present application relates to, and claims priority from, co-pending application (attorney docket number 125691) filed on the same date as the present application and entitled method and apparatus for cine eba/cta imaging. the present application relates to, and claims priority from, u.s. provisional application no. 60/358,888, filed on feb. 22, 2002, and entitled cine eba/cta. the co-pending application and provisional application name susan candell and douglas boyd as joint inventors and are incorporated by reference herein in their entirety including the specifications, drawings, claims, abstracts and the like. background of the invention the present invention generally relates to computed tomography angiography (cta)/electron beam angiography (eba). in particular, the present invention relates to cardiac cine imaging using cta/eba. medical diagnostic imaging systems encompass a variety of imaging modalities, such as x-ray systems, computerized tomography (ct) systems, ultrasound systems, electron beam tomography (ebt) systems, magnetic resonance (mr) systems, and the like. medical diagnostic imaging systems generate images of an object, such as a patient, for example, through exposure to an energy source, such as x-rays passing through a patient. the generated images may be used for many purposes. for instance, internal defects in an object may be detected. additionally, changes in internal structure or alignment may be determined. fluid flow within an object may also be represented. furthermore, the image may show the presence or absence of components in an object. the information gained from medical diagnostic imaging has applications in many fields, including medicine and manufacturing. angiography refers to techniques for imaging arteries in a body. coronary arteries of the heart are some of the more significant arteries that are commonly imaged. problems with coronary arteries account for a large percentage of deaths in the united states each year. coronary arteries are difficult to image because coronary arteries move with a cardiac cycle with speeds of up to 20 millimeters per second. observing motion of the coronary arteries may be helpful in diagnosing illnesses or defects. during the past several years, cta and eba were developed to replace invasive coronary angiography. coronary angiography uses direct injections of contrast media into the coronary arteries using a long catheter. cta and eba, on the other hand, use a less invasive approach of a simple intravenous injection of a contrast agent. current methods obtain ct images of the coronary arteries at specific phases of the cardiac cycle. since the ct images are obtained at a specific phase of the cardiac cycle using current methods, the ct images are stationary images. the stationary images form cross sectional ct images of coronary arteries. the cross section ct images may be combined to form a spatially three-dimensional image. the cross section images may be combined using techniques such as maximum intensity mip, volume rendering (vr), shaded surface display (ssd), or other types of image processing. the resulting three-dimensional image illustrates a stationary volume at one instant in time. the images are formed from data acquired during a series of scan. in order for useful data to be acquired in a scan, data acquisition has been synchronized with the cardiac cycle. gating refers to synchronizing data acquisition with the cardiac cycle. a wave of an electrocardiogram (ecg) may be used to gate or synchronize acquisition data with the cardiac cycle. there are two common types of gating, namely prospective and retrospective gating. prospective gating triggers the start of axial scanning by monitoring the patient's ecg wave and anticipating a chosen point in the interval between r-wave peaks (r-to-r interval) in an ecg cycle. the chosen point may be selected to correspond to the region of the cardiac cycle where cardiac motion is at a minimum. retrospective gating uses continuous scanning and selects particular images based on the ecg wave information. conventional systems use retrospective gating for single static images. several conditions impact scanning and image acquisition. a typical patient may hold his or her breath for about 45 seconds. to minimize motion artifacts and generate an accurate image, it is preferable in conventional systems that an entire image series be scanned during one breath. thus, a need exists for an imaging system that may capture imaging data fast enough to scan an entire series of cardiac images in one breath. additionally, heart rates vary from patient to patient such as from about 50 beats per minute (slow), or 1.2 seconds/heartbeat, to about 120 beats per minute (pediatric), or 0.5 seconds/heartbeat. current systems are incapable of easily adjusting for multiple or varied heart rates. the inability to adjust for multiple heart rates may result in image artifacts or in an inability to capture properly image data. thus, there is a need for an imaging system that supports a full range of heart rates. further, a particular patient's heart rate may vary during an imaging series. for example, a heart rate may start at about 70 beats per minute, then reduce to 60 beats per minute when a patient first holds his or her breath, and then increase to 90 beats per minute at the end of a patient's ability to hold his or her breath. also, a particular patient's heart rate may change from one heartbeat to another heartbeat due to stress and other factors. a changing heart rate may introduce motion artifacts or other image artifacts into the obtained images. thus, there is a need to accommodate a changing heart rate. furthermore, there is a need to detect irregular heartbeats. motion of a table or other apparatus used to position a patient may cause discomfort to a patient. fast motion of a table may be uncomfortable to a patient and may also cause motion artifacts. thus, a system is needed that reduces patient discomfort and motion artifacts in resulting images. heretofore, cta and eba systems have been unable to obtain moving images of the coronary arteries and more generally moving angiography. a series of images (2-d or 3-d) illustrating changes in an object with respect to time is referred to as a cine image. conventional cta and eba systems have been unable to offer cine angiography. thus, there is a need for an angiography imaging method and apparatus for reconstructing a sequence of two- or three-dimensional images that show the motion of coronary arteries during a cardiac cycle. additionally, current imaging methods require a lengthy period to acquire images. the time period required to acquire coronary arterial images is often too lengthy for the comfort of a patient. thus, a need exists for a method and apparatus for imaging coronary artery motion and cardiac activity in a short time window for accurate imaging and patient comfort. further, current imaging methods result in gaps and poor resolution in the resulting three-dimensional image due to the reconstruction techniques used, such as retrospective gating and other image reconstruction techniques, for example. thus, there is a need for an imaging method and apparatus for improved quality imaging for angiography and motion in a cardiac cycle. summary of the invention certain embodiments of the present invention provide a method for three-dimensional cine eba/cta imaging. the method includes monitoring a cardiac cycle of a patient and selecting a trigger point along the cardiac cycle. when the cardiac cycle of the patient reaches the trigger point, a computed tomography (ct) scan of the patient is initiated using a ct scanner. at least two ct scans of the patient are performed during a time period over two or more cardiac cycles. a cine angiography image is constructed from the at least two ct scans. each scan may contain sufficient information to create a complete image. in certain embodiments, the at least two ct scans are obtained during a single cardiac cycle of the patient. alternatively, the at least two ct scans may be obtained consecutively and beginning at different points within the time period. in certain embodiments, multiple parallel ct slices are obtained from separate parallel rows of detectors in the ct scanner. in certain embodiments, a complete ct scan is performed in no more than 100 milliseconds. in certain embodiments, an electron beam is swept across a target ring to perform the at least two ct scans. in certain embodiments an x-ray fan beam is utilized to obtain the at least two ct scans. in certain embodiments, the patient is moved with respect to the ct scanner between or during ct scans. additionally, the patient may be moved with respect to the ct scanner during each of the at least two ct scans to obtain spiral scans. in certain embodiments, a series of three dimensional images obtained may be combined into a three dimensional cine loop based on the at least two ct scans. the series of moving three dimensional images may also be displayed and/or stored. brief description of drawings fig. 1 illustrates an ebt imaging system in accordance with an embodiment of the present invention. fig. 2 illustrates a flow diagram for a method for obtaining motion images of coronary activity in accordance with an embodiment of the present invention. fig. 3 illustrates an ecg-triggered step-cine sequence as used for electron beam angiography in accordance with certain embodiments of the present invention. fig. 4 illustrates an example of a sweep map, which describes a scanning series in a sweep-by-sweep format in accordance with certain embodiments of the present invention. fig. 5 illustrates a time sequence before a scan 1 begins, in accordance with certain embodiments of the present invention. fig. 6 illustrates a time sequence between a sweep 1 and a sweep 2, in accordance with certain embodiments of the present invention. fig. 7 illustrates a time sequence for a scan from user confirmation to start of a sweep 1 on the target ring in accordance with certain embodiments of the present invention. fig. 8 illustrates a time sequence from start of a sweep 1 on the target ring to start of a sweep 5 on the target ring in accordance with certain embodiments of the present invention. fig. 9 illustrates a conventional mechanical ct scanner in accordance with certain embodiments of the present invention. fig. 10 illustrates a block diagram of a conventional mechanical ct scanner in accordance with certain embodiments of the present invention. fig. 11 shows a single phase of the cardiac cycle imaged at each position in accordance with certain embodiments of the present invention. fig. 12 illustrates utilizing an available time gap to acquire up to three phases in each heartbeat in accordance with certain embodiments of the present invention. fig. 13 illustrates a series of cardiac images acquired at 32 levels and 3 phases per level in accordance with certain embodiments of the present invention. fig. 14 depicts acquiring all cardiac phases for each heartbeat using continuous volume scanning with two or more multi-detector arrays in accordance with certain embodiments of the present invention. the foregoing summary, as well as the following detailed description of certain embodiments of the present invention, will be better understood when read in conjunction with the appended drawings. for the purpose of illustrating the invention, there is shown in the drawings, certain embodiments. it should be understood, however, that the present invention is not limited to the arrangements and instrumentality shown in the attached drawings. detailed description for the purpose of illustration only, the following detailed description references certain embodiments of an electron beam tomography (ebt) imaging system. it is understood that the present invention may be used with other imaging systems, such as conventional computed tomography systems and other medical diagnostic imaging systems, for example. fig. 1 illustrates an ebt imaging system 100 in accordance with an embodiment of the present invention. the system 100 includes an operator console 110 , a beam control system 120 , an ecg digitizer 122 , a high voltage generator 124 , a target ring 130 , a detector ring 140 , a patient positioner 150 , a positioner control system 155 , a data acquisition system (das) 160 , an image reconstruction module 162 , and an image display and manipulation system 164 . the operator console 110 , ecg digitizer 122 , high voltage generator 124 , and positioner control system 155 communicate with the beam control system 120 to generate and control an energy beam, such as an electron beam, for example. the beam control system 120 communicates with the positioner control system 155 to control the patient positioner 150 . the beam control system 120 causes the electron beam to sweep over the target ring 130 . a sweep may be a single traversal of the target ring 130 . the detector ring 140 receives radiation, such as x-ray radiation, for example, from the target ring 130 . the das 160 receives data from the detector ring 140 . the das 160 transmits data to the image reconstruction module 162 . the image reconstruction module 162 transmits images to the image display and manipulation system 164 . the components of the system 100 may be separate units, may be integrated in various forms, and may be implemented in hardware and/or in software. the operator console 110 selects a mode of operation for the system 100 . the operator console 110 may also input parameters or configuration information, for example, for the system 100 . the operator console 110 may set parameters such as triggering, scan type, electron beam sweep speed, and patient positioner 150 position (for example, horizontal, vertical, tilt, and/or slew), for example. an operator may input information into the system 100 using the operator console 110 . alternatively, a program or other automatic procedure may be used to initiate operations at the operator console 110 . the operator console 110 may also control operations and characteristics of the system 100 during a procedure. based on operator input, the operator console 110 transmits operating information such as scanning mode, scanning configuration information, and system parameters, for example, to the beam control system 120 . the ecg digitizer 122 transmits electrocardiogram r-wave trigger signals to the beam control system 120 to assist in timing of electron beam sweep and patient positioner 150 motion. an electrocardiogram (ecg) is a tracing of variations in electrical potential of a heart caused by excitation of heart muscle. an ecg includes waves of deflection resulting from atrial and ventricular activity changing with charge and voltage over time. a p-wave is deflection due to excitation of atria. a qrs complex includes q-, r-, and s-waves of deflection due to excitation and depolarization of ventricles. a t-wave is deflection due to repolarization of the ventricles. certain embodiments of the system 100 utilize the r-wave, an initial upward deflection of the qrs complex, for use in beam control and imaging. the ecg digitizer 122 transmits ecg r-wave triggers to the beam control system 120 to assist in controlling the electron beam and imaging sweeps. the system 100 is configured to begin and end an imaging sweep at predetermined points along an r-wave. imaging sweeps in the system 100 may also be triggered at predetermined points during the interval between r-waves (the r-to-r interval) or between r-wave peaks, for example. alternatively, sweeps may be triggered based on a predetermined time interval after a reference point in time, for example. the trigger points may be set by the operator console 110 . the high voltage generator 124 may be used by the beam control system 120 to produce an electron beam. the high voltage module 124 may be a spellman power supply with a power-on time of 80 or 130 milliseconds, for example. the electron beam is focused and angled towards the target ring 130 . the electron beam is swept over the target ring 130 . when the electron beam hits the target ring 130 , the target ring 130 emits a fan beam of radiation, such as x-rays, for example. the target ring 130 may be made of tungsten or other metal, for example. the target ring 130 may be shaped in an arc, such as in a 210-degree arc. each 210-degree sweep of the electron beam over the target ring 130 produces a fan beam, such as a 30-degree fan beam, of electrons from the target ring 130 . the x-rays emitted from the target ring 130 pass through an object, such as a patient, for example, that is located on the patient positioner 150 . the x-rays then impinge upon the detector ring 140 . the detector ring 140 may include one, two or more rows of detectors that generate signals in response to the impinging x-rays. the signals are transmitted from the detector ring 140 to the das 160 where the signals are acquired and processed. data from the detector ring 140 signals may then be sent from the das 150 to the image reconstruction module 162 . the image reconstruction module 162 processes the data to construct one or more images. the image or images may be stationary image(s), motion image(s), or a combination of stationary and motion (cine) images. the image reconstruction module 162 may employ a plurality of reconstruction processes, such as backprojection, forward projection, fourier analysis, and other reconstruction methods, for example. the image(s) are then transmitted to the image display and manipulation system 164 for adjustment, storage, and/or display. the image display and manipulation system 164 may eliminate artifacts from the image(s) and/or may also modify or alter the image(s) based on input from the operator console 110 or other image requirements, for example. the image display and manipulation system 164 may store the image(s) in internal or external memory, for example, and may also display the image(s) on a television, monitor, flat panel display, lcd screen, or other display, for example. the image display and manipulation system 164 may also print the image(s). the patient positioner 150 allows an object, such as a patient, for example, to be positioned between the target ring 130 and the detector ring 140 . the patient positioner 150 may be a table, a table bucky, a vertical bucky, a support, or other positioning device, for example. the patient positioner 150 positions the object between the target ring 130 and the detector ring 140 such that x-rays emitted from the target ring 130 after the sweep of the electron beam pass through the object on the way to the detector ring 140 . thus, the detector ring 140 receives x-rays that have passed through the object. the patient positioner 150 may be moved in steps or discrete distances. that is, the patient positioner 150 moves a certain distance and then stops. then the patient positioner 150 moves again and stops. the stop-and-go motion of the patient positioner 150 may be repeated for a desired number of repetitions, a desired time, and/or a desired distance, for example. alternatively, the patient positioner 150 may be moved continuously for a desired time, a desired number of electron beam sweeps of the target ring 130 , and/or a desired distance, for example, or the patent positioner 150 may not move. in operation, a user positions an object, such as a patient, on the patient positioner 150 . then the user selects when to trigger the scan using the operator console 110 . in certain embodiments, the scan is triggered based on an r-wave signal from the patient. the user may select a certain predetermined point, phase or percentage of an r-to-r interval between cardiac r-waves at which to begin the scan to acquire image data. that is, a point or trigger is selected to indicate at what point in time the electron beam begins a sweep of the target ring 130 . for example, the user may select a trigger at 0% (i.e., the electron beam sweeps the target ring 130 at the start of the r-to-r interval), 40% (i.e., the electron beam sweeps the target ring 130 less than half-way through the interval between r-waves), 80%, and the like. the electron beam scan is triggered after a predetermined period of time (such as 100 milliseconds 130 milliseconds, or 150 milliseconds, for example), at a predetermined point in the r-to-r interval between r-waves (0%, 40%, 80% of the interval, for example), or other predetermined criteria, for example. for example, the user may select a trigger at 130 milliseconds after a reference point in time, such as system start-up, electron beam power-up, patient heartbeat, or other such event. the electron beam in the system 100 may also execute continuous sweeps. that is, the electron beam does not wait for a trigger to sweep the target ring 130 but rather executes repeated sweeps of the target ring 130 . additionally, the electron beam may sweep as many times as the user programs or selects. image data may be acquired during a certain time period, such as 50 milliseconds or 100 milliseconds, for example. then, the sweep(s) may stop. next, the patient positioner 150 may be moved by the positioner control system 155 . for example, a patient on a table may be advanced through the space between the detector ring 140 and the target ring 130 . in certain embodiments, the object on the patient positioner 150 may not be scanned while the patient positioner is moving. after the patient positioner 150 has moved, the electron beam may again be triggered at a predetermined percentage of the r-to-r interval, and imaging may begin again. in other embodiments, the patient may be moved during an image scan. for example, a human operator may choose to trigger at 40% of an r-to-r interval. the operator may select a 40% trigger using the operator console 110 . the operator console 110 transmits imaging parameter information to the beam control system 120 . the ecg digitizer 122 triggers at the r-wave, and the beam control system 120 wait to trigger the electron beam to begin a sweep of the target ring 130 until 40% of the period between r-waves of the patient's heartbeat is measured. after a sweep of the target ring 130 , the patient positioner 150 is advanced. then, the next sweep begins at 40% of the next r-to-r interval. in certain embodiments, a contrast agent may be administered to a patient on the patient positioner 150 . the beam control system 120 waits for the contrast agent to reach the patient's heart. the beam control system 120 first sweeps the electron beam in a pre-scan of the patient to obtain background data. then, at the desired point in the heart's r-to-r interval, the electron beam begins sweeping the target ring 130 . the sweep may be set to stop before a desired end percentage in the r-to-r interval. then the table is moved. next, a subsequent sweep may be obtained. in certain embodiments, sweeps are obtained during three cardiac cycles, for example. optionally, the system 100 may scan continuously. that is, the electron beam sweeps the target ring 130 and the das 160 collects data from the detector ring 140 without triggering by the ecg digitizer 122 and the beam control system 120 . the system 100 scans through a patient's heart continuously for a certain time period as the patient positioner 150 is moving. hence, all cardiac phases and all slices are imaged in a continuous scan. the system 100 may scan continuously at a rate such that the patient positioner 150 is moving at a rate of one image slice thickness per heartbeat. therefore, all of the phases and all of the heartbeats of the heart may be obtained. for example, to obtain an image slice, one target ring 130 is swept. x-rays from the target ring 130 are received by two rows of detectors in the detector ring 140 . the patient positioner 150 is advanced at a rate of three millimeters per second, for example. in approximately thirty seconds image data for all slices of a patient's heart and all cardiac phases of the heart may be obtained, for example. a plurality of images may be obtained during a desired number of sweeps and a desired number of heartbeats. then, a cine loop of motion video may be created from the obtained images using the image reconstruction module 162 and the image display and manipulations system 164 . in certain embodiments, the image reconstruction module 162 may perform interpolation between the rows of detectors in the detector ring 140 to compensate for data falling between the parallel rows. several slices through a heart are obtained, covering every cardiac phase. for example, the heart is scanned in 6, 3 or 1.5 millimeter slices. the slices are then combined to create a cardiac image. the electron beam sweeps the stationary target ring 130 in 50 milliseconds, for example. optionally, the electron beam may sweep faster or slower. a full revolution is traversed in approximately 56 milliseconds (50 milliseconds to sweep the target ring 130 and 6 milliseconds to finish the 360-degree circle of the sweep), for example. a full revolution may be traversed in a greater or lesser amount of time. the das 160 acquires image data from the detector ring 140 after electron beam sweeps in order to create an image. the system 100 may acquire multiple images for a single r-to-r interval. for a typical heart rate of 60 beats per minute (60,000 milliseconds), the das 160 may acquire approximately 18 sweeps per r-to-r interval, for example. using two detector rings 140 , 36 completely distinct images may result, 18 images at different ecg phases, and 36 different levels of the heart, for example. the total number of levels of the heart that are scanned may depend on the pitch or speed of the patient positioner 150 . the system 100 may trigger sweeps prospectively, or in advance of event occurrence, or the system 100 may trigger retrospectively. the sweeps may be executed in 17 milliseconds, with a 33 millisecond sweep speed being a sweep speed that may remove motion artifacts due to heart motion, for example. for the 33 millisecond case (with a 38 millisecond total sweep time), the system 100 may acquire up to 26 sweeps for a 60 beats-per-minute patient, resulting in 26 different phases and 52 different levels for each r-to-r interval, for example. cine imaging is triggered in steps based on an ecg r-wave. a single image data acquisition may be obtained per heartbeat. a single acquisition per heartbeat covers a range of cardiac phases. a patient on the patient positioner 150 is stationary during image acquisition. the patient positioner 150 moves between each image acquisition. a cine-type image set is produced. distinct image data acquisitions are obtained per heartbeat. distinct acquisitions per heartbeat may cover distinct phases of the cardiac cycle. a low dose may be used when attempting to acquire data at clinically significant systole and diastole phases of a heart. sweeps may be triggered in different ways based on different criteria. triggering may be manually activated, predetermined at certain defined percentages of an r-to-r interval or an individual r-wave, set for certain time intervals after reference points in time, or set separately for each sweep. thus, each sweep of the target ring 130 may be independently configured. in the prior art, as shown in fig. 11, a single phase of the cardiac cycle is imaged at each position. for a single slice scanner, each image is obtained at a consecutive heartbeat. in fig. 12 , by utilizing an available time gap before moving the patient positioner 150 , up to 3 phases may be acquired in each heartbeat. fig. 13 illustrates a series of cardiac images acquired at 32 levels (x-axis) and 3 phases per level (y-axis). on the right are 3 static 3d images that may be rendered from each phase. the 3 images are then combined to produce a cine loop that may display the same information about moving coronary arteries usually obtained by invasive cine-coronary-angiography. thus, either cross section cine loops or a full 3d cine loop may be formed. additionally, in a certain embodiment, depicted in fig. 14 , all cardiac phases may be acquired for each heartbeat using continuous volume scanning with two or more multi-detector arrays. the following example illustrates ecg triggering in certain embodiments of the system 100 . electrodes are placed on a patient's chest and connected to an ecg monitor. the ecg monitor may be a separate unit or may be integrated into the ecg digitizer 122 , for example. the ecg monitor may display a moving, real-time ecg wave to aid in placing the electrodes. the ecg monitor may display a recent heart rate based on the r-to-r interval. an r-wave is the primary hump in an ecg wave. the time between r-waves represents the r-to-r interval. the ecg monitor generates a r-wave trigger. the trigger is output to the ecg digitizer 122 for triggering. the ecg monitor also outputs a constant analog datastream of the ecg waves. the datastream may be captured and digitized by the ecg digitizer 122 . the digitized waveforms and sweep timing indications may be attached to resulting patient images. a user may choose when to execute the image scans relative to the r wave and the r-to-r interval. first, the user may choose heartbeats on which to trigger (i.e., whether or not to skip heartbeats). certain embodiments allow the user to specify different heartbeats for every trigger. for example, the user may choose to trigger on every heartbeat for the first five sets of sweeps, then skip a beat for the next four sets of sweeps, then skip three beats for sets ten through twenty. second, the user may choose a delay after the r-wave to trigger. the delay may be based on milliseconds, for example. the delay may be a percentage of the r-to-r interval. selection options may be based on sweep speed. for example, for a 100 millisecond sweep speed, the user may choose delays in percentage between 40% and 80% completion of the r-to-r interval between consecutive r-waves. for a 100 millisecond sweep speed, the user may also choose delays in milliseconds between 246 milliseconds and 999 milliseconds from a reference point in time such as electron beam power-up, system start-up, patient heartbeat, previous r-wave, or other event, for example. for a 50 millisecond sweep speed, the user may choose a delay in percentage at 0% and/or between 40% and 80%, for example. the user may also choose a delay in milliseconds for a 50 millisecond sweep speed at 0 milliseconds and/or between 130 milliseconds and 999 milliseconds from a reference point in time, for example. the user may also choose other settings such as combinations of the number of sweeps per trigger, number of target rings, and sweep speeds to be executed in succession as part of a series description, for example. the user may also choose to move the patient positioner 150 , on which the patient is positioned, between triggers. in certain embodiments, the patient positioner 150 may be moved in differing increments per sweep or per trigger, for example. the patient positioner 150 may be moved between triggers in order to create a volume-type series of images. not moving the patient positioner 150 between triggers may create a flow-type series of images. when patient positioner 150 motion is indicated, the time of patient positioner 150 motion may be related to the patient heart rate in order to slow the motion of the patient positioner 150 . slowed patient positioner 150 motion related to heart rate may increase patient comfort for series with either short scan times (i.e., one sweep per level), for series that skip heartbeats, or for patients with slow heart rates, for example. slowed patient positioner 150 motion may also reduce patient positioner 150 motion-induced artifacts in resulting images. the user may also choose to perform scans on multiple target rings 130 . each target ring 130 may be aligned for a particular detector ring 140 or multiple target rings 130 may be arranged with respect to multiple detector rings 140 . scans on multiple target rings 130 may be performed in a flow-type series (for example, scanning target rings a, b, c, and d in the order dcba, dbca, etc.). scans on multiple target rings 130 may also be performed in a cine-type series (for example, scanning target rings in the order dddd, cccc, bbbb, aaaa, etc.). the first sweep of the target rings 130 may be triggered as described above. when a scanning protocol and user options have been accepted at the operator console 110 and downloaded to the beam control system 120 , a median patient heart rate may be calculated. the median heart rate is based on the previous seven heartbeats. the median heart rate may be used to help predict future sweep parameters, such as for timing motion of the patient positioner 150 . the median heart rate may also be used to help determine whether heartbeats may be skipped in imaging sweeps, and/or to warn of an inability to achieve a desired cardiac phase for triggering. the user may then presses a start button or other initiation key, for example, to being triggering. optionally, a timed delay or other delay may occur after the start button is pressed before the start of the first trigger. next, the scan executes to completion. optionally, the scan may be paused throughout the process. images may be displayed at the image display and manipulation system 164 as soon as available. after a series of images is complete, ecg data collection by the das 160 may be halted and uploaded to the image reconstruction module 162 . the das 160 may insert into the collected data indications of when the sweeps actually occurred. the ecg data set and sweep indications may be attached to the image data. ecg waveforms with trigger indications may be viewed by a user via the image display and manipulation system 164 . when the electron beam is turned off during a scanning series, a delay may occur before the electron beam is used again. the delay associated with electron beam warm up or initialization may be 130 milliseconds or 80 milliseconds. if the electron beam is to be triggered at a time less than the electron beam initialization delay, prediction algorithms are implemented to anticipate when the next r-wave will occur. such prediction algorithms ensure that the electron beam is generated by the high voltage generator 124 and the beam control system 120 in time for the trigger event. fig. 2 illustrates a flow diagram 200 for a method for obtaining motion images of coronary activity in accordance with an embodiment of the present invention. first, at step 205 , a patient is positioned on a patient positioner 150 or support, such as a table, in an ebt imaging system. then, at step 210 , an operator inputs configuration information for the imaging scan, such as triggers for electron beam sweeps, radiation dosage, timing, number of sweeps, resolution, and/or other configuration information. the operator selects an electron beam trigger based on percentage or phase, such as at 40% completion of an r-to-r interval. alternatively, the operator may select continuous imaging. the operator also selects step-wise, none or another type of table motion between electron beam sweeps. optionally, the operator may select continuous table motion during scanning, for example. next, at step 215 , an energy beam, such as an electron beam, is triggered to sweep the target ring 130 . the electron beam may be triggered at a predetermined point in a cardiac r-wave, a time interval from a reference point in time, and/or a defined point in the r-to-r interval between r-waves or r-wave peaks. for example, the beam sweep may be triggered at 40% completion of an r-to-r interval. at step 220 , the electron beam sweeps the target ring 130 in an arc. the electron beam may sweep in a 360-degree arc with 210-degrees of the 360-degree arc occupied by the target ring 130 . then, at step 225 , as the electron beam impinges upon the tungsten target ring 130 , the tungsten material is excited by the electron beam. x-rays or other such radiation are produced from the excitation and travel outward from the target ring 130 . the path of the x-rays depends upon the angle at which the electron beam impacted the target ring 130 . at step 230 , at least some of the x-rays pass through the patient and impinge upon the detector ring 140 . at step 235 , the data acquisition system (das) 160 receives signals from the detector ring 140 that are indicative of x-rays impacting the detector ring 140 . the received data signals vary in value depending upon the angle and intensity of the x-rays striking the detector ring 140 . a larger data value indicates an x-ray that is only slightly attenuated along the x-ray's path from the target ring 130 to the detector ring 140 . a smaller data value indicates an x-ray that is greatly attenuated by an organ or other dense mass when travelling from the target ring 130 to the detector ring 140 . when no data value is received for a certain portion of the detector ring 140 , this indicates that the x-rays impacted bone in the patient and are totally blocked. the das 160 transmits the image data to other processing units for further processing and display. the das 160 may transmit supplemental data as well, such as ecg data, timing information, triggering information, and/or patient information. alternatively, the das 160 may process the image data. the image data from a single sweep forms a complete image frame. at step 240 , the patient may be moved between or during electron beam sweeps. if moved between sweeps, the patient may be moved by the thickness of a slice (e.g. 1.5 millimeters, 3 millimeters, 6 millimeters, etc.). alternatively, the patient may be moved continuously during imaging (3 eg. at a rate of 1.5 millimeters, 3 millimeters or 6 millimeters per second). then, at step 245 , after the desired motion has occurred, another sweep may be triggered. for example, after the patient has been moved three millimeters, another electron beam sweep may be triggered at 40% of the next r-to-r interval. the steps described above may be repeated for another sweep. finally, at step 250 , after a desired number of sweeps have been executed and imaging data obtained and processed for a sequence of image frames, the image frames may be displayed as a cine loop. the cine sequence may also be stored or printed. in certain embodiments, the desired number of sweeps are executed in two or more cardiac cycles. the process described above in reference to fig. 2 may be repeated if desired. fig. 3 illustrates an ecg-triggered step-cine sequence 300 as used for electron beam angiography in accordance with an embodiment of the present invention. the sequence 300 involves a contrast injection. the sequence 300 uses an ecg-trigger with a 0.3 second r-to-r interval delay. also, the sequence 300 uses every heartbeat for scanning unless the heart rate rises above a certain speed threshold. additionally, the sequence 300 uses a 50 millisecond sweep, performing 4 sweeps per level of the heart (equals 8 slices/level with a dual-slice detector ring). the sequence 300 employs a 3.0 millimeter forward table motion between sweeps. first, the system 100 is prepared for an image scanning sequence. the patient positioner 150 is moved into position. the electron beam is first triggered (trigger(1)) after a certain point in an r-to-r interval for pre-scan configuration. a pre-scan may be used to configure or calibrate the system 100 and obtain patient position and other such information. then, a contrast agent is injected into the patient and the system 100 delays to wait for the second trigger (trigger(2)). after trigger(2) triggers a second pre-scan, a delay is observed to prepare the system 100 for another pre-scan. then, trigger(3) triggers at the start of an r-wave for the third pre-scan. after a 0.3 second delay, four imaging sweeps of the target ring 130 are executed. after the fourth sweep, the patient positioner 150 is moved 3.0 millimeters. the system 100 waits for two heartbeats. then, the electron beam is triggered at a selected point in an r-wave. after a delay (e.g., 03..seconds), four more sweeps of the target ring 130 are executed. a cine loop may be created from image data obtained during the sweeps of the target ring 130 . image frames are formed from data obtained during a sweep of the target ring 130 . the image frames may be displayed individually or displayed in sequence to show cardiac motion. cine imaging is used to animate the images and create a 2-d or 3-d effect. fig. 4 illustrates an example of a sweep map 400 , which describes a scanning series in a sweep-by-sweep format in accordance with an embodiment of the present invention. the sweep map 400 is described as follows. the sweep row in the map 400 represents a sweep number from 1 to 8. the sweep number may repeat according to the number of slices and levels chosen. the coll row in the map 400 represents collimation in the system 100 . in the map 400 , a collimation of 3 indicates the use of dual 1.5 mm slices in scanning. the ma row indicates a desired number of milliamps to drive the electron beam, for example 1000 ma. the characteristic kv indicates a desired kilivoltage for the electron beam, such as 140 kv, for example. the det parameter in the map 400 represents a number of detector rings 140 in the system 100 . a value of 3 in a two detector ring 140 system 100 indicates that both detector rings 1 and 2 are used. type represents a type of sweep to be executed. in certain embodiments, a value of 3 indicates a sweep speed of 50 milliseconds, for example. horiz indicates horizontal position of the patient positioner 150 . in the map 400 , a value of 400 indicates a 400 millimeter position relative to a user-defined zero position. a value of 397 indicates 397 millimeters, which implies that the patient positioner 150 moved back 3.0 millimeters between triggers. vert is patient positioner 150 vertical position, such as 210 millimeters, for example. slew is patient positioner 150 slew, or lateral movement beside the plane of motion. a slew of 0 degrees indicates no slew. tilt is a tilt of the patient positioner 150 , representing movement within the plane of motion. a tilt of 0 degrees indicates no tilt. the row labeled table incr lists an increment of patient positioner 150 motion during each sweep. a table increment of 0 at sweep0 indicates that the table did not move during scanning in sweep 0, for example. target represents a type of target ring 130 . for example, target3 indicates a c-ring target. the trigger row in the map 400 reflects an array indicating trigger type. a trigger type array may be in the form of trigger(a,b,c,d), for example. for example, in sweep 1 of the map 400 , trigger(5,1,7,5,9), wherein 5 equals the total entries into the trigger array; 1 indicates that a manual trigger is to be a first trigger; 7 instructs the system 100 to wait for a bolus injector trigger to be a second trigger; 5 represents the minimum number of beats to skip and directs to choose the first available trigger; and 9 indicates that a timed delay may be used after an r-wave. in sweep 5, trigger(4,8,5,9). thus, there are 4 entries into the array. array element 8 indicates that table motion is completed before a scan. array element 5 indicates that the first available trigger may be chosen. array element 9 instructs the system 100 to use a timed delay after an r-wave. the delay row in the map 400 represents a delay array associated with the trigger array. for example, delay(a,b,c,d). in sweep 1 of the map 400 , for example, delay(5,0,16,0,0.3), wherein 5 indicates 5 total entries in the delay array; 0 indicates 0 seconds timed delay after a manual trigger; 16 indicates a timed delay of 16 seconds after a bolus injector trigger; 0 determines that 0 skipped heartbeats is a minimum number to skip based on thermal modeling, sweep times, table step minimum times, and reasonable heart rate, for example; and 0.3 represents a 0.3 second delay after an r-wave to start sweep 1. in sweep 5 of the map 400 , delay(4,0.25,0,0.3). a value of 4 indicates 4 entries in the delay array. a value of 0.25 relates to a 0.25 second minimum patient positioner 150 step time between sweeps. a value of 0 in the third array position indicates a minimum of 0 skipped heartbeats. a value of 0.3 in the last position indicates a 0.3 second delay after an r-wave to start a sweep, for example. figs. 5 and 6 illustrate an eba scanning series in accordance with certain embodiments of the present invention. in figs. 5 and 6 , the electron beam may be turned on after an r-wave has been detected. that is, figs. 5 and 6 depict a scan execution in which a delay after an r-wave is less than or equal to the time period for electron beam power up. fig. 5 illustrates a time sequence 500 before scan 1 begins, in accordance with certain embodiments of the present invention. in fig. 5, a sweep includes activities before the sweep plus a traversal of the target ring 130 . the notation trigger(1:3) indicates that the trigger for sweep 1 is the third element in the trigger array. in the time sequence 500 , trigger(1:3)7, which indicates a bolus injection, for example. time stamps are indicated by tn, where n may increment. for example, the first time stamp is t0. r-waves may be shown as r(n,rn), where n may increment as r-waves are collected and rn is a time at which the nth r-wave appeared. in the time sequence 500 , t0 is the clock time at manual trigger. time stamp t1 is the clock time at the bolus injector trigger. time stamp t2 may be calculated as the t1delay(1:3), or t116 seconds, for example. in the time sequence 500 , delay(1.4) is 0 (no skipping), so r-wave r(17,r17) may be used to start scanning. time stamp t3r17delay(1:5) timepsonr170.3 seconds0.130 seconds. time t417delay(1:5)r170.3 seconds. in the time sequence 500 , after the first r-wave r(1,r1), the system 100 begins pre-scan configuration and calibration. after a bolus injection of contrast agent at t1, the system 100 may wait for the agent to affect the heart and coronary arteries. then, after r-wave r(17,r17), the electron beam may be powered on and a series of four sweeps begun on the target ring 130 . the series of sweeps will be illustrated in fig. 6 below. fig. 6 illustrates a time sequence 600 between sweep 1 and sweep 2, in accordance with certain embodiments of the present invention. assuming the same delay parameters (delay>power on time) are used from the start of sweep 1 to the start of sweep 5, the same timing may be used on each subsequent trigger. in the time sequence 600 , time taken during a sweep is represented as tsn, where n increments with the sweep number. time intervals tm equal the previous time interval tm1 plus the time taken during the previous sweep. for example, in the time sequence 600 , the time to start sweep 2 is defined as t5. in time sequence 600 , t5 t4ts1. time during a sweep in sequence 600 represents total sweep time, including retrace-on, target time, and retrace-off time, for example. horizontal table positions may be sent to the patient positioner 150 as they appear in the sweep map 400 and are represented as hn, where n is the sweep number. in time sequence 600 , table position h1 is the position of the patient positioner 150 during sweep 1 and is equal to 400. table position h5 is the patient positioner 150 position during sweep 5 and is equal to 397 (a movement of 3.0 millimeters). in the time sequence 600 , four sweeps of the target ring 130 are executed over intervals ts1 through ts4, beginning at time stamp t4. image data is obtained from each sweep. at time stamp t8, the electron beam is turned off. additionally, the patient positioner 150 may be moved after sweep 4. after a certain point in the r-wave r(18,r18), the electron beam may be powered on again. after a certain delay delay(5:4), the motion of the patient positioner 150 may cease and the next sequence of target ring 130 sweeps may begin. additional image frames may be generated from the sweeps to form a cine loop of image frames. the image display and manipulation system 164 may combine the image frames into a cine imaging loop displaying motion of the heart and coronary arteries over time and cardiac phase. figs. 7 and 8 illustrate image scanning sequences in which a delay chosen is less than the time taken to activate the power supply for the electron beam. in figs. 7 and 8 , the electron beam is turned on before an upcoming r-wave. that is, figs. 7 and 8 depict a scan execution in which a delay after an r-wave is greater than the time period for electron beam power up. if a delay is set less than the electron beam power on time, the high voltage module 124 is turned on in anticipation of the r-wave and delay. if the beam is not turned on early enough or the r-wave comes unexpectedly early, the beam may not be ready to sweep the target ring 130 . if the electron beam is not ready to sweep the target ring 130 , the beam may be deactivated and the start time recalculated for the next expected r-wave. in certain embodiments, the electron beam may be aimed at a beam stop in anticipation of an r-wave. the beam stop may absorb heat from the electron beam up to a thermal capacity based on the material used for the beam stop. if a valid r-wave does not arrive before the thermal capacity of the beam stop is reached, the series may be aborted and calculations restarted. fig. 7 illustrates a time sequence 700 for a scan from user confirmation to start of sweep 1 on the target ring 130 in accordance with certain embodiments of the present invention. the time sequence 700 is similar to the time sequence 500 , described above. in the time sequence 700 , however, the dotted line indicates electron beam power-on time. the electron beam may be powered-up by focusing it on a beam stop during the period between t5 and t7, indicated by the dotted line, for example. in the time sequence 700 , pr(17,pr77) indicates a predicted r-wave time, where n represents a number of heartbeats. the pr(17,pr17)time is used to initiate the electron beam. the time r(17,r17) indicates the actual incidence of an r-wave. after the electron beam is powered on and a delay is observed to allow the electron bream to reach a desired intensity, sweep 1 may be triggered at time t7 at a desired point in the r-wave r(17,r17). if the time between the predicted r-wave pr(17,r17) and the actual r-wave r(17,r17) exceeds a certain threshold, the beam stop may reach a thermal limit. if the beam stop's thermal limit is reached, the series of sweeps may be abandoned and restarted. fig. 8 illustrates a time sequence 800 from start of sweep 1 on the target ring 130 to start of sweep 5 on the target ring 130 in accordance with certain embodiments of the present invention. the time sequence 800 continues from the time sequence 700 . the time sequence 800 is similar to the time sequence 600 , described above. in the time sequence 800 , the electron beam is turned on at time t12. during the dotted time period t16 represents electron beam power-on time. a delay may be used to allow the electron beam to power up before another series of sweeps begin. if the heartbeat r18 occurs before the electron beam is valid at time t14, heartbeat r18 may be skipped, and the system 100 may wait for heartbeat r19, unless thermal accumulation at the beam stop exceeds the thermal threshold of the beam stop. in an alternative embodiment, trigger delays may be calculated using a formula based on patient heart rate. the heart rate may be a heart rate at the start of a series of imaging sweeps or a median heart rate throughout a series of sweeps, for example. alternatively, trigger delays may be obtained for each trigger based on a lookup table of predetermined values. additionally, triggering may be implemented with a pattern of delays and/or patient positioner 150 increments. for example, a first trigger may be executed at 0% after an r-wave and a sweep may acquire a full heartbeat. then, a second sweep may be triggered at 40% after an r-wave with a small patient positioner 150 move. next, a third sweep may be triggered at 80% after an r-wave, followed by a larger move of the patient positioner 150 . furthermore, in an alternative embodiment, an operator may be allowed to pause the system 100 . for example, a user may pause the electron beam between sweeps to allow a patient to take a breath. after the patient takes a breath, the user may resume the scanning series, for example. in an alternative embodiment, multiple sweeps may be executed during a single r-to-r interval. for example, a first sweep may be executed at 40% completion of an r-to-r interval, and then a second sweep of the target ring 130 may be executed after 80% of the r-to-r interval. thus, multiple images may be obtained in an r-to-r interval. additionally, the patient positioner 150 may be moved between sweeps. that is, a sweep is triggered at 40%, then the patient positioner 150 is moved after the sweep, and then another sweep is triggered at 80% of the r-to-r interval. the pattern may be repeated with further movement of the patient positioner 150 . thus, two image acquisitions may be obtained per heartbeat (e.g., one image at 40% and a second image at 80%), for example. the images may be used in a cine loop or may be viewed as individual images. in an alternative embodiment, a conventional mechanical computed tomography scanner may be used for cine imaging. fig. 9 illustrates a conventional mechanical ct scanner 900 in accordance with certain embodiments of the present invention. fig. 10 illustrates a block diagram of a conventional mechanical ct scanner 1000 in accordance with certain embodiments of the present invention. figs. 9 and 10 illustrate a ct imaging system as described in u.s. pat. no. 6,385,292 to dunham et al. in certain embodiments, a cine angiography series of images may be obtained from a conventional ct scanner, such as the ct scanner described in figs. 9 and 10 . x-rays from an x-ray source 14 may irradiate a patient 22 and impinge upon a detector 18 . the das 32 may collect image data based on the x-rays impinging upon the detector 18 and form a cine loop of motion images using an image reconstructor 34 and a computer 36 . the patient 22 is positioned on a table 36 . the table 43 may be moved during scanning. a cine sequence of images depicting patient cardiac activity may be obtained as described above. while the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the invention. in addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
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134-585-322-102-073
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JP
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[
"US"
] |
G03G5/043,G03G5/082,G03G5/147
| 1986-04-30T00:00:00 |
1986
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[
"G03"
] |
light receiving member for use in electrophotography with a surface layer comprising non-single-crystal material containing tetrahedrally bonded boron nitride
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improved light receiving members which are characterized by having an special surface layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride or a non-monocrystalline material containing said boron nitride and trihedrally bonded boron nitride in mingled state or by having an especial surface layer constituted with a lower layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride and an upper layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state. the improved light receiving members excel particularly in moisture resistance, repeating use characteristic, electrical voltage withstanding property environmental use characteristic and durability. and the improved light receiving member are particularly advantageous when used as an image-making member in electrophotography since they always exhibit substantially stable electric characteristics without depending upon the working circumstances, maintain a high photosensitivity and a high s/n ratio, do not invite any undesirable influence due to residual voltage even when used repeatedly for a long period of time, cause either defective image nor image flow and have a wealth of cleaning properties.
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1. an improved light receiving member for use in electrophotography comprising a substrate and a light receiving layer having at least a 3 to 100 .mu.m thick photoconductive layer comprising an amorphous material containing silicon atoms as the matrix and at least one kind of atom selected from the group consisting of hydrogen and halogen in a total amount of 1 to 40 atomic % and a 0.003 to 30 .mu.m thick surface layer being disposed in this order from the side of the substrate, characterized in that said surface layer comprises a non-signle-crystal material consisting essentially of tetrahedrally bonded boron nitride and at least one kind of atom selected from the group consisting of hydrogen and halogen. 2. the light receiving member according to claim 1, wherein the surface layer contains a p-type dopant selected from the group consisting of ge, zn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 3. the light receiving member according to claim 1, wherein the surface layer contains an n-type dopant selected from the group consisting of si, sn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 4. the light receiving member according to claim 1, wherein the light receiving layer further contains one or more constituent layers. 5. the light receiving member according to claim 4, wherein the light receiving layer contains a charge injection inhibition layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from group consisting of hydrogen and halogen, and an element selected from the group consisting of group iii and v elements of the periodic table. 6. the light receiving member according to claim 4, wherein the light receiving layer contains a long wavelength light absorptive layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of germanium and tin, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 7. the light receiving member according to claim 4, wherein the light receiving layer contains an adhesiveness enhancing contact layer between the photoconductive layer and the substrate or between the photoconductive layer and the layer thereunder, which comprises a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of oxygen, carbon and nitrogen, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 8. the light receiving member according to claim 4, wherein the light receiving layer contains an intermediate layer between the photoconductive layer and the surface layer, which comprises a non-single-crystal material containing silicon atoms as the matrix, carbon atoms and at least one kind of atom selected from the group consisting of hydrogen and halogen. 9. an improved light receiving member for use in electrophotography comprising a substrate and a light receiving layer having at least a 3 to 100 .mu.m thick photoconductive layer comprising an amorphous material containing silicon atoms as the matrix and at least one kind of atom selected from the group consisting of hydrogen and halogen in a total amount of 1 to 40 atomic % and a 0.003 to 30 .mu.m thick surface layer being disposed in this order from the side of the substrate, characterized in that said surface layer comprises a non-single-crystal material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state wherein the weight ratio of tetrahedrally bonded boron nitride to trihedrally bonded boron nitride is at least about 1:1 and at least one kind of atom selected from the group consisting of hydrogen and halogen. 10. the light receiving member according to claim 9, wherein the surface layer contains a p-type dopant selected from the group consisting of ge, zn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 11. the light receiving member according to claim 9, wherein the surface layer contains an n-type dopant selected from the group consisting of si, sn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 12. the light receiving member according to claim 9, wherein the light receiving layer further contains one or more constituent layers. 13. the light receiving member according to claim 12, wherein the light receiving layer contains a charge injection inhibition layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of hydrogen and halogen, and an element selected from the group consisting of group iii and v elements of the periodic table. 14. the light receiving member according to claim 12, wherein the light receiving layer contains a long wavelength light absorptive layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of germanium and tin, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 15. the light receiving member according to claim 12, wherein the light receiving layer contains an adhesiveness enhancing contact layer between the photoconductive layer and the substrate or between the photoconductive layer and the layer thereunder, which comprises a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of oxygen, carbon and nitrogen, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 16. the light receiving member according to claim 12, wherein the light receiving layer contains an intermediate layer between the photoconductive layer and the surface layer, which comprises a non-single-crystal material containing silicon atoms as the matrix, carbon atoms and at least one kind of atom selected from the group consisting of hydrogen and halogen. 17. an improved light receiving member for use in electrophotography comprising a substrate and a light receiving layer having at least a 3 to 100 .mu.m thick photoconductive layer comprising an amorphous material containing silicon atoms as the matrix and at least one kind of atom selected from the group consisting of hydrogen and halogen in a total amount of 1 to 40 atomic % and a 0.003 to 30 .mu.m thick surface layer being disposed in this order from the side of the substrate, characterized in that said surface layer is constituted by a lower layer and an upper layer: said lower layer comprising a non-single-crystal material containing tetrahedrally bonded boron nitride and at least one kind of atom selected from the group consisting of hydrogen and halogen and said upper layer comprising a non-single-crystal material containing tetrahedrally bonded boron nitride and trihedrally bonded boron in mingled state wherein the weight ratio of tetrahedrally bonded boron nitride to trihedrally bonded boron nitride is at least about 1:1 and at least one kind of atom selected from the group consisting of hydrogen and halogen. 18. the light receiving member according to claim 17, wherein the surface layer contains a p-type dopant selected from the group consisting of ge, zn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 19. the light receiving member according to claim 17, wherein the surface layer contains an n-type dopant selected from the group consisting of si, sn and a mixture thereof in an amount of less than 1.times.10.sup.3 atomic ppm. 20. the light receiving member according to claim 17, wherein the light receiving layer further contains one or more constituent layers. 21. the light receiving member according to claim 20, wherein the light receiving layer contains a charge injection inhibition layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of hydrogen and halogen, and an element selected from the group consisting of group iii and v elements of the periodic table. 22. the light receiving member according to claim 20, wherein the light receiving layer contains a long wavelength light absorptive layer comprising a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected from the group consisting of germanium and tin, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 23. the light receiving member according to claim 20, wherein the light receiving layer contains an adhesiveness enhancing contact layer between the photoconductive layer and the substrate or between the photoconductive layer and the substrate or between the photoconductive layer and the layer thereunder, which comprises a non-single-crystal material containing silicon atoms as the matrix, at least one kind of atom selected for the group consisting of oxygen, carbon and nitrogen, and at least one kind of atom selected from the group consisting of hydrogen and halogen. 24. the light receiving member according to claim 20, wherein the light receiving layer contains an intermediate layer between the photoconductive layer and the surface layer, which comprises a non-single-crystal material containing silicon atoms as the matrix, carbon atoms and at least one kind of atom selected from the group consisting of hydrogen and halogen. 25. an electrophotographic process comprising the steps of: (a) applying an electric field to the light receiving member of claim 1; and (b) applying an electromagnetic wave to said light receiving member thereby forming an electrostatic image. 26. an electrophotographic process comprising the steps of: (a) applying an electric field to the light receiving member of claim 9; and (b) applying an electromagnetic wave to said light receiving member thereby forming an electrostatic image. 27. an electrophotographic process comprising the comprising the steps of: (a) applying an electric field to the light receiving member of claim 17; and (b) applying an electromagnetic wave to said light receiving member thereby forming an electrostatic image.
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field of the invention this invention relates to the improvements in the light receiving member comprising a substrate and a light receiving layer having at least a photoconductive layer formed of an amorphous material containing silicon atom as the main layer constituent and a surface layer. more particularly, it relates to an improved light receiving member suited especially for use in electrophotography which has a light receiving layer having a surface layer formed of an amorphous material containing tetrahedrally bonded boron nitride or both said boron nitride and trihedrally bonded boron nitride being disposed on said photoconductive layer. background of the invention for the light receiving members for use in electrophotography and the like, the public attention has been focused on such light receiving members that have a photoconductive layer formed of an amorphous material containing silicon atom as the main layer constituent and hydrogen atom or/and halogen atom [hereinafter referred to as "a--si(h,x)"] as disclosed in unexamined japanese patent publications sho. 54(1979)-86341 and sho. 56(1981)-83746, since said photoconductive layer has a high vickers hardness in addition to having an excellent matching property in the photosensitive region in comparison with that in other kinds of light receiving member and it is not harmful to living things as well as man upon the use. by the way, in any case, such light receiving member comprises a substrate and a photoconductive layer formed of a--si(h,x). in this respect, it is known to provide a surface layer on the photoconductive layer, which functions to prevent the photoconductive layer from being injected by charges from its free surface side when it is engaged in charging process and to improve the moisture resistance, repeating use characteristics, breakdown voltage resistance, use environmental characteristics and durability of the photoconductive layer, and further in order to make it possible to maintain the quality of the images to be obtained for a long period of time. and there have been made various proposals to form such surface layer using a high resistant and phototransmissive non-monocrystalline material such as amorphous material and polycrystalline material. among those proposals, there is a proposal to form such surface layer using a boron-nitrogen series amorphous material as disclosed in unexamined japanese patent publications sho. 59(1984)12448 and sho. 60(1985)-61760. however, the boron(b)-nitrogen(n) series amorphous materials to form the foregoing surface layer which are disclosed in said publications are: boron atom and nitrogen atom are contained in unevenly distributed state and in addition, in large amount of hydrogen atom is contained; b--h bond, n--h bond and b--b bond are present in abundance; and the presence of b--n bond is slight and three dimensional structure by b--n bond is little present. because of this, for the light receiving members disclosed in said publications which has a surface layer formed of said boron-nitrogen series amorphous material, there are still unresolved problems that the surface layer is apt to be easily deteriorated not only with corona discharge in the charging process but also due to various mechanical actions during the contacts with a cleaning blade or other members of the device and as the layer deteriorates, it loses the functions required therefor. in addition to the above problems, the foregoing light receiving member has other problems that it is insufficient in charging efficiency so that it often brings about defective images such as those accompanied with undesired ghosts in the case where it is used in an image-making device. summary of the invention this invention is aimed at eliminating the foregoing problems principally relative to the surface layer in the conventional light receiving member and providing an improved light receiving member having a desirable surface layer which can continuously exhibit the original functions required therefor without accompaniment of the foregoing problems even in repeating use for a long period of time. another object of this invention is to provide an improved light receiving member for use in electrophotography which always maintains a stable and effective charging efficiency and makes it possible to obtain high quality images even in the case of repeating use for a long period of time. the present inventors have conducted extensive studies for overcoming the foregoing problems on the conventional light receiving members and attaining the objects as described above and, as a result, have accomplished this invention on the findings as below described. that is, the present inventors have experimentally confirmed that the composition of the above mentioned surface layer formed of the foregoing boron-nitrogen series amorphous material is the very factor in order to solve the foregoing problems in the conventional light receiving member. in view of the above, the present inventors have firstly investigated about the situation of influences of various boron nitrides in the cases when they are incorporated into a surface layer of a light receiving member for use in electrophotography. as a result, the findings as below mentioned were obtained and on the basis of those findings, the present inventors have come to the result of acknowledging that not all but only limited kinds of boron nitride are effectively usable as the constituent of said surface layer. that is, one finding is that the hexagonal system boron nitride of which cordination number being 3 is of the same structure as graphite, very soft, and 2 for mohs hardness, and that in the case where the surface layer is formed of such boron nitride, the resultant light receiving member will become such that is weak against the impacts of active substances such as ion, ozone, electron etc. which will be generated by electric corona and that is apt to be easily deteriorated to lose the functions required therefor when it is mechanically damaged due to contacts with cleaning blade or other members of the electrophotographic copying system. further, since the hexagonal system boron nitride is of a relatively low electrical resistance, the light receiving member having a surface layer containing such boron nitride is undesirably low for the charging efficiency so that it often bring about defective images as such accompanied with undesired ghosts. another finding is that the cubic system boron nitride of which cordination number being 4 is of a large mohs hardness, sufficiently resistant not only against the impacts of the above mentioned active substances but also against mechanical impacts and large enough for electrical resistance, and that in the case where the surface layer is formed of such cubic system boron nitride, the resultant light receiving member will become such desirable one that has a sufficient discharging efficiency and can make high quality images. in view of the above, as far as the strength is concerned, it can be said that the surface layer is desirable to be formed of an amorphous material containing the hexagonal system boron nitride. however, related various factors as below mentioned should be taken into consideration for the preparation of a desirable light receiving member particularly for use in electrophotography. that is, the image-making process using a light receiving member in electrophotographic copying system comprises, typically, corona charging, image exposing, image developing with toner, image transferring to a paper and light receiving member cleaning. in this respect, the surface of the light receiving member will come to contact with plural members respectively of a different quality of the material in each step. therefore, the quality of an image to be transferred to a paper will largely depend upon whether the contact of the light receiving member with the respective members in the respective steps is suitable or not. for instance, in the case of the cleaning step using a blade, when the surface of the light receiving member is excessively hard, the blade will be worn away at an early stage and as a result, cleaning deficiency is apt to occur. and in that case, since the blade will be short-lived, the maintenance expenses of the copying system eventually become costly. on the other hand, in the case where the surface of the light receiving member is excessively soft, it is easily shaved by the blade to result in bringing about undesirable defects on an image to be made and other than this, the blade will be short-lived. therefore, the maintenance expenses of the copying system eventually become costly also in this case. in view of the above, it is necessary for the hardness of the surface of the light receiving member to be decided while having due regards on the harmonization thereof with the hardnesses of the respective members with which the light receiving member will contact in the respective steps of the above mentioned image-making process in electrophotographic copying system. particularly in the case where the surface layer of the light receiving member is tried to form using the foregoing cubic system boron nitride, further appropriate improvements are required in the respective members in the respective steps of the above mentioned image-making process. as a result of further continued studies on the basis of the above findings, the present inventors have come to obtain an acknowledge that either in the case where the surface layer of the light receiving member is made to be such that is formed of a non-monocrystalline material containing at least tetrahedrally bonded boron nitride or both tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state or in the case where the surface layer is made to be such that is constituted with a lower layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride and an upper layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state, the resultant light receiving member having any of the above surface layers becomes to have a desirable harmonization between the hardness of the surface of the light receiving member and the hardnesses of the respective members of the respective steps of the image-making process in electrophotographic copying system. this invention has been completed based on the foregoing various findings, and it typically concerns an improved light receiving member comprising a substrate and a light receiving layer having at least a photoconductive layer formed of an amorphous material containing silicon atom as the main constituent atom and at least one kind atom selected from hydrogen atom and halogen atom and a surface layer, which is characterized in that said surface layer is formed of (1) a non-monocrystalline material containing tetrahedrally bonded boron nitride or (2) a non-monocrystalline material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride, or is constituted with a lower layer formed of a non-monocrystalline material containing tetrahedrally bonded boron nitride and an upper layer formed of a non-monocrystalline material containing trihedrally bonded boron nitride in mingled state. and in a preferred embodiment of the improved light receiving member according to this invention, the above mentioned surface layer may further contain dopants, either p-type or n-type. in that case, there is provided a further desirable light receiving member which can exhibit additional functions to prevent accumulation of charges in the surface layer after image exposure and also to further effectively prevent the occurrence of problems relative to image flow and residual voltage. that is, in the case of the conventional light receiving member, the accumulation of charges often occurs in the surface layer after image exposure and the charges accumulated move horizontally near the interface between the surface layer and the photoconductive layer to thereby invite the occurrence of image flow on the resultant image. however, according to the light receiving member having of this invention which has such surface layer containing dopants, either p-type or n-type, charges which are moving into the surface layer after image exposure are mobilized to the free surface of the surface layer so that the occurrence of the problems relative to image flow and also to residual voltage which is often found on the conventional light receiving member can be effectively prevented. brief description of the drawings fig. 1(a) through fig. 1(i) are schematic views illustrating the typical layer constitution of a representative light receiving member according to this invention; fig. 1(a') through fig. 1(i') are schematic views illustrating modifications of the light receiving members shown in fig. 1(a) through fig. 1(i). fig. 2 is a schematic explanatory view of a glow discharging fabrication apparatus for preparing the light receiving member of this invention; and fig. 3 and fig. 4 are schematic fragmentary sectional views of a substrate which can be used in the light receiving member of this invention. detailed description of the invention representative embodiments of the light receiving member according to this invention will now be explained more specifically referring to the drawings. the description is not intended to limit the scope of this invention. representative light receiving members for use in electrophotography according to this invention are as shown in fig. 1(a) through fig. 1(i) and also in fig. 1(a') through fig. 1(i'), in which are shown substrate 101, photoconductive layer 102, surface layer 103, charge injection inhibition layer 104, long wavelength light absorptive layer (hereinafter referred to as "ir absorptive layer") 105, contact layer 106, free surface 107, intermediate layer 108, lower constituent layer of the surface layer (hereinafter referred to as "lower layer") 103' and upper constituent layer of the surface layer (hereinafter referred to as "upper layer") 103". fig. 1(a) and fig. 1(a') are schematic views illustrating typical representative layer constitutions of this invention, which are shown: (1) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(a)]; and (2) a modification of the light receiving member (1) of which surface layer 103 being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(a')]. fig. 1(b) and fig. 1(b') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (3) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the charge injection inhibition layer 104, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(b)]; and (4) a modification of the light receiving member (3) of which surface layer 103 being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(b')]. fig. 1(c) and fig. 1(c') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (5) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the ir absorptive layer 105, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(c)]; and (6) a modification of the light receiving member (5) of which surface layer 103 being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(c')]. fig. 1(d) and 1(d') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (7) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the contact layer 106, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(d)]; and (8) a modification of the light receiving member (7) of which surface layer being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(d')]. fig. 1(e) and fig. 1(e') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (9) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the charge injection inhibition layer 104, the contact layer 106, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(e)]; and (10) a modification of the light receiving member (9) of which surface layer being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(e')]. fig. 1(f) and fig. 1(f') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (11) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the ir absorptive layer 105, the contact layer 106, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(f)]; and (12) a modification of the light receiving member (11) of which surface layer being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(f')]. fig. 1(g) and fig. 1(g') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (13) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the ir absorptive layer 105, the charge injection inhibition layer 104, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(g)]; and (14) a modification of the light receiving member (13) of which surface layer 103 being lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(g')]. fig. 1(h) and fig. 1(h') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (15) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the ir absorptive layer 105, the charge injection inhibition layer 104, the contact layer 106, the photoconductive layer 102 and the surface layer 103 having the free surface 107 [fig. 1(h)]; and (16) a modification of the light receiving member (15) of which surface layer 103 being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(h')]. fig. 1(i) and fig. 1(i') are schematic views illustrating another representative layer constitutions of this invention, which are shown: (17) the light receiving member comprising the substrate 101 and the light receiving layer constituted by the charge injection inhibition layer 104, the photoconducting layer 102, the intermediate layer 108 and the surface layer 103 having the free surface 107 [fig. 1(i)]; and (18) a modification of the light receiving member (17) of which surface layer 103 being constituted by lower layer 103' and upper layer 103" having the free surface 107 [fig. 1(i')]. substrate 101 the substrate 101 for use in this invention may either be electroconductive or insulative. the electroconductive substrate can include, for example, metals such as nicr, stainless steels, al, cr, mo, au, nb, ta, v, ti pt and pb or the alloys thereof. the electrically insulative substrate can include, for example, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic and paper. it is preferred that the electrically insulative substrate is applied with electroconductive treatment to at least one of the surfaces thereof and disposed with a light receiving layer on the thus treated surface. in the case of glass, for instance, electroconductivity is applied by disposing, at the surface thereof, a thin film made of nicr, al, cr,, mo, au, ir, nb, ta, v, ti, pt, pd, in.sub.2 o.sub.3, sno.sub.2, ito (in.sub.2 o.sub.3 +sno.sub.2), etc. in the case of the synthetic resin film such as a polyester film, the electroconductivity is provided to the surface by disposing a thin film of metal such as nicr, al, ag, pv, zn, ni, au, cr, mo, ir, nb, ta, v, tl and pt by means of vaccum deposition, electron beam vapor deposition, sputtering, etc., or applying lamination with the metal to the surface. the substrate may be of any configuration such as cylindrical belt-like or plate-like shape, which can be properly determined depending on the application uses. the thickness of the substrate is properly determined so that the light receiving member as desired can be formed. in the case where flexibility is required for the light receiving member, it can be made as thin as possible within a range capable of sufficiently providing the function as the substrate. however, the thickness is usually greater than 10 .mu.m in view of the fabrication and handling or mechanical strength of the substrate. and, it is possible for the surface of the substrate to be uneven in order to eliminate occurrence of defective images caused by a so-called interference fringe pattern being apt to appear in the formed images in the case where the image making process is conducted using coherent monochromatic light such as laser beams. charge injection inhibition layer 104 the charge injection inhibition layer is to dispose under the photoconductive layer 102. the charge injection inhibition layer in the light receiving member is constituted with an a--si(h,x) material containing group iii element as a p-type dopant or group v element as an n-type dopant [hereinafter referred to as "a--si(iii,v):(h,x)"], a poly-si(h,x) material containing group iii element or group v element [hereinafter referred to as "poly-si(iii,v):(h,x)"] or a non-monocrystalline material containing the above two materials [hereinafter referred to as "non-si(iii,v):(h,x)"]. the charge injection inhibition layer in the light receiving member of this invention functons to maintain an electric charge at the time when the light receiving member is engaged in electrification process and also to contribute to improving the photoelectrographic characteristics of the light receiving member. in view of the above, to incorporate either the group iii element or the group v element into the charge injection inhibition layer is an important factor to efficiently exhibit the foregoing functions. specifically, the group iii element can include b (boron), al (aluminum), ga (gallium), in (indium) and tl (thallium). the group v element can include, for example, p (phosphor), as (arsenic), sb (antimony) and bi (bismuth). among these elements, b, ga, p and as are particularly preferred. and the amount of either the group iii element or the group v element to be incorporated into the charge injection inhibition layer is preferably 3 to 5.times.10.sup.4 atomic ppm, more preferably 50 to 1.times.10.sup.4 atomic ppm, and most preferably 1.times.10.sup.2 to 5.times.10.sup.3 atomic ppm. as for the hydrogen atoms(h) and the halogen atoms(x) to be incorporated into the charge injection inhibition layer, the amount of the hydrogen atoms(h), the amount of the halogen atoms(x) or the sum of the amounts of the hydrogen atoms and the halogen atoms(h+x) is preferably 1.times.10.sup.3 to 7.times.10.sup.5 atomic ppm, and most preferably, 1.times.10.sup.3 to 2.times.10.sup.5 atomic ppm in the case where the charge injection inhibition layer is constituted with a poly-si(iii,v):(h,x) material and 1.times.10.sup.4 to 6.times.10.sup.5 atomic ppm in the case where the charge injection inhibition layer is constituted with an a--si(iii,v):(h,x) material. further, it is possible to incorporate at least one kind atoms selected from oxygen atoms, nitrogen atoms and carbon atoms into the charge injection inhibition layer aiming at improving the bondability of the charge injection inhibition layer not only with the substrate but also with other layer such as the photoconductive layer and also improving the matching of an optical band gap(egopt). in this respect, the amount of at least one kind atoms selected from oxygen atoms, nitrogen atoms and carbon atoms to be incorporated into the charge injection inhibition layer is preferably 1.times.10.sup.-3 to 50 atomic %, more preferably 2.times.10.sup.-3 to 40 atomic %, and most preferably 3.times.10.sup.-3 30 atomic %. the thickness of the charge injection inhibition layer in the light receiving member is an important factor also in order to make the layer to efficiently exhibit its functions. in view of the above, the thickness of the charge injection inhibition layer is preferably 0.03 to 15 .mu.m, more preferably 0.04 to 10 .mu.m, and most preferably 0.05 to 8 .mu.m. ir absorptive layer 105 the ir absorptive layer 105 in the light receiving member of this invention is to dispose under the photoconductive layer 102 or the charge injection inhibition layer 104. the ir absorptive layer in the light receiving member of this invention functions to effectively absorb the long wavelength light remained unabsorbed in the photoconductive layer to thereby prevent the appearance of interference phenomena due to reflection of long wavelength light at the substrate surface. the ir absorptive layer 105 is constituted with an a--si(h,x) material containing germanium atoms(ge) or/and tin atoms(sn) [hereinafter referred to as "a--si(ge,sn) (h,x)"], a poly--si(h,x) material containing germanium atoms (ge) or/and tin atoms(sn) [hereinafter referred to as "poly--si(ge,sn) (h,x)"]or a non-monocrystalline material containing at least one of the above two materials [hereinafter referred to as "non--si(ge,sn) (h,x)"]. as for the germanium atoms(ge) and the tin atoms(sn) to be incorporated into the ir absorptive layer, the amount of the germanium atoms(ge), the amount of the tin atoms(sn) or the sum of the amounts of the germanium atoms and the tin atoms(ge+sn) is preferably 1 to 1.times.10.sup.6 atomic ppm, more preferably 1.times.10.sup.2 to 9.times.10.sup.5 atomic ppm, and most preferably, 5.times.10.sup.2 to 8.times.10.sup.5 atomic ppm. as for the hydrogen atoms(h) and the halogen atoms(x) to be incorporated into the ir absorptive layer, the amount of the hydrogen atoms(h), the amount of the halogen atoms(x) or the sum of the amounts of the hydrogen atoms and the halogen atoms(h+x) is preferably 1.times.10.sup.3 to 3.times.10.sup.5 atomic ppm, and most preferably, 1.times.10.sup.3 to 2.times.10.sup.5 atomic ppm in the case where it is constituted with a poly--si(ge,sn) (h,x) material and 1.times.10.sup.4 to 6.times.10.sup.5 atomic ppm in the case where it is constituted with an a--si(ge,sn) (h,x) material. and, the thickness of the ir absorptive layer 105 is preferably 0.05 to 25 .mu.m, more preferably 0.07 to 20 .mu.m, and most preferably 0.1 to 15 .mu.m. contact layer 106 the contact layer 106 in the light receiving member of this invention is to dispose under the photoconductive layer. the main object of disposing the contact layer in the light receiving member of this invention is to enhance the bondability between the substrate and the photoconductive layer, between the charge injection inhibition layer and the photoconductive layer or between the ir absorptive layer and the photoconductive layer. the contact layer 106 is constituted with an a--si(h,x) material containing at least one kind atom selected from oxygen atom, carbon atom and nitrogen atom [hereinafter referred to as "a--si(o,c,n) (h,x)"], a poly--si(h,x) material containing at least one kind atom selected from oxygen atom, carbon atom and nitrogen atom [hereinafter referred to as "poly--si(o,c,n) (h,x)"] or a non--si(h,x) material containing at least one kind atom selected from oxygen atom, carbon atom and nitrogen atom [hereinafter referred to as "non--si(o,c,n) (h,x)"]. in the light receiving member of this invention, the amount of nitrogen atoms, oxygen atoms, or carbon atoms to be incorporated in the contact layer is properly determined according to the use purposes. however, the amount of one or more kind atoms of them to be contained in the contact layer is preferrably 1.times.10.sup.2 to 9.times.10.sup.5 atomic ppm and more preferrably 1.times.10.sup.2 tp 4.times.10.sup.5 atomic ppm. as for the hydrogen atoms(h) and the halogen atoms(x) to be contained in the contact layer, the amount of the hydrogen atoms(h), the amount of the halogen atoms(x) or the sum of the amounts of the hydrogen atoms and the halogen atoms(h+x) is preferably 10 to 7.times.10.sup.5 atomic ppm, and most preferably, 10 to 2.times.10.sup.5 atomic ppm in the case where it is constituted with a poly--si(o,c,n) (h,x) material, and 1.times.10.sup.3 to 7.times.10.sup.5 atomic ppm in the case where it is constituted with an a--si(o,c,n) (h,x) material. and the thickness of the contact layer 106 is preferably 20 .ang. to 5 .mu.m, more preferably 50 .ang. to 3 .mu.m, and most preferably, 100 .ang. to 1 .mu.m. by the way, in the light receiving member of this invention, it is possible to selectively combine the foregoing charge injection inhibition layer 104, ir absorptive layer 105 and contact layer 106. representative embodiments in that case are shown in fig. 1(e) to 1(h) and figs. 1(e') to 1(h'). further, in the light receiving member of this invention, it is possible to make the foregoing charge injection inhibition layer 104 or ir absorptive layer to be such that can function not only as that layer but also as the contact layer. in that case, the object can be attained by incorporating at least one kind atom selected from oxygen atom, carbon atom and nitrogen atom into the corresponding layer. further in addition, it is also possible to make either the foregoing ir absorptive layer 105 or the foregoing charge injection inhibition layer to be such that can exhibit the functions of the two layers by incorporating the group iii element or the group v element into the foregoing ir absorptive layer or by incorporating germanium atom or tin atom into the foregoing charge injection inhibition layer. now, for the formation of each of the above mentioned constitutent layers, that is, charge injection inhibition layer 104, ir absorptive layer 105 and contact layer 106 of the light receiving member of this invention, any of the known film forming processes such as thermal induced chemical vapor deposition process, plasma chemical vapor deposition process, reactive sputtering process and light induced chemical vapor deposition process can be selectively employed. and among these processes, the plasma chemical vapor deposition process is the most appropriate. for instance, in the case of forming such layer constituted with a poly--si(h,x) series material by means of plasma chemical vapor deposition (commonly abbreviated to "plasma cvd"), the layer forming operation is practiced while maintaining the substrate at a temperature from 400.degree. to 450.degree. c. in a deposition chamber. in an alternative process, firstly, an amorphous-like film is formed on the substrate being maintained at about 250.degree. c. in a deposition chamber by means of plasma cvd, and secondly the resultant film is annealed by heating the substrate at a temperature of 400.degree. to 450.degree. c. for about 20 minutes or by irradiating laser beam onto the substrate for about 20 minutes to thereby form said layer. photoconductive layer 102 the photoconductive layer in the light receiving member according to this invention is constituted with an a--si(h,x) material or a germanium(ge) or tin(sn) containing a--si(h,x) material [hereinafter referred to as "a--si(ge,sn) (h,x)"]. the photoconductive layer 102 may contain the group iii element or the group v element respectively having a relevant function to control the conductivity of the photoconductive layer, whereby the photosensitivity of the layer can be improved. as the group iii element or the group v element to be incorporated in the photoconductive layer 102, it is possible to use the same element as incorporated into the charge injection inhibition layer 104. it is also possible to use such element having an opposite polarity to that of the element to be incorporated into the charge injection inhibition layer. and, in the case where the element having the same polarity as that of the element to be incorporated into the charge injection inhibition layer is incorporated into the photoconductive layer 102, the amount may be lesser than that to be incorporated into the charge injection inhibition layer. specifically, the group iii element can include b (boron), al (aluminum), ga (gallium), in (indium) and ti (thallium), b and ga being particularly preferred. the group v element can include, for example, p (phosphor), as (arsenic), sb (antimony) and bi (bismuth), p and sb being particularly preferred. the amount of the group iii element or the group v element to be incorporated in the photoconductive layer 102 is preferably 1.times.10.sup.-3 to 1.times.10.sup.3 atomic ppm, more preferably, 5.times.10.sup.-2 to 5.times.10.sup.2 atomic ppm, and most preferably, 1.times.10.sup.-1 to 2.times.10.sup.2 atomic ppm. the halogen atoms(x) to be incorporated in the layer in case where necessary can include fluorine, chlorine, bromine and iodine. and among these halogen atoms, fluorine and chlorine are particularly preferred. the amount of the hydrogen atoms(h), the amount of the halogen atoms(x) or the sum of the amounts for the hydrogen atoms and the haogen atoms(h+x) to be incorporate in the photoconductive layer is preferably 1 to 4.times.10 atomic %, more preferably, 5 to 3.times.10 atomic %. further, in order to improve the quality of the photoconductor layer and to increase it dark resistance, at least one kind atom selected from oxygen atom, carbon atom and nitrogen atom can be incorporated in the photoconductive layer. the amount of these atoms to be incorporated in the photoconductive layer is preferably 1.times.10.sup.-3 to 50 atomic ppm, more preferably 2.times.10.sup.-3 to 40 atomic ppm, and, most preferably, 3.times.10.sup.-3 to 30 atomic ppm. the sensitivity of the photoconductive layer 102 in the light receiving member of this invention against long wavelength light such as laser beam can be further improved by incorporating germanium atom(ge) or/and tin atom(sn) thereinto. the amount of the germanium atom or/and the tin atoms in that case is preferred to be in the range of 1 to 9.5.times.10.sup.5 atomic ppm. the thickness of the photoconductive layer 102 is an important factor in order to effectively attain the object of this invention. the thickness of the photoconductive layer is, therefore, necessary to be carefully determined having due regards so that the resulting light receiving member becomes accompanied with desitred characteristics. in view of the above, the thickness of the photoconductive layer 102 is preferably 3 to 100 .mu.m, more preferably 5 to 80 .mu.m, and most preferably 7 to 50 .mu.m. surface layer 103 the surface layer 103 in the light receiving member of this invention has a free surface 107 and is disposed on the foregoing photoconductive layer 102. and, the surface layer 103 in the light receiving member of this invention serves not only to improve various characteristics commonly required for a light receiving member such as the humidity resistance, deterioration resistance upon repeating use, breakdown voltage resistance, use-environmental characteristics and durability of the light receiving member but also to effectively prevent electric charges from being injected into the photoconductive layer 102 from the side of fthe free surface 107 at the time when the light receiving layer is engaged in the charging process. the surface layer 103 in the light receiving member of this invention is formed of: (1) a non-monocrystalline material or a polycrystalline material respectively containing tetrahedrally bonded boron nitride [the former will be hereinafter referred to as "non--bn" or "a--bn" and the latter will be hereinafter referred to as "poly--bn"] or (2) a non--bn material containing trihedrally bonded boron nitride and tetrahedrally bonded boron nitride in mingled state, or (3) is constituted with a lower constituent layer 103' formed of a non-bn material containing tetrahdedrally bonded boron nitride and an upper constituent layer 103" containing trihedrally bonded boron nitride and tetrahedrally bonded boron nitride in mingled state. the surface layer 103 in the light receiving member of this invention may contain hydrogen atom(h) or/and halogen atom(x) [hereinafter referred to as "a--bn(h, x)", "poly-bn(h,x)" or "non--bn(h,x)"]. the surface layer 103 in the light receiving member of this invention may contain dopants, either p-type or n-type. in this case, the surface layer further effectively serves to mobilize charges which are moving thereinto after the image exposure to its free surface to thereby prevent the occurrence of the problems relative to image flow and also to residual voltage which is often found on the conventional light receiving member. the p-type dopant can include germanium atom(ge), zinc atom(zn) and a mixture of them (ge+zn). and, the n-type dopant can include silicon atom (si), tin atom (sn) or a mixture of them (si+sn). the amount of such dopant to be contained in the surface layer 103 is preferably less than 1.times.10.sup.3 atomic ppm, more preferably less than 7.times.10.sup.2 atomic ppm, and most preferably 5.times.10.sup.2 atomic ppm. now, the foregoing non--bn(h,x) of which the surface layer 103 is formed can be expressed by th formula: [bx(n.sub.1-x)].sub.1-y :(h,x).sub.y and the ratios of the layer constituents are desired to satisfy the following conditions: (i) in the case of where the surface layer is formed of said non--bn series material containing tetrahedrally bonded boron nitride; with respect to x; preferably, 0.25.ltoreq.x.ltoreq.0.75, more preferably, 0.3.ltoreq.x.ltoreq.0.7, and most preferably, 0.4.ltoreq.x.ltoreq.0.6, and with respect to y; preferably, 0.004.ltoreq.y.ltoreq.0.4, more preferably 0.005.ltoreq.y.ltoreq.0.3 and most preferably 0.01.ltoreq.y.ltoreq.0.2. (ii) in the case where the surface layer is formed of said non--bn series material containing trihedrally bonded boron nitride and tetrahedrally bonded boron nitride in mingled state; with respect to x; preferably, 0.1.ltoreq.x.ltoreq.0.9, more preferably, 0.2.ltoreq.x.ltoreq.0.8, and most preferably, 0.3.ltoreq.x.ltoreq.0.7, and with respect to y; preferably 0.004.ltoreq.y.ltoreq.0.4, more preferably 0.005.ltoreq.y.ltoreq.0.3, and most preferably, 0.01.ltoreq.y.ltoreq.0.2. the thickness of the surface layer 103 in the light receiving member of this invention is appropriately determined depending upon the desired purpose. it is, however, also necessary that the thickness be determined in view of relative and organic relationship in accordance with the amounts of the constituent atoms to be contained in the layer or the characteristics required in the relationship with the thickness of other layer. further, it should be determined also in economical viewpoints such as productivity or mass productivity. in view of the above, the thickness of the surface layer 103 is preferably 3.times.10.sup.-3 to 30 .mu.m, more preferably, 4.times.10.sup.-3 to 20 .mu.m, and, most preferably, 5.times.10.sup.-3 to 10 .mu.m. intermediate layer 108 the intermediate layer 108 in the light receiving member of this invention is to dispose between the photoconductive layer 102 and the surface layer 103 and it principally serves to improve breakdown voltage resistance of the light receiving layer. the intermediate layer 108 is formed of either an a--si(h,x) material or a poly-si(h,x) material respectively containing carbon atom in an amount of preferably 20 to 90 atomic %, more preferably 30 to 85 atomic %, and most preferably, 40 to 80 atomic %. as for the hydrogen atom(h) and halogen atom(x) to be optionally contained in the intermediate layer, the amount of hydrogen atoms or halogen atoms, or the sum of the amount of hydrogen atoms and the amount of halogen atoms is preferably 1 to 7.times.10 atomic %, more preferably 2 to 65 atomic %, and most preferably, 5 to 60 atomic %. the thickness of the intermediate layer 108 is preferably 3.times.10.sup.-2 to 30 .mu.m, more preferably 4.times.10.sup.-2 to 20 .mu.m, and most preferably, 5.times.10.sup.-2 to 10 .mu.m. formation of layers the method of forming the light receiving layer of the light receiving member will be now explained. each layer to constitute the light receiving layer of the light receiving member of this invention can be properly prepared by vacuum deposition method utilizing the discharge phenomena such as glow discharging, reactive sputtering and ion plating processes wherein relevant raw material gases are selectively used. these production methods are properly used selectively depending on the factors such as the manufacturing conditions, the installation cost required, production scale and properties required for the light receiving members to be prepared. the glow discharging method or sputtering method is suitable since the control for the condition upon preparing the light receiving members having desired properties are relatively easy, and hydrogen atoms, halogen atoms and other atoms can be introduced easily together with silicon atoms. the glow discharging method and the sputtering method may be used together in one identical system. formation of surface layer basically when a surface layer composed of non--bh(h,x) is formed by the glow discharging process, a feed gas capable of supplying boron atoms(b), a feed gas capable of supplying nitrogen atoms(n) and an inert gas are introduced, if necessary, together with a feed gas for introducing hydrogen atoms(h) or/and a feed gas for introducing halogen atoms(x) into a deposition chamber the inner pressure of which can be reduced properly, glow discharge is generated in the deposition chamber, and a layer composed of non--bn (h,x) to be the surface layer is formed on a substrate placed in the deposition chamber. and in order to form a surface layer composed of a non--bn(h,x) material containing dopants by the glow discharging process, basically, a feed gas to liberate boron atoms(b), a feed gas to liberate nitrogen atoms(n), either a feed gas to liberate silicon atoms(si) or/and tin atoms (sn) or a feed gas to liberate germanium atoms(ge) or/and zinc atoms(zn), and an inert gas are introduced, if necessary, together with a feed gas to liberate hydrogen atoms(h) or/and a feed gas to liberate halogen atoms(h) into a deposition chamber the inner pressure of which can be reduced properly, glow discharge is generated in the deposition chamber, and a layer composed of a non--bn(h,x) material containing dopants to be the surface layer is formed on a substrate placed in the deposition chamber. the raw material for supplying b can include gaseous or gasifiable compounds such as b.sub.2 h.sub.6, b.sub.4 h.sub.10, b.sub.5 h.sub.9, b.sub.5 h.sub.11, b.sub.6 h.sub.12, bf.sub.3 and bcl.sub.3. the raw material for supplying n can include gaseous or gasifiable compounds such as n.sub.2, nh.sub.3, nf.sub.2 cl, nfcl.sub.2, ncl.sub.3, n.sub.2 f.sub.2, n.sub.2 f.sub.4, nh.sub.2 cl, nhf.sub.2 and nh.sub.2 f. the raw material for supplying si can include gaseous or gasifiable compounds such as sih.sub.4, si.sub.2 h.sub.6, si.sub.3 h.sub.8, si.sub.4 h.sub.10, sif.sub.4 and sicl.sub.4. the raw material for supplying sn can include gaseous or gasifiable compounds such as snh.sub.4, snf.sub.4 and sncl.sub.4. the raw material for supplying ge can include gaseous or gasificable germanium compounds such as geh.sub.4, ge.sub.2 h.sub.6 and gef.sub.4. the raw material for supplying zn can include gaseous or gasifiable zinc compounds such as zn(ch.sub.3).sub.2. the raw material for supplying halogen atoms can include halogen gases such as f.sub.2, cl.sub.2, i.sub.2, br.sub.2 and fcl. the raw material for supplying hydrogen atoms can include gaseous or gasifiable compounds such as hf, hcl, hbr, hi, b.sub.2 h.sub.6, b.sub.4 h.sub.10, nh.sub.3, sih.sub.4, si.sub.2 h.sub.6, snh.sub.4, geh.sub.4 and ge.sub.2 h.sub.6. in the case of forming a layer composed of a non--bn (h,x) material containing tetrahedrally bonded boron nitride by the sputtering process, basically, a bn target is subjected to sputtering with gas plasmas in a gas atmosphere containing a raw material gas for supplying b which is diluted with an inert gas such as ar gas in an appropriate sputtering deposition chamber the inner pressure of which can be reduced properly to thereby form said layer on a substrate placed in said chamber. further, the formation of a layer composed of a dopant containing non--bn(h,x) material containing tetrahedrally bonded boron nitride may be practiced by using a bn target and by introducing a raw material gas for supplying si or/and sn or raw material gas for supplying ge or/and zn together with an inert gas such as ar gas into the above sputtering deposition chamber to form plasma atmosphere and sputtering said bn target with the gas plasmas. in the above case, it is possible to use a zn target or a ge target and to introduce a raw material gas for supplying b and a raw material gas for supplying n together with an inert gas such as ar gas into the above sputtering deposition chamber. the formation of a layer composed of a non--bn(h,x) containing tetrahdedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state by the sputtering process may be practiced by using a bn target and by introducing a raw material gas for supplying n together with an inert gas such as he gas into the foregoing sputtering deposition chamber to form plasma atmosphere and sputtering said bn target. in this case, it is possible to form said layer by using a b target and by introducing a large amount of a raw material gas for supplying n together with said inert gas to form plasma atmosphere and sputtering said b target with gas plasmas. the formation of a layer composed of a dopant containing non--bn(h,x) containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state may be practiced by using a bn target and by introducing a raw material gas for supplying n and a raw material gas for supplying dopants together with an inert gas such as he gas into the foregoing sputtering deposition chamber to form plasma atmosphere and sputtering said bn target with gas plasmas. in this case, it is possible to form said layer by using a b target and introducing a large amount of a raw material gas for supplying n and a raw material gas for supplying dopants together with said inert gas into the foregoing sputtering deposition chamber to form plasma atmosphere and sputtering said b target with gas plasmas. the conditions upon forming the surface layer 103 in the light receiving member of this invention, for example, the temperature of the substrate, the gas pressure in the deposition chamber and the electric discharging power are important factors for obtaining an objective surface layer having desired properties and they are properly selected while considering the functions of the layer to be formed. further, since these layer forming conditions may be varied depending on the kind and the amount of each of the atoms contained in the layer, the conditions have to be determined also taking the kind or the amount of the atoms to be contained into consideration. specifically, in the case of forming a layer composed of a non--bn(h,x) material containing tetrahedrally bonded boron nitride by plasma cvd method using high frequency of 13.56 mhz, the gas pressure in the deposition chamber is preferably 10.sup.-2 to 10 torr, more preferably 5.times.10.sup.-2 to 2 torr, and most preferably, 1.times.10.sup.-1 to 1 torr. the temperature of the substrate is preferably 50.degree. to 700.degree. c., and more preferably, 50.degree. to 400.degree. c. in the case of forming a layer composed of a non--bn(h,x) series material, and 200.degree. to 700.degree. c. in the case of forming a layer compoed of a poly--bn(h,x) series material. as for the electrical discharging power, it is preferably 0.01 to 5w/cm.sup.2, and most preferably, 0.02 to 2w/cm.sup.2. further, as for the flow ratios relative to the raw material gas for supplying b, the raw material gas for supplying n and ar gas, the flow ratio b/n is controlled to be preferably 1/5 to 100/1, and most preferably 1/4 to 80/1, and at the same time, the flow ratio ar/b+n is controlled to be preferably 1/10 to 100/1 and most preferably 1/7 to 80/1. and in the case of forming the above mentioned layer by plasma cvd method using microwave of 2.45 ghz, the gas pressure in the deposition chamber is preferably 1.times.10.sup.-4 to 2 torr, more preferably 5.times.10.sup.-4 to 1.0 torr, and most preferably, 5.times.10.sup.-4 to 0.7 torr. the electrical discharging power is preferably 0.1 to 50 w/cm.sup.2, and most preferably, 0.2 to 30 w/cm.sup.2. in this case, the temperature of the substrate and the flow ratios of the gases used are the same as those in the foregoing case using high frequency. in the case of forming a layer composed of a non--bn (h,x) material containing tetrahedrally bonded boron nitride by the sputtering process, the gas pressure in the deposition chamber is preferably 1.times.10.sup.-4 to 1.0 torr, and most preferably, 5.times.10.sup.-4 to 0.7 torr. the electrical charging power is preferably 0.01 to 10 w/cm.sup.2, and most preferably, 0.05 to 8 w/cm.sup.2. in this case, the temperature of the substrate and the flow ratios of the gases used are the same as those in the foregoing case by plasma cvd method using high frequency. in the case of forming a layer composed of a non--bn (h,x) material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state by plasma cvd method using high frequency of 13.56 mhz, the gas pressure in the deposition chamber is preferably 1.times.10.sup.-2 to 10 torr, more preferably 5.times.10.sup.-2 to 2 torr, and most preferably, 0.1 to 1 torr. the temperature of the substrate is preferably 50.degree. to 700.degree. c., and more preferably, 50.degree. to 400.degree. c. in the case of forming a layer composed of a non--bn(h,x) material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state, and 200.degree. to 700.degree. c. in the case of forming a layer composed of a poly--bn(h,x) containing the above two kinds of boron nitride in mingled state. as for the electrical discharging power, it is preferably 0.05 to 5 w/cm.sup.2, and most preferably, 0.02 to 2 w/cm.sup.2. further, as for the flow ratios relative to the raw material gas for supplying b, the raw material gas for supplying n and he gas, the ratio b/n is controlled to be preferably 1/100 to 5/1, and most preferably, 1/80 to 4/1, and at the same time, the flow ratio he/b+n is controlled to be 1/10 to 0. in the case of forming a layer composed of a non--bn (h,x) material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state by plasma cvd method using microwave of 2.45 ghz, the gas pressure in the deposition chamber is preferably 1.times.10.sup.-4 to 2 torr, more preferably 5.times.10.sup.-4 to 1.0 torr, and most preferably, 5.times.10.sup.-4 to 0.7 torr. the electrical discharging power is preferably 0.1 to 50 w/cm.sup.2, and most preferably 0.2 to 30 w/cm.sup.2. and, in this case, the temperature of the substrate and the flow ratios of the gases used are the same as those in the foregoing case using high frequency. in addition, in the case of forming a layer composed of a non--bn(h,x) material containing tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state by the sputtering process, the gas pressure in the deposition chamber is preferably 1.times.10.sup.-4 to 1.0 torr, and most preferably, 5.times.10.sup.-4 to 0.7 torr. as for the electrical discharging power, it is preferably 0.01 to 10 w/cm.sup.2 and most preferably, 0.05 to 8 w/cm.sup.2. in this case, the temperature of the substrate and the flow ratios of the gases used are the same as those in the case by plasma cvd method using high frequency. formation of other layers basically, when a layer constituted with a--si(h,x) is formed, for example, by the glow discharging process, gaseous starting material capable of supplying silicon atoms(si) is introduced together with gaseous starting material for introducing hydrogen atoms(h) and/or halogen atoms(x) into a deposition chamber the inside pressure of which can be reduced, glow discharge is generated in the deposition chamber, and a layer composed of a--si(h,x) is formed on the surface of a predetermined substrate disposed previously at a predetermined position. the gaseous starting material for supplying si can include gaseous or gasifiable silicon hydrides (silanes) such as sih.sub.4, si.sub.2 h.sub.6, si.sub.4 h.sub.10, etc., sih.sub.4 and si.sub.2 h.sub.6 being particularly preferred in view of the easy layer forming work and the good efficiency for the supply of si. further, various halogen compounds can be mentioned as the gaseous starting material for introducing the halogen atoms and gaseous or gasifiable halogen compounds, for example, gaseous halogen, halides, inter-halogen compunds and halogen-substituted silane derivatives are preferred. specifically, they can include halogen gas such as of fluorine, chlorine, bromine, and iodine; inter-halogen compounds such as brf, clf, clf.sub.3, brf.sub.2, brf.sub.3, if.sub.7, ic1, ibr, etc.; and silicon halides such as sif.sub.4, si.sub.2 h.sub.6, sic.sub.4, and sibr.sub.4. the use of the gaseous or gasifiable silicon halide as described above is particularly advantageous since the layer constituted with halogen atom-containing a--si can be formed with no additional use of the gaseous starting material for supplying si. the gaseous starting material usable for supplying hydrogen atoms can include those gaseous or gasifiable materials, for example, hydrogen gas halides such as hf, hcl, hbr, and hi, silicon hydrides such as sih.sub.4, si.sub.2 h.sub.6, si.sub.3 h.sub.8, and si.sub.4 o.sub.10, or halogen-substituted silicon hydrides such as sih.sub.2 f.sub.2, sih.sub.2 i.sub.2, sih.sub.2 cl.sub.2, sihcl.sub.3, sih.sub.2 br.sub.2, and sihbr.sub.3. the use of these gaseous starting material is advantageous since the content of the hydrogen atoms(h), which are extremely effective in view of the control for the electrical or photoelectronic properties, can be controlled with ease. then, the use of the hydrogen halide or the halogen-substituted silicon hydride as described above is particularly advantageous since the hydrogen atoms(h) are also introduced together with the introduction of the halogen atoms. in the case of forming a layer comprising a--si(h,x) by means of the reactive sputtering process or ion plating process, for example, by the sputtering process, the halogen atoms are introduced by introducing gaseous halogen compounds or halogen atom-containing silicon compounds into a deposition chamber thereby forming a plasma atmosphere with the gas. further, in the case of introducing the hydrogen atoms, the gaseous starting material for introducing the hydrogen atoms, for example, h.sub.2 or gaseous silanes are described above are introduced into the sputtering deposition chamber thereby forming a plasma atmosphere with the gas. for instance, in the case of the reactive sputtering process, a layer comprising a--si(h,x) is formed on the support by using an si target and by introducing a halogen atom-introducing gas and h.sub.2 together with an inert gas such as he or ar as required into a deposition chamber thereby forming a plasma atmosphere and then sputtering the si target. to form the layer of a--sige(h,x) by the glow discharge process, a feed gas to liberate silicon atoms(si), a feed gas to liberate germanium atoms, and a feed gas to liberate hydrogen atoms(h) and/or halogen atoms(x) are introduced into an evacuatable deposition chamber, in which the glow discharge is generated so that a layer of a--sige(h,x) is formed on the properly positioned support. the feed gases to supply silicon atoms, halogen atoms, and hydrogen atoms are the same as those used to form the layer of a--si(h,x) mentioned above. the feed gas to liberate ge includes gaseous or gasifiable germanium halides such as geh.sub.4, ge.sub.2 h.sub.6, ge.sub.3 h.sub.8, ge.sub.4 h.sub.10, ge.sub.5 h.sub.12, ge.sub.6 h.sub.14, ge.sub.7 h.sub.16, ge.sub.8 h.sub.18, and ge.sub.9 h.sub.20, with geh.sub.4, ge.sub.2 h.sub.6, and ge.sub.3 h.sub.8, being preferable on account of their ease of handling and the effective liberation of germanium atoms. to form the layer of a--sige(h,x) by the sputtering process, two targets (a silicon target and a germanium target) or a single target composed of silicon and germanium is subjected to sputtering in a desired gas atmosphere. to form the layer of a--sige(h,x) by the ion-plating process, the vapors of silicon and germanium are allowed to pass through a desired gas plasma atmosphere. the silicon vapor is produced by heating polycrystal silicon or single crystal silicon held in a boat, and the germanium vapor is produced by heating polycrystal germanium or single crystal germanium held in a boat. the heating is accomplished by resistance heating or electron beam method (e.b. method). in either case where the sputtering process or the ion-plating process is employed, the layer may be incorporated with halogen atoms by introducing one of the above-mentioned gaseous halides or halogen-containing silicon compounds into the deposition chamber in which a plasma atmosphere of the gas is produced. in the case where the layer is incorporated with hydrogen atoms, a feed gas to liberate hydrogen is introduced into the deposition chamber in which a plasma atmosphere of the gas is produced. the feed gas may be gaseous hydrogen, silanes, and/or germanium hydrides. the feed gas to liberate halogen atoms includes the above-mentioned halogen-containing silicon compounds. other examples of the feed gas include hydrogen halides such as hf, hcl, hbr and hi; halogen-substituted silanes such as sih.sub.2 f.sub.2, sih.sub.2 i.sub.2, sih.sub.2 cl.sub.2, sihcl.sub.3, sih.sub.2 br.sub.2, and sihbr.sub.3 ; germanium hydride halide such as gehf.sub.3, geh.sub.2 f.sub.2, geh.sub.3 f, gehcl.sub.3, geh.sub.2 cl.sub.2, geh.sub.3 cl, gehbr.sub.3, geh.sub.2 br.sub.2, geh.sub.3 br, gehi.sub.3, geh.sub.2 i.sub.2, and geh.sub.3 i; and germanium halides such as gef.sub.4, gecl.sub.4, gebr.sub.4, gei.sub.4, gef.sub.2, gecl.sub.2, gebr.sub.2, and gei.sub.2. they are in the gaseous form or gasifiable substances. to form the light receiving layer composed of amorphous silicon containing tin atoms (hereinafter referred to as a--sisn(h,x)) by the glow-discharge process, sputtering process, or ion-plating process, a starting material (feed gas) to release tin atoms(sn) is used in place of the starting material to release germanium atoms which is used to form the layer composed of a--sige(h,x) as mentioned above. the process is properly controlled so that the layer contains a desired amount of tin atoms. examples of the feed gas to release tin atoms(sn) include tin hydride(snh.sub.4) and tin halides (such as snf.sub.2, snf.sub.4, sncl.sub.2, sncl.sub.4, snbr.sub.2, snbr.sub.4, sni.sub.2, and sni.sub.4) which are in the gaseous form or gasifiable. tin halides are preferable because they form on the substrate a layer of a--si containing halogen atoms. among tin halides, sncl.sub.4, is particularly preferable because of its ease of handling and its efficient tin supply. in the case where solid sncl.sub.4 is used as a starting material to supply tin atoms(sn), it should preferably be gasified by blowing (bubbling) an inert gas (e.g., ar and he) into it while heating. the gas thus generated is introduced, at a desired pressure, into the evacuated deposition chamber. the layer may be formed from an amorphous material a--si(h,x) or a--si(ge,sn)(h,x) which further contains the group iii atoms or group v atoms, nitrogen atoms, oxygen atoms, or carbon atoms, by the glow-discharge process, sputtering process, or ion-plating process. in this case, the above-mentioned starting material for a--si(h,x) or a--si(ge,sn)(h,x) is used in combination with the starting materials to introduce the group iii atoms or group v atoms, nitrogen atoms, oxygen atoms, or carbon atoms. the supply of the starting materials should be properly controlled so that the layer contains a desired amount of the necessary atoms. if, for example, the layer is to be formed by the glow-discharge process from a--si(h,x) containing atoms (o,c,n) or from a--si(ge,sn)(h,x) containing atoms (o,c,n), the starting material to form the layer of a--si(h,x) or a--si(ge,sn)(h,x) should be combined with the starting material used to introduce atoms (o,c,n). the supply of these starting materials should be properly controlled so that the layer contains a desired amount of the necessary atoms. the starting material to introduce the atoms(o,c,n) may be any gaseous substance or gasifiable substance composed of any of oxygen, carbon, and nitrogen. examples of the starting materials used to introduce oxygen atoms(o) include oxygen(o.sub.2), ozone(o.sub.3), nitrogen dioxide(no.sub.2), nitrous oxide(n.sub.2 o), dinitrogen trioxide(n.sub.2 o.sub.3), dinitrogen tetroxide(n.sub.2 o.sub.4), dinitrogen pentoxide(n.sub.2 o.sub.5), and nitrogen trioxide(no.sub.3). additional examples include lower siloxanes such as disiloxane(h.sub.3 siosih.sub.3) and trisiloxane(h.sub.3 siosih.sub.2 osih.sub.3) which are composed of silicon atoms(si), oxygen atoms(o), and hydrogen atoms(h). examples of the starting materials used to introduce carbon atoms include saturated hydrocarbons having 1 to 5 carbon atoms such as methane(ch.sub.4), ethane (c.sub.2 h.sub.6), propane(c.sub.3 h.sub.8), n-butane(n--c.sub.4 h.sub.10), and pentane(c.sub.5 h.sub.12); ethylenic hydrocarbons having 2 to 5 carbon atoms such as ethylene(c.sub.2 h.sub.4), propylene(c.sub.3 h.sub.6), butene--1(c.sub.4 h.sub.8), butene-2 (c.sub.4 h.sub.8), isobutylene(c.sub.4 h.sub.8), and pentene(c.sub.5 h.sub.10); and acetylenic hydrocarbons having 2 to 4 carbon atoms such as acetylene (c.sub.2 h.sub.2), methyl acetylene(c.sub.3 h.sub.4), and butine(c.sub.4 h.sub.6). examples of the starting materials used to introduce nitrogen atoms include nitrogen(n.sub.2), ammonia(nh.sub.3), hydrazine(h.sub.2 nnh.sub.2), hydrogen azide(hn.sub.3), ammonium azide(nh.sub.4 n.sub.3), nitrogen trifluoride(f.sub.3 n), and nitrogen tetrafluoride(f.sub.4 n). in the case of using the glow discharging process for forming the layer or layer region containing oxygen atoms, starting material for introducing the oxygen atoms is added to those selected from the starting materials as desired for forming the light receiving layer. as the starting material for introducing the oxygen atoms, most of those gaseous or gasifiable materials can be used that comprise at least oxygen atoms as the constituent atoms. for instance, it is possible to use a mixture of gaseous starting material comprising silicon atoms(si) as the constituent atoms, gaseous starting material comprising oxygen atoms(o) as the constituent atom and, as required, gaseous starting material comprising hydrogen atoms(h) and/or halogen atoms(x) as the constituent atoms in a desired mixing ratio, a mixture of gaseous starting material comprising silicon atoms(si) as the constituent atoms and gaseous starting material comprising oxygen atoms(o) and hydrogen atoms(h) as the constituent atoms in a desired mixing ratio, or a mixture of gaseous starting material comprising silicon atoms(si) as the constituent atoms and gaseous starting material comprising silicon atoms(si), oxygen atoms(o) and hydrogen atoms(h) as the constituent atoms. further, it is also possible to use a mixture of gaseous starting material comprising silicon atoms (si) and hydrogen atoms (h) as the constituent atoms and gaseous starting material comprising oxygen atoms (o) as the constituent atoms. specifically, there can be mentioned, for example, oxygen (o.sub.2), ozone (o.sub.2), nitrogen monoxide (no), nitrogen dioxide (no.sub.2), dinitrogen oxide (n.sub.2 o), dinitrogen trioxide (n.sub.2 o.sub.3), dinitrogen tetraoxide (n.sub.2 o.sub.4), dinitrogen pentoxide (n.sub.2 o.sub.5), nitrogen trioxide (no.sub.3), lower siloxanes comprising silicon atoms (si), oxygen atoms (o) and hydrogen atoms (h) as the constituent atoms, for example, disiloxane (h.sub.3 siosih.sub.3) and trisiloxane (h.sub.3 siosih.sub.2 osih.sub.3), etc. in the case of forming the layer or layer region containing oxygen atoms by way of the sputtering process, it may be carried out by sputtering a single crystal or polycrystalline si wafer or sio.sub.2 wafer, or a wafer containing si and sio.sub.2 in admixture is used as a target and sputtered in various gas atmospheres. for instance, in the case of using the si wafer as the target, a gaseous starting material for introducing oxygen atoms and, optionally, hydrogen atoms and/or halogen atoms is diluted as required with a dilution gas, introduced into a sputtering deposition chamber, gas plasmas with these gases are formed and the si wafter is sputtered. alternatively, sputtering may be carried out in the atmosphere of a dilution gas or in a gas atmosphere containing at least hydrogen atoms (h) and/or halogen atoms (x) as constituent atoms as a sputtering gas by using individually si and sio.sub.2 targets or a single si and sio.sub.2 mixed target. as the gaseous starting material for introducing the oxygen atoms, the gaseous starting material for introducing the oxygen atoms shown in the examples for the glow discharging process as described above can be used as the effective gas also in the sputtering. the light receiving layer containing carbon atoms, for example, may be formed through the glow discharging process, by using a mixture of gaseous starting material comprising silicon atoms (si) as the constituent atoms, gaseous starting material comprising carbon atoms (c) as the constituent atoms and, optionally, gaseous starting material comprising hydrogen atoms (h) and/or halogen atoms (x) as the constituent atoms in a desired mixing ratio, a mixture of gaseous starting material comprising silicon atoms (si) as the constituent atoms and gaseous starting material comprising carbon atoms (c) and hydrogen atoms (h) as the constituent atoms also in a desired mixing ratio, a mixture of gaseous starting material comprising silicon atoms (si) as the constituent atoms and gaseous starting material comprising silicon atoms (si), carbon atoms (c) and hydrogen atoms (h) as the constituent atoms, or a mixture of gaseous starting material comprising silicon atoms (si) and hydrogen atoms (h) as the constituent atoms and gaseous starting material comprising carbon atoms (c) as constituent atoms. those gaseous starting materials that are effectively usable herein can include gaseous silicon hydrides comprising c and h as the constituent atoms, such as silanes, for example, sih.sub.4, si.sub.2 h.sub.6, si.sub.3 h.sub.8 and si.sub.4 h.sub.10, as well as those comprising c and h as the constituent atoms, for example, saturated hydrocarbons of 1 to 4 carbon atoms, ethylenic hydrocarbons of 2 to 4 carbon atoms and acetylenic hydrocarbons of 2 to 3 carbon atoms. specifically, the saturated hydrocarbons can include methane (ch.sub.4), ethane (c.sub.2 h.sub.6), propane (c.sub.3 h.sub.8), n-butane (n--c.sub.4 h.sub.10) and pentane (c.sub.5 h.sub.12), the ethylenic hydrocarbons can include ethylene (c.sub.2 h.sub.4), propylene (c.sub.3 h.sub.6), butene-1 (c.sub.4 h.sub.8), butene-2 (c.sub.4 h.sub.8), isobutylene (c.sub.4 h.sub.8) and pentene (c.sub.5 h.sub.10) and the acetylenic hydrocarbons can include acetylene (c.sub.2 h.sub.2), methylacetylene (c.sub.3 h.sub.4) and butine (c.sub.4 h.sub.6). the gaseous starting material comprising si, c and h as the constituent atoms can include silicided alkyls, for example, si(ch.sub.3).sub.4 and si(c.sub.2 h.sub.5).sub.4. in addition to these gaseous starting materials, h.sub.2 can of course be used as the gaseous starting material for introducing h. the layer or layer region constituted with a--sic(h,x) may be formed through the sputtering process by using a single crystal or polycrystalline si wafer, a c (graphite) wafer or a wafer containing a mixture of si and c as a target and sputtering them in a desired gas atmosphere. in the case of using, for example a si wafer as a target, gaseous starting material for introducing carbon atoms, and hydrogen atoms and/or halogen atoms is introduced while being optionally diluted with a dilution gas such as ar and he into a sputtering deposition chamber thereby forming gas plasmas with these gases and sputtering the si wafer. alternatively, in the case of using si and c as individual targets or as a single target comprising si and c in admixture, gaseous starting material for introducing hydrogen atoms and/or halogen atoms as the sputtering gas is optionally diluted with a dilution gas, introduced into a sputtering deposition chamber thereby forming gas plasmas and sputtering is carried out. as the gaseous starting material for introducing each of the atoms used in the sputtering process, those gaseous starting materials used in the glow discharging process as described above may be used as they are. in the case of using the glow discharging process for forming the layer or the layer region containing the nitrogen atoms, starting material for introducing nitrogen atoms is added to the material selected as required from the starting materials for forming the light receiving layer as described above. as the starting material for introducing the nitrogen atoms, most of gaseous or gasifiable materials can be used that comprise at least nitrogen atoms as the constituent atoms. for instance, it is possible to use a mixture of gaseous starting material comprising silicon atoms (si) as the constituent atoms, gaseous starting material comprising nitrogen atoms (n) as the constituent atoms and, optionally, gaseous starting material comprising hydrogen atoms (h) and/or halogen atoms (x) as the constituent atoms mixed in a desired mixing ratio, or a mixture of starting gaseous material comprising silicon atoms (si) as the constituent atoms and gaseous starting material comprising nitrogen atoms (n) and hydrogen atoms (h) as the constituent atoms also in a desired mixing ratio. alternatively, it is also possible to use a mixture of gaseous starting material comprising nitrogen atoms (n) as the constituent atoms gaseous starting material comprising silicon atoms (si) and hydrogen atoms (h) as the constituent atoms. the starting material that can be used effectively as the gaseous starting material for introducing the nitrogen atoms (n) used upon forming the layer or layer region containing nitrogen atoms can include gaseous or gasifiable nitrogen, nitrides and nitrogen compounds such as azide compounds comprising n as the constituent atoms or n and h as the constituent atoms, for example, nitrogen (n.sub.2), ammonia (nh.sub.3), hydrazine (h.sub.2 nnh.sub.2), hydrogen azide (hn.sub.3) and ammonium azide (nh.sub.4 n.sub.3). in addition, nitrogen halide compounds such as nitrogen trifluoride (f.sub.3 n) and nitrogen tetrafluoride (f.sub.4 n.sub.2) can also be mentioned in that they can also introduce halogen atoms (x) in addition to the introduction of nitrogen atoms (n). the layer or layer region containing the nitrogen atoms may be formed through the sputtering process by using a single crystal or polycrystalline si wafer or si.sub.3 n.sub.4 wafer or a wafer containing si and si.sub.3 n.sub.4 in admixture as a target and sputtering them in various gas atmospheres. in the case of using a si wafer as a target, for instance, gaseous starting material for introducing nitrogen atoms and, as required, hydrogen atoms and/or halogen atoms is diluted optionally with a dilution gas, introduced into a sputtering deposition chamber to form gas plasmas with these gases and the si wafer is sputtered. alternatively, si and si.sub.3 n.sub.4 may be used as individual targets or as a single target comprising si and si.sub.3 n.sub.4 in admixture and then sputtered in the atmosphere of a dilution gas or in a gaseous atmosphere containing at least hydrogen atoms (h) and/or halogen atoms (x) as the constituent atoms as for the sputtering gas. as the gaseous starting material for introducing nitrogen atoms, those gaseous starting materials for introducing the nitrogen atoms described previously shown in the example of the glow discharging can be used as the effective gas also in the case of the sputtering. in addition, in the case of forming a layer or layer region constituted with a--si(h,x) containing the group iii or group v atoms by using the glow discharging, sputtering or ion plating process, the starting material for introducing the group iii or group v atoms are used together with the starting material for forming a--si(h,x) upon forming the layer constituted with a--si(h,x) as described above and they are incorporated while controlling the amount of them into the layer to be formed. referring specifically to the boron atom introducing materials as the starting material for introducing the group iii atoms, they can include boron hydrides such as b.sub.2 h.sub.6, b.sub.4 h.sub.10, b.sub.5 h.sub.9, b.sub.5 h.sub.11, b.sub.6 h.sub.10, b.sub.6 h.sub.12 and b.sub.6 h.sub.14 and boron halides such as bf.sub.3, bcl.sub.3 and bbr.sub.3. in addition, alcl.sub.3, cacl.sub.3, ga(ch.sub.3).sub.2, incl.sub.3, tlcl.sub.3 and the like can also be mentioned. referring to the starting material for introducing the group v atoms and, specifically to, the phosphor atom introducing materials, they can include, for example, phosphor hydrides such as ph.sub.3 and p.sub.2 h.sub.6 and phosphor halide such as ph.sub.4 i, pf.sub.3, pf.sub.5, pcl.sub.3, pcl.sub.5, pbr.sub.3, pbr.sub.5 and pi.sub.3. in addition, ash.sub.3, asf.sub.5, ascl.sub.3, asbr.sub.3, asf.sub.3, sbh.sub.3, sbf.sub.3, sbf.sub.5, sbcl.sub.3, sbcl.sub.5, bih.sub.3, sicl.sub.3 and bibr.sub.3 can also be mentioned to as the effective starting material for introducing the group v atoms. in the case of forming the respective constituent layers other than the surface layer of the light receiving layer in the light receiving member of this invention by means of the glow discharging, reactive sputtering or ion plating process, the amount of each of the layer constituent atoms to be contained in a layer to be formed is controlled by appropriately regulating the flow rate of each of the raw material gases and the flow ratio among the raw material gases to be introduced into the deposition chamber. the conditions upon forming each of such layers, for example, the temperature of the substrate, the gas pressure in the deposition chamber and the electrical discharging power are important factors for obtaining a light receiving member having desired properties and they are properly selected while considering the functions of the layer to be formed. further, since these layer forming conditions may be varied depending on the kind and the amount of each of the atoms contained in the layer, the conditions have to be determined also taking the kind or the amount of the atoms to be contained into consideration. specifically, in the case of forming a layer composed of an a--si(h,x) material containing nitrogen atom, oxygen atom, carbon atom, etc., the temperature of the substrate is preferably 50.degree. to 350.degree. c., and more preferably, 50.degree. to 250.degree. c. the gas pressure in the deposition chamber is preferably 0.01 to 1 torr, and most preferably, 0.1 to 0.5 torr. and, the electrical discharging power is preferably 0.005 to 50 w/cm.sup.2, more preferably 0.01 to 30 w/cm.sup.2, and most preferably, 0.01 to 20 w/cm.sup.2. and in the case of forming a layer composed of either an a--sige(h,x) material or an a--sige(m,x) containing the group iii atom or the group v atom, the temperature of the substrate is preferably 50.degree. to 350.degree. c., more preferably, 50.degree. to 300.degree. c., and most preferably, 100.degree. to 300.degree. c. the gas pressure in the deposition chamber is preferably 0.01 to 5 torr, more preferably 0.01 to 3 torr, and most preferably, 0.01 to 1 torr. and, the electrical discharging power is preferably 0.005 to 50 w/cm.sup.2, more preferably 0.01 to 30 w/cm.sup.2, and most preferably, 0.01 to 20 w/cm.sup.2. however, the actual conditions for forming the layer such as temperature of the substrate, discharging power and the gas pressure in the deposition chamber can not usually the determined with ease independent of each other. accordingly, the conditions optimal to the layer formation are desirably determined based on relative and organic relationships for forming the amorphous material layer having desired properties. description of the preferred embodiments the invention will be described more specifically while referring to examples 1 through 312, but the invention is not intended to limit the scope only to these examples. in each of the examples, the light receiving layer was formed using the fabrication apparatus shown in fig. 2 in accordance with the glow discharging process. in the apparatus shown in fig. 2, gas reservoirs 202, 203, 204, 205, 206, 241 and 247 are charged with raw material gases for forming the respective layers of the light receiving member of this invention, that is, for instance, sih.sub.4 gas (99.999% purity) in the reservoir 203, b.sub.2 h.sub.6 gas diluted with h.sub.2 gas (99.999% purity, hereinafter referred to as "b.sub.2 h.sub.6 /h.sub.2 gas" in the reservoir 203, no gas (99.5% purity) in the reservoir 204, b.sub.2 h.sub.6 gas diluted with ar gas (99.999% purity, hereinafter referred to as "b.sub.2 h.sub.6 /ar gas") in the reservoir 205, b.sub.2 h.sub.6 gas diluted with he gas (99.999% purity, hereinafter referred to as "b.sub.2 h.sub.6 /he gas") in the reservoir 206, sih.sub.4 gas diluted with he gas (99.999% purity, hereinafter referred to as "sih.sub.4 /he gas") in the reservoir 241 and nh.sub.3 gas (99.999% purity) in the reservoir 247. in the case for introducing halogen atoms (x) into a layer, the reservoir for sih.sub.4 is replaced by another reservoir for sif.sub.4 gas for instance. prior to the entrance of these gases into a deposition chamber 201, it is confirmed that valves for the reservoirs 202 through 206, 241 and 247 and a leak valve 235 are closed and that exit valves 217 through 221, 244 and 250, and sub-valves 232 and 233 are opened. then, a main valve 234 is at first opened to evacuate the inside of the deposition chamber 201 and gas pipings. then, upon observing that the reading on the vacuum gauge 236 became about 5.times.10.sup.-6 torr, the sub-valves 232 and 233 and the exit valves 217 through 221, 244 and 250. now, reference is made to an example in the case of forming a light receiving layer on an al cylinder as a substrate 237. sih.sub.4 gas from the reservoir 202, b.sub.2 h.sub.6 /h.sub.2 gas from the reservoir 203 and no gas from the reservoir 204 are caused to flow into the mass flow controllers 207, 208 and 209 respectively by opening the valves 222, 223 and 224, controlling the pressure of each of the exit pressure gauges 227, 228 and 229 to 1 kg/cm.sup.2. subsequently, the exit valves 217, 218 and 219, and the sub-valve are gradually opened to enter the raw material gases into the deposition chamber 201. in this case, the exit valves 217, 218 and 219 are adjusted so as to a desired value for the ratio among the sih.sub.4 gas, b.sub.2 h.sub.6 /h.sub.2 gas and the no gas. the sih.sub.4 gas flow rate, the b.sub.2 h.sub.6 /h.sub.2 gas flow rate and the no gas flow rate, and the opening of the main valve 234 is adjusted while observing the reading on the vacuum gauge 236 so as to obtain a desired value for the pressure inside the deposition chamber 201. then, after confirming that the temperature of the al cylinder 237' on the substrate holder 237 has been set by a heater 238 within a range from 50.degree. to 350.degree. c., a power source 240 is set to a predetermined electrical power to cause glow discharging in the deposition chamber 201 while controlling the above gas flow rates to thereby form a layer to be the first layer on the al cylinder 237'. in the above case, it is possible to further improve the film forming speed by using appropriately selected raw material gases. for instance, in the case where si.sub.2 f.sub.6 gas is used in stead of the sih.sub.4 gas, the film forming speed will be raised by some holds in comparison with the above case. in order to form a layer to be the second layer on the already formed first layer, closing the exit valves 217 through 221, 244 and 247 opening the subvalves 232 and 233 and entirely opening the main valve 234 to evacuate the inside of the deposition chamber 201 and the gas pipings to be a high vacuum, b.sub.2 h.sub.6 /ar gas, b.sub.2 h.sub.6 /he gas, nh.sub.3 gas, an appropriate dopant imparting raw material gas and sih.sub.4 /he gas are fed into the deposition chamber 201 by operating the related valves in the same was as in the case of forming the first layer and the power source 240 is set to a predetermined electric power to cause glow discharging in the deposition chamber while controlling the flow rates of the raw material gases to thereby form the second layer. in the case where the amount of hydrogen atom to be contained in the second layer is desired to be changed, it can be carried out by purposely adding h.sub.2 gas to an appropiate raw material gas and by varying its flow rate as desired. further, in the case where hydrogen atom is desired to be introduced into the second layer, it can be carried out by feeding nf.sub.3 gas together with an appropiate raw material gas into the deposition chamber 201. all of the exit valves other than those required for upon forming the respective layers are of course closed. further, upon forming the respective layers, the inside of the system is once evacuated to a high vacuum degree as required by closing the exit valves 217 through 221, 244 and 250 while opening the sub-valves 232 and 233 and fully opening the main valve 234 for avoiding that the gases having been used for forming the previous layer are left in the deposition chamber 201 and in the gas pipeways from the exit valves 217 through 221, 244 and 250 to the inside of the reaction chamber 201. further, during the film formation process for the respective layers, the substrate 237' is rotated at a predetermined rotation speed by operating motor 239 in order to attain the uniformness fo the layer to be formed. example 1 a light receiving member for use in electrophotography having a light receiving layer disposed on an al cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 1 using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer on an aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, deterioration on photosensitivity and increase of defective images after 1,500 thousand times repeated shots were respectively examined. further, the situation of an image flow on the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further, in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 2. as table 2 illustrates, superiorities in every evaluation item of the initial electrification efficiency (initial charging efficiency), defective image, surface abrasion, breakdown voltage and abrasion resistance for the drum were acknowledged. as for the samples, the cordination number of boron nitride contained therein was examined in accordance with exafs (extended x-ray absorption fine structure ). as a result, it was found that tetrahedrally bonded boron nitrides were contained therein. example 2 the procedures of example 1 were repeated under the conditions shown in table 3 wherein h.sub.2 gas is additionally used in the formation of a surface layer to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 1. the results obtained were as shown in table 4. and as a result of examining a cordination number of boron nitride contained in the samples, it was aknowledged that tetrahedrally bonded boron nitrides were contained therein. example 3 the procedures of example 1 were repeated under the same conditions as shown in the foregoing table 1, except that the vias voltage of the aluminum cylinder was controlled to -150v, to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 1. the results obtained were as shown in table 5. as table 5 illustrates, desirable results as those in example 1 were acknowledged. as for the boron nitrides contained in the surface layer, it was acknowledged that they were tetrahedrally bonded boron nitrides. example 4 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an aluminum cylinder was prepared under the conditions shown in table 6 and following the procedures of example 1. the resultant drum was evaluated by the same manners as in example 1. the results obtained were as shown in table 7. as table 7 illustrates, superiorities in respective evaluation items were acknowledged for the drum. example 5 an aluminum cylinder was subjected to anodic oxidation to form an aluminum oxide (al.sub.2 o.sub.3 ) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 8 following the procedures of example 1 the resultant drum was evaluated by the same manners as in example 1. the results obtained were as shown in table 9. as table 9 illustrates, superiorities in the respective evaluation items were acknowledged. example 6 a drum having an ir absorptive layer, a photoconductive layer and a surface laywr was prepared under the conditions shown in table 10 and following the procedures of example 1. the resultant drum was evoluted by the same manners as in example 1. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelengths as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 11. as table 11 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that any infringe pattern did not appear on an image to be made. example 7 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 12 and following the procedures of example 1. the resultant drum was evaluated by the same manners as in example 1. the results obtained were as shown in table 13. as table 13 illustrates, superiorities in the respective evaluation items were acknowledged. example 8 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 14 and following the procedures of example 1. the resultant drum was evaluated in the same way as in example 6. the results obtained were as shown in table 15. as table 15 illustrates, superiorities in the respective evaluation items were acknowledged. example 9 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 16 and following the procedures of example 1. the resultant drum was evaluated in the same way as in example 1. the results obtained were as shown in table 17. as table 17 illustrates, superiorities in the respective evaluation items were acknowledged. example 10 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 18 and following the procedures of example 1. the resultant drum was evaluated in the same way as in example 6. the results obtained were as shown in table 19. as table 19 illustrates, superiorities in the respective evaluation items were acknowledged. example 11 the procedures of example 1 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 20, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 12 the procedures of example 2 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 21,to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 13 the procedures of example 3 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 22, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 14 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 23, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 15 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 26. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 16 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 28, to thereby prepare multiple drums as shown in table 29. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 17 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 30, to thereby prepare multiple drums as shown in table 31. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 18 the procedures of example 5 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 19 the procedures of example 5 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 28, to thereby prepare multiple drums as shown in table 33. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 20 the procedures of example 5 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 30, to thereby prepare multiple drums as shown in table 34. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 21 the procedures of example 6 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 37. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 22 the procedures of example 6 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 39. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 23 the procedures of example 6 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 28, to thereby prepare multiple drums as shown in table 40. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 24 the procedures of example 6 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 30, to thereby prepare multiple drums as shown in table 41. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 25 the procedures of example 7 were repeated, except that the contact layer forming conditions were changed as shown in table 42, to thereby prepare multiple drums as shown in table 43. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 26 the procedures of example 7 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 45. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 27 the procedures of example 7 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 28, to thereby prepare multiple drums as shown in table 46. the resultant drums were evluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 28 the procedures of example 4 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 30, to thereby prepare multiple drums as shown in table 29. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 29 the procedures of example 8 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 48. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 30 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown respectively in table 35 and table 38, to thereby prepare multiple drums as shown in table 50. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 31 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 28, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 52. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 32 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 30, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 53. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 33 the procedures of example 9 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 55. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 34 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 58. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 35 the procedures of example 9 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 28, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 59. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 36 the procedures of example 9 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 30, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 60. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 37 the procedures of example 10 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 62. the resultant drums wre evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 38 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 65. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 39 the procedures of example 10 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 28, to thereby prepare multiple drums as shown in table 67. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 40 the procedures of example 10 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 30, to thereby prepare multiple drums as shown in table 68. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 41 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 70, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 71. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 42 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 70, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 73. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 43 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 28, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 74. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 44 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 28, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 75. the resultant drums wre evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 45 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 30, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 76. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 46 the procedures of example 8 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 30, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 77. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 47 the procedures of example 4 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 79, to thereby prepare multiple drums as shown in table 79. the resultant drums were evaluated in the same way as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 48 the procedures of example 8 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 81, to thereby prepare multiple drums as shown in table 81. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 49 the procedures of example 10 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions wre changed as shown in table 83, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 6. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 50 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 84 and following the procedures of example 1. the resultant drum was evaluated in the same way as in example 1, superiorities in the respective evaluation items were acknowledged. example 51 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 1. the resulting drums were evaluated with the same procedures as in example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 52 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and of a cross section pattern of table 86 were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 1. the resulting drums were evaluated with the same procedures of example 1. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 53 a light receiving member for use in electrophotography having a light receiving layer disposed on al cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 87 using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer on an aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, the situation of surface abrasion and increase of defective image after 1,500 thousand times repeated shots were respecting examined. then, the situation of an image flow on the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. further, the situation of superiority or inferiority in the cleaning property of the drum in accordance with the degree of background fogginess appearing on a blank image was examined by purposely replacing the original cleaning blade by another cleaning blade having a worn edge. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 88. as table 88 illustrates, superiorities in the respective evaluation items, particularly of the items relative to defective image, image flow and cleaning property for the drum were acknowledged. as for the samples, the cordination number of boron nitride contained therein was examined in accordance with exafs(extended x-ray absorption fine structure). as a result, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state. then, as for the sample on the si-monocrystal wafer, the residual stress was observed by making stripes of .quadrature./mm in checker form on its surface and by peeling off the adhesive tape adhered thereon. as a result, it was found that the sample excels in the residual stress. example 54 the procedures of example 53 were repeated under the conditions shown in table 89 wherein h.sub.2 gas is additionally used in the formation of a surface layer to therby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 53. the results obtained were as shown in table 90. as table 90 illustrates, superiorities in the respective evaluation items were acknowleged. and, as a result of examining a cordination number of boron nitride contained in the samples, it was found that there are contained tetrahedrally bonded boron nitride and trihedrelly bonded boron nitridde in mingled state. example 55 the procedures of example 53 were repeated under the same conditions as shown in the foregoing table 87, except that the vias voltage of the aluminum cylinder was controlled to +100 v, to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 53. the results obtained were shown in table 91. as table 91 illustrates, desirable results as those in example 53 were acknowledged. as for the situations of tetrahedrally bonded boron nitride and trihedrally bonded boron nitride and trihedrally bonded boron nitride in the samples, it was found that both of them are contained in mingled state. example 56 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an alminum cylinder was prepared under the conditions shown in table 92 and following the procedures of example 53. the resultant drum was evaluated by the same manners as in example 53. the results obtained were as shown in table 93. as table 93 illustrates, superiorities in respective evaluation items were acknowledged for the drum. example 57 an alminum cylinder was subjected to anodic oxidation to form an aluminum oxide (al.sub.2 o.sub.3) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 44 following the procedures of example 53. the resultant drum was evaluated by the same manners as in example 53. the results obtained were as shown in table 95. as table 95 illustrates, superiorities in the respective evaluation items were acknowledged. example 58 a drum having an ir absorptive layer, a photoconductive layer and a surface layer was prepared under the condition shown in table 96 and following the procedures of example 53. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelength as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 97. as table 97 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that any infringe pattern did not appear on an image to be made. example 59 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 98 and following the procedures of example 53. the resultant drum was evaluated by the same manners as in example 53. the results obtained were as shown in table 99. as table 99 illustrates, superiorities in the respective evaluation items were acknowledged. example 60 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 100 and following the procedures of example 53. the resultant drum was evaluated in the same way as in example 58. the results obtained were as shown in table 101. as table 101 illustrates, superiorities in the respective evaluation items were acknowledged. example 61 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 102 and following the procedures of example 53. the resultant drum was evaluated in the same way as in example 53. the results obtained were as shown in table 103. as table 103 illustrates, superiorities in the respective evaluation items were acknowledged. example 62 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 104 and following the procedures of example 53. the resultant drum was evaluated in the same way as in example 58. the results obtained were as shown in table 105. as table 105 illustrates, superiorities in the respective evaluation items were acknowledged. example 63 the procedures of example 53 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 20, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 64 the procedures of example 54 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 21, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 65 the procedures of example 55 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 22, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 66 the procedures of example 56 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 23, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 67 the procedures of example 56 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 106. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 68 the procedures of example 56 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 107, to thereby prepare multiple drums as shown in table 108. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 69 the procedures of example 56 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 109, to thereby prepare multiple drums as shown in table 110. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 70 the procedures of example 57 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 111, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 71 the procedures of example 5 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 107, to thereby prepare multiple drums as shown in table 112. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 72 the procedures of example 57 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 109, to thereby prepare multiple drums as shown in table 113. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 73 the procedures of example 58 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 114. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 74 the procedures of example 58 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 115. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 75 the procedures of example 58 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 107, to thereby prepare multiple drums as shown in table 116. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 76 the procedures of example 6 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 109, to thereby prepare multiple drums as shown in table 117. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 77 the procedures of example 59 were repeated, except that the contact layer forming conditions were changed as shown in table 42, to thereby prepare multiple drums as shown in table 118. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 78 the procedures of example 59 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 119. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 79 the procedures of example 59 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 107, to thereby prepare multiple drums as shown in table 120. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 80 the procedures of example 59 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 109, to thereby prepare multiple drums as shown in table 121. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 81 the procedures of example 60 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 122. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 82 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 153. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 83 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 107, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 124. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 84 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 125, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 125. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 85 the procedures of example 61 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 126. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 86 the procedures of example 61 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 127. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 87 the procedures of example 61 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 107, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 128. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 88 the procedures of example 61 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 109, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 129. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 89 the procedures of example 62 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 130. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 90 the procedures of example 62 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 131. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 91 the procedures of example 62 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 107, to thereby prepare multiple drums as shown in table 132. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 92 the procedures of example 62 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 109, to thereby prepare multiple drums as shown in table 133. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 93 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 134, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 135. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 94 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 134, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 136. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 95 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 107, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 137. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 96 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 107, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 138. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 97 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 109, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 139. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 98 the procedures of example 60 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 109, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 140. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 99 the procedures of example 56 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 109, to thereby prepare multiple drums as shown in table 141. the resultant drums were evaluated in the same way as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 100 the procedures of example 60 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 107, to thereby prepare multiple drums as shown in table 142. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 101 the procedures of example 62 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions were changed as shown in table 109, to thereby prepare multiple drums, as shown in table 143. the resultant drums were evaluated in the same way as in example 58. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 102 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 144 and following the procedures of example 53. the resultant drum was evaluated in the same way as in example 53. as a result, superiorities in the respective evaluation items were acknowledged. example 103 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 53. the resulting drums were evaluated with the same procedures as in example 53. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 104 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and of a cross section pattern of table 86 were provided these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 53. the resulting drums were evaluated with the same procedures of example 53. as a result, it was found that every drum is provided with practically applicable desired electrophotographic characteristics. example 105 a light receiving member for use in electrophotography having a light receiving layer disposed on an al cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 145 using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer comprising an upper layer and a lower layer on an aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, the situation of surface abrasion and increase of defective images after 1,500 thousand times repeated shots were respectively examined. then, the situation of an image flow of the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. further, the situation of superiority or inferiority in the cleaning property of the drum in accordance with the degree of background fogginess appearity on a blank image was examined by purposely replacing the original cleaning blade by another cleaning blade having a worn edge. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 146. as table 146 illustrates, superiorities in the respective evaluation items, particularly of the items relative to defective image, image flow and cleaning property for the drum were acknowledged. as for each of the samples, the cordination number of boron nitride contained in each of the upper and the lower layer was examined in accordance with exafs (extended x-ray absorption fine structure). as a result, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 106 the procedures of example 105 were repeated under the conditions shown in table 147 wherein h.sub.2 gas is additionally used in the formation of a surface layer to therby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 105. the results obtained were as shown in table 148. as table 148 illustrates, superiorities in the respective evaluation items were acknowledged. and as a result of examining the cordination number of boron nitride contained in each of the samples, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 107 the procedures of example 105 were repeated, except that the vias voltage of the cylinder in the case of forming a lower layer and the vias voltage in the case of forming an upper layer were controlled to be -150 v and +100 v respectively at the time of forming a surface layer, to thereby prepare a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 105. the results obtained were as shown in table 149. as table 149 illustrates, desirable results as those in example 105 were acknowledged. as for the situations of tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in each of the samples, it was found that there were contained trihedrally bonded boron nitride and tetrahedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 108 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an alminum cylinder was prepared under the conditions shown in table 150 and following the procedures of example 105. the resultant drum was evaluated by the same manners as in example 105. the results obtained were as shown in table 151. as table 151 illustrates, superiorities in respective evaluation items were acknowledged for the drum. example 109 an alminum cylinder was subjected to anodic oxidation to form an aluminum oxide (al.sub.2 o.sub.3) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 152 following the procedures of example 105. the resultant drum was evaluated by the same manners as in example105. the results obtained were as shown in table 153. as table 153 illustrates, superiorities in the respective evaluation items were acknowledged. example 110 a drum having an ir absorptive layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 154 and following the procedures of example 105. the resultant drum was evaluated by the same manners as in example 105. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelength as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 155. as table 155 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that any infringe pattern did not appear on an image to be made. example 111 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 156 and following the procedures of example 105. the resultant drum was evaluated by the same manners as in example 105. the results obtained were as shown in table 157. as table 157 illustrates, superiorities in the respective evaluation items were acknowledged. example 112 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 158 and following the procedures of example 105. the resultant drum was evaluated in the same way as in example 110. the results obtained were as shown in table 159. as table 159 illustrates, superiorities in the respective evaluation items were acknowledged. example 113 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 160 and following the procedures of example 105. the resultant drum was evaluated in the same way as in example 105. the results obtained were as shown in table 161. as table 161 illustrates, superiorities in the respective evaluation items were acknowledged. example 114 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 162 and following the procedures of example 105. the resultant drum was evaluated in the same way as in example 110. the results obtained were as shown in table 163. as table 163 illustrates, superiorities in the respective evaluation items were acknowledged. example 115 the procedures of example 105 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 20, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 116 the procedures of example 106 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 21, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 117 the procedures of example 107 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 22, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 118 the procedures of example 108 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 23, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 119 the procedures of example 108 were repeated, except that the charge injection inhibiton layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 164. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 120 the procedures of example 108 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 165, to thereby prepare multiple drums as shown in table 166. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 121 the procedures of example 108 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 167, to thereby prepare multiple drums as shown in table 168. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 122 the procedures of example 109 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 169. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 123 the procedure of example 109 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 165, to thereby prepare multiple drums as shown in table 170. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 124 the procedures of example 109 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 167, to thereby prepare multiple drums as shown in table 171. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 125 the procedures of example 110 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 172. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 126 the procedures of example 110 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 173. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 127 the procedures of example 110 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 165, to thereby prepare multiple drums as shown in table 174. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 128 the procedures of example 110 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 167, to thereby prepare multiple drums as shown in table 175. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 129 the procedures of example 111 were repeated, except that the contact layer forming conditions were changed as shown in table 42, to thereby prepare multiple drums as shown in table 176. the resulant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 130 the procedures of example 111 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 177. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 131 the procedures of example 111 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 165, to thereby prepare multiple drums as shown in table 178. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 132 the procedures of example 111 were repeated, except that the contact layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 167, to thereby prepare multiple drums as shown in table 179. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 133 the procedures of example 112 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 180. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 134 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 181. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 135 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 165, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 182. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 136 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 167, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 183. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 137 the procedures of example 113 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 184. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 138 the procedures of example 113 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 185. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 139 the procedures of example 113 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 165, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 186. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 140 the procedures of example 113 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 167, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 187. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 141 the procedures of example 114 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 188. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 142 the procedures of example 114 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 189. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 143 the procedures of example 114 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 165, to thereby prepare multiple drums as shown in table 190. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 144 the procedures of example 114 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 167, to thereby prepare multiple drums as shown in table 191. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 145 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51. table 69 and table 192, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 193. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 146 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 192, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 194. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 147 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 165, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 195. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 148 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 165, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 196. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 149 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 167, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 197. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 150 the procedures of example 112 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 167, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 198. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 151 the procedures of example 108 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 167, to thereby prepare multiple drums as shown in table 199. the resultant drums were evaluated in the same way as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 152 the procedures of example 112 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 167, to thereby prepare multiple drums as shown in table 200. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 153 the procedures of example 114 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions were changed as shown in table 167, to thereby prepare multiple drums as shown in table 201. the resultant drums were evaluated in the same way as in example 110. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 154 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 202 and following the procedures of example 105. the resultant drum was evaluated in the same way as in example 105. as a result, superiorities in the respective evaluation items were acknowledged. example 155 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 105. the resulting drums were evaluated with the same procedures as in example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 156 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and of a cross section pattern of table 86 were provided these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 105. the resulting drums were evaluated with the same procedures of example 105. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 157 a light receiving member for use in electrophotography having a light receiving layer disposed on an a1 cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 203(a) and table 203(b) using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer on an aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, the situation of surface abrasion and increase of defective images after 1,500 thousand times repeated shots were respectively examined. then, the situation of an image flow on the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. further, the situation of superiority or inferiority in the cleaning property of the drum in accordance with the degree of background fogginess appearing on a blank image was examined by purposely replacing the original cleaning blade by another cleaning blade having a worn edge. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 204. as table 204 illustrates, extreme superiorities in every evaluation item of the initial electrification efficiency (initial charging efficiency), defective image, surface abrasion, breakdown voltage and abrasion resistance for the drum were acknowledged. as for each of the samples, the cordination number of boron nitride contained therein was examined in accordance with exafs (extended x-ray absorption fine structure). as a result, it was found that every sample contained tetrahedrally bonded boron nitride. example 158 the procedures of example 157 were repeated under the conditions shown in table 205(a) and table 205(b) wherein h.sub.2 gas is additionally used in the formation of a surface layer to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 157. the results obtained were as shown in table 206. as table 206 illustrates, superiorities in the respective evaluation items were acknowledged for the drum. and, as for each of the samples, it was found that every sample contained tetrahedrally bonded boron nitride. example 159 the procedures of example 157 were repeated under the same conditions as shown in the foregoing table 203(a) and table 203(b), except that the vias voltage of the aluminum cylinder was controlled to -150 v, to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 157. the results obtained were shown in table 207. as table 207 illustrated, desirable results as those in example 157 were acknowledged. as for the boron nitrides contained in the surface layer, it was acknowledged that every sample contained tetrahedrally bonded boron nitride. example 160 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an aluminum cylinder was prepared under the conditions shown in table 208(a) and table 208(b) and following the procedures of example 157. the resultant drum was evaluated by the same manners a s in example 157. the results obtained were as shown in table 7. as table 7 illustrates, superiorities in the respective evaluation items were acknowledged for the drum. example 161 an aluminum cylinder was subjected to anodic oxidation to form an aluminum oxide (al.sub.2 o.sub.3) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 210(a) and table 210(b) following the procedures of example 157. the resultant drum was evaluated by the same manners as in example 157. the results obtained were as shown in table 211. as table 211 illustrates, superiorities in the respective evaluation items were acknowledged. example 162 a drum having an ir absorptive layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 212(a) and table 212(b) and following the procedures of example 157. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelength as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 213. as table 213 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that any infringe pattern did not appear on an image to be made. example 163 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 214(a) and table 214(b) and following the procedures of example 157. the resultant drum was evaluated by the same manners as in example 157. the results obtained were as shown in table 215. as table 215 illustrates, superiorities in the respective evaluation items were acknowledged. example 164 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 216(a) and table 216(b) and following the procedures of example 157. the resultant drum was evaluated in the same way as in example 162. the results obtained were as shown in table 217. as table 217 illustrates, superiorities in the respective evaluation items were acknowledged. example 165 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 218(a) and table 218(b) and following the procedures of example 157. the resultant drum was evaluated in the same way as in example 157. the results obtained were as shown in table 219. as table 219 illustrates, superiorities in the respective evaluation items were acknowledged. example 166 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 220(a) and table 220(b) and following the procedures of example 157. the resultant drum was evaluated in the same way as in example 162. the results obtained were as shown in table 221. as table 221 illustrates, superiorities in the respective evaluation items were acknowledged. example 167 the procedures of example 157 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 222, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 168 the procedures of example 158 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 223, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 169 the procedures of example 159 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 224, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 170 the procedures of example 160 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 225, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 171 the procedures of example 160 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 226. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 172 the procedures of example 160 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 227, to thereby prepare multiple drums as shown in table 228. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 173 the procedures of example 160 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 229, to thereby prepare multiple drums as shown in table 230. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 174 the procedures of example 161 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 231. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 175 the procedures of example 161 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 227, to thereby prepare multiple drums as shown in table 232. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 176 the procedures of example 161 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 229, to thereby prepare multiple drums as shown in table 233. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 177 the procedures of example 162 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 234. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 178 the procedures of example 162 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 235. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 179 the procedures of example 162 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 227, to thereby prepare multiple drums as shown in table 236. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 180 the procedures of example 162 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 229, to thereby prepare multiple drums as shown in table 237. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 181 the procedures of example 163 were repeated, except that the contact layer forming conditions were changed as shown in table 163, to thereby prepare multiple drums as shown in table 238. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 182 the procedures of example 163 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 239. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 183 the procedures of example 163 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44. table 27 and table 277, to thereby prepare multiple drums as shown in table 240. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 184 the procedures of example 163 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 279, to thereby prepare multiple drums as shown in table 241. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 185 the procedures of example 164 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 242. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 186 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 243. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 187 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 227, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 244. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 188 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 229, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 245. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 189 the procedures of example 165 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 246. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 190 the procedures of example 165 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 247. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 191 the procedures of example 165 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 227, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 248. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 192 the procedures of example 165 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 229, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 249. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 193 the procedures of example 166 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 250. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 194 the procedures of example 166 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 251. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 195 the procedures of example 166 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 227, to thereby prepare multiple drums as shown in table 252. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 196 the procedures of example 166 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 229, to thereby prepare multiple drums as shown in table 253. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 197 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 254, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 255. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 198 the procedure of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 254, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 256. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 199 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 227, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 257. the resultant drums were evauated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 200 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 227, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 258. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 201 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 229, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 259. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 202 the procedures of example 164 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 229, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 260. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 203 the procedures of example 160 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 227, to thereby prepare multiple drums as shown in table 261. the resultant drums were evaluated in the same way as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 204 the procedures of example 164 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 229, to thereby prepare multiple drums as shown in table 262. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 205 the procedures of example 166 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions were changed as shown in table 229, to thereby prepare multiple drums as shown in table 263. the resultant drums were evaluated in the same way as in example 162. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 206 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 264 and following the procedures of example 157. the resultant drum was evaluated in the same way as in example 157, superiorities in the respective evaluation items were acknowledged. example 207 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 157. the resulting drums were evaluated with the same procedures as in example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 208 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and a cross section pattern of table 86 were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 157. the resulting drums were evaluated with the same procedures of example 157. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 209 a light receiving member for use in electrophotography having a light receiving layer disposed on an al cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 265(a) and table 265(b) using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer on an aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, the situation of surface abrasion and increase of defective images after 1,500 thousand times repeated shots were respectively examined. then, the situation of an image flow on the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. further, the situation of superiority or inferiority in the cleaning property of the drum in accordance with the degree of background fogginess appearing on a blank image was examined by purposely replacing the original cleaning blade by another cleaning blade having a worm edge. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 266. as table 266 illustrates, superiorities in the respective evaluation items, particularly of the items relative to defective image, image flow and cleaning property for the drum were acknowledged. as for the samples, the cordination number of boron nitride contained therein was examined in accordance with exafs (extended x-ray absorption fine structure). as a result, it was found that there were contained tetrahedrally bonded boron nitrides and trihedrally bonded boron nitride in mingled state. then, as for the sample on the si-monocrystal wafer, the residual stress was observed by making stripes of .quadrature./mm in checker from on its surface and by peeling off the adhesive tape adhered thereon. as a result, it was found that the sample exceled in the residual stress. example 210 the procedures of example 209 were repeated under the conditions shown in table 267(a) and table 276(b) wherein h.sub.2 gas is additionally used in the formation of a surface layer, to therby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 209. the results obtained were as shown in table 268. as table 268 illustrates, superiorities in the respective evaluation items were acknowledged. and as a result of examining the cordination number of boron nitride contained in each of the samples, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state. example 211 the procedures of example 209 were repeated under the same conditions as shown in the foregoing table 265(a) and table 265(b), except that the vias voltage of the aluminum cylinder was controlled to +100 v, to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 209. the results obtained were as shown in table 269. as table 269 illustrates, desirable results as those in example 209 were acknowledged. as for the situations of tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in each of the samples. it was found that both of them were contained in mingled state. example 212 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an aluminum cylinder was prepared under the conditions shown in table 270(a) and table 270(b) and following the procedures of example 209. the resultant drum was evaluated by the same manners as in example 209. the results obtained were as shown in table 271. as table 271 illustrates, superiorities in respective evaluation items were acknowledged for the drum. example 213 an aluminum cylinder was subjected to anodic oxidation to form an aluminium oxide (al.sub.2 o.sub.3) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 272(a) and table 272(b) following the procedures of example 209. the resultant drum was evaluated by the same manners as in example 209. the results obtained were as shown in table 273. as table 273 illustrates, superiorities in the respective evaluation items were acknowledged. example 214 a drum having an ir absorptive layer, a photoconductive layer and a surface layer was prepared under the condition shown in table 274(a) and table 274(b) and following the procedures of example 209. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelength as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 275. as table 275 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that many infringe pattern did not appear on an image to be made. example 215 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 276(a) and table 276(b) and following the procedures of example 209. the resultant drum was evaluated by the same manners as in example 209. the results obtained were as shown in table 277. as table 277 illustrates, superiorities in the respective evaluation items were acknowledged. example 216 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 278(a) and table 278(b) and following the procedures of example 209. the resultant drum was evaluated in the same way as in example 214. the results obtained were as shown in table 279. as table 279 illustrates, superiorities in the respective evaluation items were acknowledged. example 217 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 280(a) and table 280(b) and following the procedures of example 209. the resultant drum was evaluated in the same way as in example 209. the results obtained were as shown in table 281. as table 281 illustrates, superiorities in the respective evaluation items were acknowledged. example 218 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 282(a) and table 282(b) and following the procedures of example 209. the resultant drum was evaluated in the same way as in example 214. the results obtained were as shown in table 283. as table 283 illustrates, superiorities in the respective evaluation items were acknowledged. example 219 the procedures of example 209 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 284, to thereby prepare multiple drum. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 220 the procedures of example 210 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 285, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 221 the procedures of example 211 was repeated, except that the photoconductive layer forming conditions were changed as shown in table 286, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotograhic characteristics. example 222 the procedures of example 212 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 287, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 223 the procedures of example 212 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 288. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 224 the procedures of example 212 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 289, to thereby prepare multiple drums as shown in table 290. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 225 the procedures of example 212 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 291, to thereby prepare multiple drums as shown in table 292. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 226 the procedures of example 213 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 293. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 227 the procedures of example 213 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 289, to thereby prepare multiple drums as shown in table 294. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 228 the procedures of example 213 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 291, to thereby prepare multiple drums as shown in table 295. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 229 the procedures of example 214 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 296. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 230 the procedures of example 214 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 297. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 231 the procedures of example 214 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 289, to thereby prepare multiple drums as shown in table 298. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 232 the procedures of example 214 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 291. to thereby prepare multiple drums as shown in table 299. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 233 the procedures of example 215 were repeated, except that the contact layer forming conditions were changed as shown in table 42, to thereby prepare multiple drums as shown in table 300. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 234 the procedures of example 215 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 301. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 235 the procedures of example 215 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 289, to thereby prepare multiple drums as shown in table 302. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electophotographic characteristics. example 236 the procedures of example 215 were repeated except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 291, to thereby prepare multiple drums as shown in table 303. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 237 the procedures of example 216 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 304. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 238 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 305. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 239 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 289, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 306. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 240 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 291, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 307. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 241 the procedures of example 217 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 308. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 242 the procedures of example 217 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 309. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 243 the procedures of example 217 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 289, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 310. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 244 the procedures of example 217 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 30, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 311. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 245 the procedures of example 218 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 312. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 246 the procedures of example 218 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 313. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 247 the procedures of example 218 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 281, to thereby prepare multiple drums as shown in table 314. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 248 the procedures of example 218 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 291, to thereby prepare multiple drums as shown in table 315. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 249 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 316, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 317. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 250 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 316, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 318. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 251 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 289, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 319. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 252 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 289, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 320. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 253 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 291, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 321. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 254 the procedures of example 216 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 291, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 322. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 255 the procedures of example 212 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 291, to thereby prepare multiple drums as shown in table 323. the resultant drums were evaluated in the same way as in example 209. as a result, it was found that every drum was provided with practically applicable desired electophotographic characteristics. example 256 the procedures of example 216 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 291, to thereby prepare multiple drums as shown in table 324. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 257 the procedures of example 218 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions were changed as shown in table 291, to thereby prepare multiple drums as shown in table 325. the resultant drums were evaluated in the same way as in example 214. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 258 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 326 and following the procedures of example 209. the resultant drum was evaluated in the same way as in example 209, as a result superiorities in the respective evaluation items were acknowledged. example 259 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 209. the resulting drums were evaluated with the same procedures as in example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 260 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and of a cross section pattern of table 86 were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 209. the resulting drums were evaluated with the same procedures of example 209. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 261 a light receiving member for use in electrophotography having a light receiving layer disposed on an a1 cylinder having a mirror grinded surface was prepared under the layer forming conditions shown in table 327(a) and table 327(b) using the fabrication apparatus shown in fig. 2. and samples were provided by forming only a surface layer comprising an upper layer and a lower layer on the aluminum plate and on a si-monocrystal wafer respectively placed on the substrate holder in the same manner for forming the surface layer in the above case using the same kind fabrication apparatus as shown in fig. 2. for the resulting light receiving member (hereinafter this kind light receiving member is referred to as "drum"), it was set with the conventional electrophotographic copying machine, and electrophotographic characteristics such as initial electrification efficiency (initial charging efficiency), residual voltage and appearance of a ghost were examined, then decrease in the electrification efficiency, the situation of surface abration and increase of defective images after 1,500 thousand times repeated shots were respectively examined. then, the situation of an image flow on the drum under high temperature and high humidity atmosphere at 35.degree. c. and 85% humidity was also examined. further, the situation of superiority or inferiority in the cleaning property of the drum in accordance with the degree of background fogginess appearing on a blank image was examined by purposely replacing the original cleaning blade by another cleaning blade having a worn edge. in addition, the situation of breakdown voltage for the drum was observed by applying a high direct current voltage onto the drum. further in addition, the abrasion resistance of the drum was examined by wearing its surface using a metallic needle having a round top while applying a predetermined load thereon. the results obtained were as shown in table 328. as table 328 illustrates, superiorities in the respective evaluation items, particularly of the items relative to defective image, image flow abrasion registance, breakdown voltage and cleaning property for the drum were acknowledged. as for each of the samples, the cordination number of boron nitride contained in each of the upper layer and the lower layer was examined in accordance with exafs (extended x-ray absorption fine structure). as a result, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 262 the procedures of example 261 were repeated under the conditions shown in table 329(a) and table 329(b) wherein h.sub.2 gas is additionally used in the formation of a surface layer to thereby obtain a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 261. the results obtained were as shown in table 330. as table 330 illustrates, superiorities in the respective evaluation items were acknowledged. and as a result of examining a cordination number of boron nitride contained in each of the samples, it was found that there were contained tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 263 the procedures of example 261 were repeated, except that the vias voltage of the cylinder in the case of forming a lower layer and the vias voltage in the case of forming an upper layer were controlled to be -150 v and +100 v respectively at the time of forming a surface layer, to thereby prepare a drum and samples. the resultant drum and samples were evaluated by the same manners as in example 261. the results obtained were shown in table 331. as table 331 illustrates, desirable results as those in example 261 were acknowledged. as for the situation of tetrahedrally bonded boron nitride and trihedrally bonded boron nitride in each of the samples, it was found that there were contained trihedrally bonded boron nitride and tetrahedrally bonded boron nitride in mingled state in the upper layer and there was contained tetrahedrally bonded boron nitride in the lower layer. example 264 a drum having a charge injection inhibition layer, a photoconductive layer and a surface layer on an aluminum cylinder was prepared under the conditions shown in table 332(a) and table 332(b) and following the procedures of example 261. the resultant drum was evaluated by the same manners as in example 261. the results obtained were as shown in table 333. as table 333 illustrates, superiorities in respective evaluation items were acknowledged for the drum. example 265 an aluminum cylinder was subjected to anodic oxidation to form an aluminum oxide (al.sub.2 o.sub.3) layer to be a charge injection inhibition layer thereon, and a photoconductive layer then a surface layer were continuously formed on the previously formed charge injection inhibition layer under the conditions shown in table 334(a) and table 334(b) following the procedure of example 261. the resultant drum was evaluated by the same manners as in example 261. the results obtained were as shown in table 335. as table 335 illustrates, superiorities in the respective evaluation items were acknowledged. example 266 a drum having an ir absorptive layer, a photoconductive layer and a surface layer was prepared under the condition shown in table 336(a) and table (b) and following the procedures of example 261. the resultant drum was evaluated by the same manners as in example 261. in addition, the drum was set with the conventional electrophotographic copying machine using a semiconductor laser beam of 785 nm in wavelength as the light source for image exposure in order to examine whether an infringe pattern appears or not on an image to be made. the results obtained were as shown in table 337. as table 337 illustrates, superiorities in the respective evaluation items were acknowledged, and it was found that any infringe pattern did not appear on an image to be made. example 267 a drum having a contact layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 338(a) and table 338(b) and following the procedures of example 261. the resultant drum was evaluated by the same manners as in example 261. the results obtained were as shown in table 339. as table 339 illustrates, superiorities in the respective evaluation items were acknowledged. example 268 a drum having an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 340(a) and table 340(b) and following the procedures of example 261. the resultant drum was evaluated in the same way as in example 266. the results obtained were as shown in table 341. as table 341 illustrates, superiorities in the respective evaluation items were acknowledged. example 269 a drum having a contact layer, a charge injection inhibition layer, a photoconductive layer and a surface layer were prepared under the conditions shown in table 342(a) and table 342(b) and following the procedures of example 261. the resultant drum was evaluated in the same way as in example 261. the results obtained were as shown in table 343. as table 343 illustrates, superiorities in the respective evaluation items were acknowledged. example 270 a drum having a contact layer, an ir absorptive layer, a charge injection inhibition layer, a photoconductive layer and a surface layer was prepared under the conditions shown in table 344(a) and table 344(b) and following the procedures of example 261. the resultant drum was evaluated in the same way as in example 266. the results obtained were as shown in table 345. as table 345 illustrates, superiorities in the respective evaluation items were acknowledged. example 271 the procedures of example 261 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 346, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 272 the procedures of example 262 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 347, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 273 the procedures of example 263 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 348, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 274 the procedures of example 264 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 349, to thereby prepare multiple drums. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 275 the procedures of example 264 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 24 and table 25, to thereby prepare multiple drums as shown in table 350. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 276 the procedures of example 264 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24. table 27 and table 351, to thereby prepare multiple drums as shown in table 352. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 277 the procedures of example 264 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24, table 27 and table 353, to thereby prepare multiple drums as shown in table 354. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 278 the procedures of example 265 were repeated, except that the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 354. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 279 the procedures of example 265 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 351, to thereby prepare multiple drums as shown in table 356. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 280 the procedures of example 265 were repeated, except that the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 353, to thereby prepare multiple drums as shown in table 357. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 281 the procedures of example 266 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 358. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 282 the procedures of example 266 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38 and the photoconductive layer forming conditions were changed as shown in table 25, to thereby prepare multiple drums as shown in table 359. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 283 the procedures of example 266 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 351, to thereby prepare multiple drums as shown in table 360. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 284 the procedures of example 266 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, and the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 27 and table 353, to thereby prepare multiple drums as shown in table 361. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 285 the procedures of example 267 were repeated, except that the contact layer forming conditions were changed as shown in table 42, to thereby prepare multiple drums as shown in table 362. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 286 the procedures of example 267 were repeated, except that the contact layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 44 and table 25, to thereby prepare multiple drums as shown in table 363. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 287 the procedures of example 267 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44. table 27 and table 351, to thereby prepare multiple drums as shown in table 364. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 288 the procedures of example 267 were repeated, except that the contact layer forming conditions, photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 44, table 27 and table 353, to thereby prepare multiple drums as shown in table 365. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 289 the procedures of example 268 were repeated, except that the ir absorptive layer forming conditions were changed as shown in table 35 and table 36, to thereby prepare multiple drums as shown in table 366. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 290 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 49 and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 367. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 291 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 351, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 368. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 292 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51 and table 353, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 369. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 293 the procedures of example 269 were repeated, except that the contact layer forming conditions were changed as shown in table 44 and table 54, to thereby prepare multiple drums as shown in table 370. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 294 the procedures of example 269 were repeated, except that the change injection inhibition layer forming conditions were changed as shown in table 56, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 371. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 295 the procedures of example 269 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 351, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 372. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 296 the procedures of example 269 were repeated, except that the charge injection inhibition layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 24 and table 353, and the contact layer forming conditions were changed as shown in table 44 and table 57, to thereby prepare multiple drums as shown in table 373. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 297 the procedures of example 270 were repeated, except that the charge injection inhibition layer forming conditions were changed as shown in table 61, to thereby prepare multiple drums as shown in table 374. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 298 the procedures of example 270 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed respectively as shown in table 64 and table 63, to thereby prepare multiple drums as shown in table 375. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 299 the procedures of example 270 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 351, to thereby prepare multiple drums as shown in table 376. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 300 the procedures of example 270 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 64, table 66 and table 353, to thereby prepare multiple drums as shown in table 377. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 301 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51. table 69 and table 378, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 379. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 302 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 378, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 380. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 303 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 351, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 381. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 304 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 351, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 382. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 305 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 69 and table 353,and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 383. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 306 the procedures of example 268 were repeated, except that the charge injection inhibition layer forming conditions, the photoconductive layer forming conditions and the surface layer forming conditions were changed respectively as shown in table 51, table 72 and table 353, and the ir absorptive layer forming conditions were changed as shown in table 35 and table 38, to thereby prepare multiple drums as shown in table 384. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 307 the procedures of example 264 were repeated, except that the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 78 and the surface layer forming conditions were changed as shown in table 353, to thereby prepare multiple drums as shown in table 385. the resultant drums were evaluated in the same way as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 308 the procedures of example 268 were repeated, except that the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 80 and the surface layer forming conditions were changed as shown in table 353, to thereby prepare multiple drums as shown in table 386. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 309 the procedures of example 270 were repeated, except that the contact layer forming conditions, the ir absorptive layer forming conditions, the charge injection inhibition layer forming conditions and the photoconductive layer forming conditions were changed as shown in table 82 and the surface layer forming conditions were changed as shown in table 353, to thereby prepare multiple drums as shown in table 387. the resultant drums were evaluated in the same way as in example 266. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 310 a drum having a charge injection inhibition layer, a photoconductive layer, an intermediate layer and a surface layer was prepared under the conditions shown in table 388 and following the procedures of example 261. the resultant drum was evaluated in the same way as in example 261, superiorities in the respective evaluation items were acknowledged. example 311 the mirror grinded cylinders were supplied for grinding process with cutting tool having various degrees. with the patterns of fig. 3 and various cross section patterns as described in table 85, multiple cylinders were provided. these cylinders were set to the fabrication apparatus of fig. 2 accordingly, and used to prepare multiple drums under the same layer forming conditions of example 261. the resulting drums were evaluated with the same procedures as in example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. example 312 the surface of mirror grinded cylinder was treated by dropping lots of bearing balls thereto to thereby form uneven shape composed of a plurality of fine dimples at the surface, and multiple cylinders having a cross section form of fig. 4 and of a cross section pattern of table 86 were provided these cylinders were set to the fabrication apparatus of fig. 2 accordingly and used for the preparation of multiple drums under the same layer forming conditions of example 261. the resulting drums were evaluated with the same procedures of example 261. as a result, it was found that every drum was provided with practically applicable desired electrophotographic characteristics. table 1 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 2 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 3 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer h.sub.2 100 nh.sub.3 100 __________________________________________________________________________ table 4 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 5 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practicle use x: poor table 6 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 7 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 8 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 9 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 10 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 11 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion interference efficiency voltage ghost image flow image abrasion voltage resistance fringe __________________________________________________________________________ .circle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x poor table 12 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 13 __________________________________________________________________________ initial increase electri- of break fication residual defective image defective surface down abrasion efficiency voltage ghost image flow image abrasion voltage resistance __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 14 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 15 __________________________________________________________________________ initial electri- residual defective image increase of surface break down abrasion interference fication efficiency voltage ghost image flow defective image abrasion voltage resistance fringe __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 16 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 17 __________________________________________________________________________ initial electri- residual defective image increase of surface break abrasion fication efficiency voltage ghost image flow defective image abrasion down voltage resistance __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 18 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 19 __________________________________________________________________________ intial electri- residual defective image increase of surface break down abrasion interference fication efficiency voltage ghost image flow defective image abrasion voltage resistance fringe __________________________________________________________________________ .circleincircle. .circle. .circleincircle. .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ .circleincircle. : excellent .circle. : good .delta. : applicable for practical use x: poor table 20 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 1101 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 1102 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 1103 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 1104 sih.sub.4 200 250 250 0.40 20 ar 200 1105 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ table 21 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 1201 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 1202 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 1203 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 1204 sih.sub.4 200 250 250 0.40 20 ar 200 1205 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ table 22 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 1301 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 1302 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 1303 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 1304 sih.sub.4 200 250 250 0.40 20 ar 200 1305 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ table 23 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 1401 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm geh.sub.4 10 no 10 1402 sih.sub.4 80 250 170 0.25 3 sif.sub.4 20 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm snh.sub.4 5 no 5 1403 sih.sub.4 100 250 130 0.25 3 b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 1404 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 ph.sub.3 (against sih.sub.4) 800 ppm 1405 sih.sub.4 100 250 130 0.25 3 ph.sub.3 (against sih.sub.4) 800 ppm geh.sub.4 10 no 10 1406 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no* 10 no** 10.fwdarw. 0 *** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 1 .mu.m ***constantly changed table 24 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 1 no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 2 geh.sub.4 10 no 10 charge sih.sub.4 80 250 170 0.25 3 injection sif.sub.4 20 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 3 snh.sub.4 5 no 5 charge sih.sub.4 100 250 130 0.25 3 injection b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm inhibition no 4 layer 4 n.sub.2 4 ch.sub.4 6 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer 5 charge sih.sub. 4 100 250 130 0.25 3 injection ph.sub.3 (against sih.sub.4) 800 ppm inhibition geh.sub.4 10 layer 6 no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10.fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 25 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer 1 no 4 photo- sih.sub.4 200 250 300 0.40 20 conductive he 200 layer 2 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 3 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 photo- sih.sub.4 200 250 250 0.40 20 conductive ar 200 layer 5 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 6 h.sub.2 200 __________________________________________________________________________ table 26 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 1501 1506 1511 1516 1521 1526 1531 conductive layer 1 photo- 1502 1507 1512 1517 1522 1527 1532 conductive layer 2 photo- 1503 1508 1513 1518 1523 1528 1533 conductive layer 3 photo- 1504 1509 1514 1519 1524 1529 1534 conductive layer 5 photo- 1505 1510 1515 1520 1525 1530 1535 conductive layer 6 __________________________________________________________________________ table 27 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer 1 no 4 photo- sih.sub.4 200 250 300 0.40 20 conductive he 200 layer 2 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 3 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer 4 photo- sih.sub.4 200 250 250 0.40 20 conductive ar 200 layer 5 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 6 h.sub.2 200 __________________________________________________________________________ table 28 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer h.sub.2 100 nh.sub.3 100 __________________________________________________________________________ table 29 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 1601 1607 1613 1619 1625 1631 1637 conductive layer 1 photo- 1602 1608 1614 1620 1626 1632 1638 conductive layer 2 photo- 1603 1609 1615 1621 1627 1633 1639 conductive layer 3 photo- 1604 1610 1616 1622 1628 1634 1640 conductive layer 4 photo- 1605 1611 1617 1623 1629 1635 1641 conductive layer 5 photo- 1606 1612 1618 1624 1630 1636 1642 conductive layer 6 __________________________________________________________________________ table 30 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 bias voltage of the cyclinder-150 v __________________________________________________________________________ table 31 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 1701 1707 1713 1719 1725 1731 1737 conductive layer 1 photo- 1702 1708 1714 1720 1726 1732 1738 conductive layer 2 photo- 1703 1709 1715 1721 1727 1733 1739 conductive layer 3 photo- 1704 1710 1716 1722 1728 1734 1740 conductive layer 4 photo- 1705 1711 1717 1723 1729 1735 1741 conductive layer 5 photo- 1706 1712 1718 1724 1730 1736 1742 conductive layer 6 __________________________________________________________________________ table 32 ______________________________________ photo- photo- photo- photo- photo- conduc- conduc- conduc- conductive conductive tive tive tive layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ drum 1801 1802 1803 1804 1805 no. ______________________________________ table 33 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 1901 1902 1903 1904 1905 1906 no. __________________________________________________________________________ table 34 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 2001 2002 2003 2004 2005 2006 no. __________________________________________________________________________ table 35 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 1 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 2 no 10 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 3 no 10 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 4 n.sub.2 4 no 4 ch.sub.4 6 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 5 n.sub.2 4 no 4 ch.sub.4 6 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 6 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 7 b.sub. 2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 ch.sub.4 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 8 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm ch.sub.4 20 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 9 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 10 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 4 n.sub.2 4 ch.sub.4 6 __________________________________________________________________________ table 36 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 11 sif.sub.4 10 ph.sub.3 (against sih.sub.4) 800 ppm ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 12 ph.sub.3 (against sih.sub.4) 800 ppm no 10 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 13 ph.sub.3 (against sih.sub.4) 800 ppm n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 14 ph.sub.3 (against sih.sub.4) 800 ppm no 10 ir sih.sub.4 100 250 170 0.35 1 absorptive snh.sub.4 50 layer 15 ph.sub.3 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub. 4 50 layer 17 ph.sub.3 (against sih.sub.4) 800 ppm ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 18 snh.sub.4 50 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 19 snh.sub.4 50 no 4 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4* 50 layer 20 geh.sub.4** 50 .fwdarw. 0*** h.sub.2 100 __________________________________________________________________________ *substrate side 0.7 .mu.m **surface layer side 0.3 .mu.m ***constantly decreased table 37 ______________________________________ drum no. ______________________________________ ir absorptive 2101 layer 1 ir absorptive 2102 layer 2 ir absorptive 2103 layer 3 ir absorptive 2104 layer 4 ir absorptive 2105 layer 5 ir absorptive 2106 layer 6 ir absorptive 2107 layer 7 ir absorptive 2108 layer 8 ir absorptive 2109 layer 9 ir absorptive 2110 layer 10 ir absorptive 2111 layer 11 ir absorptive 2112 layer 12 ir absorptive 2113 layer 13 ir absorptive 2114 layer 14 ir absorptive 2115 layer 15 ir absorptive 2116 layer 17 ir absorptive 2117 layer 18 ir absorptive 2118 layer 19 ir absorptive 2119 layer 20 ______________________________________ table 38 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 11 sif.sub.4 10 ph.sub.3 (against sih.sub.4) 800 ppm ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 12 ph.sub.3 (against sih.sub.4) 800 ppm no 10 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 13 ph.sub.3 (against sih.sub.4) 800 ppm n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 14 ph.sub.3 (against sih.sub.4) 800 ppm no 10 ir sih.sub.4 100 250 170 0.35 1 absorptive snh.sub.4 50 layer 15 ph.sub.3 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 16 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive snh.sub.4 50 layer 17 ph.sub.3 (against sih.sub.4) 800 ppm ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 18 snh.sub.4 50 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4 50 layer 19 snh.sub.4 50 no 4 h.sub.2 100 ir sih.sub.4 100 250 150 0.35 1 absorptive geh.sub.4* 50 layer 20 geh.sub.4** 50 .fwdarw. 0*** h.sub.2 100 __________________________________________________________________________ *substrate side 0.7 .mu.m **surface layer side 0.3 .mu.m ***constantly decreased table 39 ______________________________________ photo- photo- photo- photo- photo- con- con- con- con- con- drum ductive ductive ductive ductive ductive no. layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ ir absorptive 2201 2221 2241 2261 2281 layer 1 ir absorptive 2202 2222 2242 2262 2282 layer 2 ir absorptive 2203 2223 2243 2263 2283 layer 3 ir absorptive 2204 2224 2244 2264 2284 layer 4 ir absorptive 2205 2225 2245 2265 2285 layer 5 ir absorptive 2206 2226 2246 2266 2286 layer 6 ir absorptive 2207 2227 2247 2267 2287 layer 7 ir absorptive 2208 2228 2248 2268 2288 layer 8 ir absorptive 2209 2229 2249 2269 2289 layer 9 ir absorptive 2210 2230 2250 2270 2290 layer 10 ir absorptive 2211 2231 2251 2271 2291 layer 11 ir absorptive 2212 2232 2252 2272 2292 layer 12 ir absorptive 2213 2233 2253 2273 2293 layer 13 ir absorptive 2214 2234 2254 2274 2294 layer 14 ir absorptive 2215 2235 2255 2275 2295 layer 15 ir absorptive 2216 2236 2256 2276 2296 layer 16 ir absorptive 2217 2237 2257 2277 2297 layer 17 ir absorptive 2218 2238 2258 2278 2298 layer 18 ir absorptive 2219 2239 2259 2279 2299 layer 19 ir absorptive 2220 2240 2260 2280 22100 layer 20 ______________________________________ table 40 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 2301 2321 2341 2361 2381 23101 layer 1 ir absorptive 2302 2322 2342 2362 2382 23102 layer 2 ir absorptive 2303 2323 2343 2363 2383 23103 layer 3 ir absorptive 2304 2324 2344 2364 2384 23104 layer 4 ir absorptive 2305 2325 2345 2365 2385 23105 layer 5 ir absorptive 2306 2326 2346 2366 2386 23106 layer 6 ir absorptive 2307 2327 2347 2367 2387 23107 layer 7 ir absorptive 2308 2328 2348 2368 2388 23108 layer 8 ir absorptive 2309 2329 2349 2369 2389 23109 layer 9 ir absorptive 2310 2330 2350 2370 2390 23110 layer 10 ir absorptive 2311 2331 2351 2371 2391 23111 layer 11 ir absorptive 2312 2332 2352 2372 2392 23112 layer 12 ir absorptive 2313 2333 2353 2373 2393 23113 layer 13 ir absorptive 2314 2334 2354 2374 2394 23114 layer 14 ir absorptive 2315 2335 2355 2375 2395 23115 layer 15 ir absorptive 2316 2336 2356 2376 2396 23116 layer 16 ir absorptive 2317 2337 2357 2377 2397 23117 layer 17 ir absorptive 2318 2338 2358 2378 2398 23118 layer 18 ir absorptive 2319 2339 2359 2379 2399 23119 layer 19 ir absorptive 2320 2340 2360 2380 23100 23120 layer 20 __________________________________________________________________________ table 41 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 2401 2421 2441 2461 2481 24101 layer 1 ir absorptive 2402 2422 2442 2462 2482 24102 layer 2 ir absorptive 2403 2423 2443 2463 2483 24103 layer 3 ir absorptive 2404 2424 2444 2464 2484 24104 layer 4 ir absorptive 2405 2425 2445 2465 2485 24105 layer 5 ir absorptive 2406 2426 2446 2466 2486 24106 layer 6 ir absorptive 2407 2427 2447 2467 2487 24107 layer 7 ir absorptive 2408 2428 2448 2468 2488 24108 layer 8 ir absorptive 2409 2429 2449 2469 2489 24109 layer 9 ir absorptive 2410 2430 2450 2470 2490 24110 layer 10 ir absorptive 2411 2431 2451 2471 2491 24111 layer 11 ir absorptive 2412 2432 2452 2472 2492 24112 layer 12 ir absorptive 2413 2433 2453 2473 2493 24113 layer 13 ir absorptive 2414 2434 2454 2474 2494 24114 layer 14 ir absorptive 2415 2435 2455 2475 2495 24115 layer 15 ir absorptive 2416 2436 2456 2476 2496 24116 layer 16 ir absorptive 2417 2437 2457 2477 2497 24117 layer 17 ir absorptive 2418 2438 2458 2478 2498 24118 layer 18 ir absorptive 2419 2439 2459 2479 2499 24119 layer 19 ir absorptive 2420 2440 2460 2480 21400 24120 layer 20 __________________________________________________________________________ table 42 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer 2 no 20 contact sih.sub.4 20 250 150 0.25 0.5 layer 3 ch.sub.4 400 h.sub.2 100 contact sih.sub.4 10 250 100 0.25 0.5 layer 4 sif.sub.4 10 no 10 n.sub.2 50 ch.sub.4 200 __________________________________________________________________________ table 43 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 2501 2502 2503 no. ______________________________________ table 44 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer 1 n.sub.2 100 contact sih.sub.4 20 250 100 0.25 0.5 layer 2 no 10 contact sih.sub.4 20 250 150 0.25 0.5 layer 3 ch.sub.4 400 h.sub.2 100 contact sih.sub.4 10 250 100 0.25 0.5 layer 4 sif.sub.4 10 no 10 n.sub.2 50 ch.sub.4 200 __________________________________________________________________________ table 45 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 2601 2607 2613 2619 conductive layer 1 photo- 2602 2608 2614 2620 conductive layer 2 photo- 2603 2609 2615 2621 conductive layer 3 photo- 2604 2610 2616 2622 conductive layer 4 photo- 2605 2611 2617 2623 conductive layer 5 photo- 2606 2612 2618 2624 conductive layer 6 ______________________________________ table 46 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 2701 2707 2713 2719 conductive layer 1 photo- 2702 2708 2714 2720 conductive layer 2 photo- 2703 2709 2715 2721 conductive layer 3 photo- 2704 2710 2716 2722 conductive layer 4 photo- 2705 2711 2717 2723 conductive layer 5 photo- 2706 2712 2718 2724 conductive layer 6 ______________________________________ table 47 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 2801 2807 2813 2819 conductive layer 1 photo- 2802 2808 2814 2820 conductive layer 2 photo- 2803 2809 2815 2821 conductive layer 3 photo- 2804 2810 2816 2822 conductive layer 4 photo- 2805 2811 2817 2823 conductive layer 5 photo- 2806 2812 2818 2824 conductive layer 6 ______________________________________ table 48 ______________________________________ drum drum no. no. ______________________________________ ir absorptive 2901 ir absorptive 2911 layer 1 layer 11 ir absorptive 2902 ir absorptive 2912 layer 2 layer 12 ir absorptive 2903 ir absorptive 2913 layer 3 layer 13 ir absorptive 2904 ir absorptive 2914 layer 4 layer 14 ir absorptive 2905 ir absorptive 2915 layer 5 layer 15 ir absorptive 2906 ir absorptive 2917 layer 6 layer 17 ir absorptive 2907 ir absorptive 2918 layer 7 layer 18 ir absorptive 2908 ir absorptive 2919 layer 8 layer 19 ir absorptive 2909 ir absorptive 2920 layer 9 layer 20 ir absorptive 2910 layer 10 ______________________________________ table 49 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 130 0.25 3 injection b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm inhibition no 4 layer 4 n.sub.2 4 ch.sub.4 6 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer 5 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10 .fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 50 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5 layer 7 ______________________________________ ir absorptive 3001 3021 3041 layer 1 ir absorptive 3002 3022 3042 layer 2 ir absorptive 3003 3023 3043 layer 3 ir absorptive 3004 3024 3044 layer 4 ir absorptive 3005 3025 3045 layer 5 ir absorptive 3006 3026 3046 layer 6 ir absorptive 3007 3027 3047 layer 7 ir absorptive 3008 3028 3048 layer 8 ir absorptive 3009 3029 3049 layer 9 ir absorptive 3010 3030 3050 layer 10 ir absorptive 3011 3031 3051 layer 11 ir absorptive 3012 3032 3052 layer 12 ir absorptive 3013 3033 3053 layer 13 ir absorptive 3014 3034 3054 layer 14 ir absorptive 3015 3035 3055 layer 15 ir absorptive 3016 3036 3056 layer 16 ir absorptive 3017 3037 3057 layer 17 ir absorptive 3018 3038 3058 layer 18 ir absorptive 3019 3039 3059 layer 19 ir absorptive 3020 3040 3060 layer 20 ______________________________________ table 51 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 1 no 10 charge sih.sub.4 100 250 130 0.25 3 injection b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm inhibition no 4 layer 4 n.sub.2 4 ch.sub.4 6 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer 5 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10 .fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 52 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 3101 3121 3141 3161 layer 1 ir absorptive 3102 3122 3142 3162 layer 2 ir absorptive 3103 3123 3143 3163 layer 3 ir absorptive 3104 3124 3144 3164 layer 4 ir absorptive 3105 3125 3145 3165 layer 5 ir absorptive 3106 3126 3146 3166 layer 6 ir absorptive 3107 3127 3147 3167 layer 7 ir absorptive 3108 3128 3148 3168 layer 8 ir absorptive 3109 3129 3149 3169 layer 9 ir absorptive 3110 3130 3150 3170 layer 10 ir absorptive 3111 3131 3151 3171 layer 11 ir absorptive 3112 3132 3152 3172 layer 12 ir absorptive 3113 3133 3153 3173 layer 13 ir absorptive 3114 3134 3154 3174 layer 14 ir absorptive 3115 3135 3155 3175 layer 15 ir absorptive 3116 3136 3156 3176 layer 16 ir absorptive 3117 3137 3157 3177 layer 17 ir absorptive 3118 3138 3158 3178 layer 18 ir absorptive 3119 3139 3159 3179 layer 19 ir absorptive 3120 3140 3160 3180 layer 20 ______________________________________ table 53 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 3201 3221 3241 3261 layer 1 ir absorptive 3202 3222 3242 3262 layer 2 ir absorptive 3203 3223 3243 3263 layer 3 ir absorptive 3204 3224 3244 3264 layer 4 ir absorptive 3205 3225 3245 3265 layer 5 ir absorptive 3206 3226 3246 3266 layer 6 ir absorptive 3207 3227 3247 3267 layer 7 ir absorptive 3208 3228 3248 3268 layer 8 ir absorptive 3209 3229 3249 3269 layer 9 ir absorptive 3210 3230 3250 3270 layer 10 ir absorptive 3211 3231 3251 3271 layer 11 ir absorptive 3212 3232 3252 3272 layer 12 ir absorptive 3213 3233 3253 3273 layer 13 ir absorptive 3214 3234 3254 3274 layer 14 ir absorptive 3215 3235 3255 3275 layer 15 ir absorptive 3216 3236 3256 3276 layer 16 ir absorptive 3217 3237 3257 3277 layer 17 ir absorptive 3218 3238 3258 3278 layer 18 ir absorptive 3219 3239 3259 3279 layer 19 ir absorptive 3220 3240 3260 3280 layer 20 ______________________________________ table 54 ______________________________________ substrate layer gas used and its temper- rf inner thick- name of flow rate ature power pressure ness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) ______________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer 6 no 2 contact sih.sub.4 20 250 50 0.05 0.5 layer 7 ch.sub.4 40 h.sub.2 50 contact sih.sub.4 10 250 50 0.05 0.5 layer 8 sif.sub.4 10 no 4 n.sub.2 4 ch.sub.4 6 ______________________________________ table 55 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 3301 3302 3303 3304 3305 3306 3307 no. __________________________________________________________________________ table 56 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 2 geh.sub.4 10 no 10 charge sih.sub.4 80 250 170 0.25 3 injection sif.sub.4 20 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 3 snh.sub.4 5 no 5 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10 .fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 57 ______________________________________ substrate layer gas used and its temper- rf inner thick- name of flow rate ature power pressure ness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) ______________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer 5 n.sub.2 10 contact sih.sub.4 20 250 50 0.05 0.5 layer 6 no 2 contact sih.sub.4 20 250 50 0.05 0.5 layer 7 ch.sub.4 40 h.sub.2 50 contact sih.sub.4 10 250 50 0.05 0.5 layer 8 sif.sub.4 10 no 4 n.sub.2 4 ch.sub.4 6 ______________________________________ table 58 __________________________________________________________________________ charge charge charge charge charge charge injection injection injection injection injection injection inhibition inhibition inhibition inhibition inhibition inhibition drum no. layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact layer 1 3401 3409 3417 3425 3433 3441 contact layer 2 3402 3410 3418 3426 3434 3442 contact layer 3 3403 3411 3419 3427 3435 3443 contact layer 4 3404 3412 3420 3428 3436 3444 contact layer 5 3405 3413 3421 3429 3437 3445 contact layer 6 3406 3414 3422 3430 3438 3446 contact layer 7 3407 3415 3423 3431 3439 3447 contact layer 8 3408 3416 3424 3432 3440 3448 __________________________________________________________________________ table 59 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 3501 3509 3517 3525 3533 3541 3549 layer 1 contact 3502 3510 3518 3526 3534 3542 3550 layer 2 contact 3503 3511 3519 3527 3535 3543 3551 layer 3 contact 3504 3512 3520 3528 3536 3544 3552 layer 4 contact 3505 3513 3521 3529 3537 3545 3553 layer 5 contact 3506 3514 3522 3530 3538 3546 3554 layer 6 contact 3507 3515 3523 3531 3539 3547 3555 layer 7 contact 3508 3516 3524 3532 3540 3548 3556 layer 8 __________________________________________________________________________ table 60 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 3601 3609 3617 3625 3633 3641 3649 layer 1 contact 3602 3610 3618 3626 3634 3642 3650 layer 2 contact 3603 3611 3619 3627 3635 3643 3651 layer 3 contact 3604 3612 3620 3628 3636 3644 3652 layer 4 contact 3605 3613 3621 3629 3637 3645 3653 layer 5 contact 3606 3614 3622 3630 3638 3646 3654 layer 6 contact 3607 3615 3623 3631 3639 3647 3655 layer 7 contact 3608 3616 3624 3632 3640 3648 3656 layer 8 __________________________________________________________________________ table 61 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 130 0.25 3 injection b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm inhibition no 4 layer 4 n.sub.2 4 ch.sub.4 6 charge sih.sub.4 100 250 130 0.25 3 injection ph.sub.3 (against sih.sub.4) 800 ppm inhibition geh.sub.4 10 layer 6 no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10 .fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 62 ______________________________________ charge injection charge injection charge injection inhibition layer 4 inhibition layer 6 inhibition layer 7 ______________________________________ drum 3701 3702 3703 no. ______________________________________ table 63 ______________________________________ substrate layer gas used and temper- rf inner thick- name of its flow rate ature power pressure ness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) ______________________________________ photo- sih.sub.4 200 250 250 0.40 20 conductive ar 200 layer 5 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 6 h.sub.2 200 ______________________________________ table 64 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 1 no 10 charge sih.sub.4 100 250 130 0.25 3 injection b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm inhibition no 4 layer 4 n.sub.2 4 ch.sub.4 6 charge sih.sub.4 100 250 130 0.25 3 injection ph.sub.3 (against sih.sub.4) 800 ppm inhibition geh.sub.4 10 layer 6 no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer 7 no* 10 no** 10 .fwdarw. 0*** __________________________________________________________________________ *substrate side 2 .mu.m **surface layer side 2 .mu.m ***constantly changed table 65 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 3801 3803 3805 3807 conductive layer 5 photo- 3802 3804 3806 3808 conductive layer 6 ______________________________________ table 66 ______________________________________ substrate layer gas used and temper- rf inner thick- name of its flow rate ature power pressure ness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) ______________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer 4 photo- sih.sub.4 200 250 250 0.40 20 conductive ar 200 layer 5 photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer 6 h.sub.2 200 ______________________________________ table 67 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 3901 3904 3907 3910 conductive layer 4 photo- 3902 3905 3908 3911 conductive layer 5 photo- 3903 3906 3909 3912 conductive layer 6 ______________________________________ ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 4001 4004 4007 4010 conductive layer 4 photo- 4002 4005 4008 4011 conductive layer 5 photo- 4003 4006 4009 4012 conductive layer 6 ______________________________________ table 70 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer 1 nh.sub.3 100 __________________________________________________________________________ table 69 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.40 20 conductive ar 200 layer __________________________________________________________________________ table 71 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4101 4121 4141 4161 layer 1 ir absorptive 4102 4122 4142 4162 layer 2 ir absorptive 4103 4123 4143 4163 layer 3 ir absorptive 4104 4124 4144 4164 layer 4 ir absorptive 4105 4125 4145 4165 layer 5 ir absorptive 4106 4126 4146 4166 layer 6 ir absorptive 4107 4127 4147 4167 layer 7 ir absorptive 4108 4128 4148 4168 layer 8 ir absorptive 4109 4129 4149 4169 layer 9 ir absorptive 4110 4130 4150 4170 layer 10 ir absorptive 4111 4131 4151 4171 layer 11 ir absorptive 4112 4132 4152 4172 layer 12 ir absorptive 4113 4133 4153 4173 layer 13 ir absorptive 4114 4134 4154 4174 layer 14 ir absorptive 4115 4135 4155 4175 layer 15 ir absorptive 4116 4136 4156 4176 layer 16 ir absorptive 4117 4137 4157 4177 layer 17 ir absorptive 4118 4138 4158 4178 layer 18 ir absorptive 4119 4139 4159 4179 layer 19 ir absorptive 4120 4140 4160 4180 layer 20 ______________________________________ table 72 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 150 250 350 0.40 20 conductive sif.sub.4 50 layer h.sub.2 200 __________________________________________________________________________ table 73 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4201 4221 4241 4261 layer 1 ir absorptive 4202 4222 4242 4262 layer 2 ir absorptive 4203 4223 4243 4263 layer 3 ir absorptive 4204 4224 4244 4264 layer 4 ir absorptive 4205 4225 4245 4265 layer 5 ir absorptive 4206 4226 4246 4266 layer 6 ir absorptive 4207 4227 4247 4267 layer 7 ir absorptive 4208 4228 4248 4268 layer 8 ir absorptive 4209 4229 4249 4269 layer 9 ir absorptive 4210 4230 4250 4270 layer 10 ir absorptive 4211 4231 4251 4271 layer 11 ir absorptive 4212 4232 4252 4272 layer 12 ir absorptive 4213 4233 4253 4273 layer 13 ir absorptive 4214 4234 4254 4274 layer 14 ir absorptive 4215 4235 4255 4275 layer 15 ir absorptive 4216 4236 4256 4276 layer 16 ir absorptive 4217 4237 4257 4277 layer 17 ir absorptive 4218 4238 4258 4278 layer 18 ir absorptive 4219 4239 4259 4279 layer 19 ir absorptive 4220 4240 4260 4280 layer 20 ______________________________________ table 74 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4301 4321 4341 4361 layer 1 ir absorptive 4302 4322 4342 4362 layer 2 ir absorptive 4303 4323 4343 4363 layer 3 ir absorptive 4304 4324 4344 4364 layer 4 ir absorptive 4305 4325 4345 4365 layer 5 ir absorptive 4306 4326 4346 4366 layer 6 ir absorptive 4307 4327 4347 4367 layer 7 ir absorptive 4308 4328 4348 4368 layer 8 ir absorptive 4309 4329 4349 4369 layer 9 ir absorptive 4310 4330 4350 4370 layer 10 ir absorptive 4311 4331 4351 4371 layer 11 ir absorptive 4312 4332 4352 4372 layer 12 ir absorptive 4313 4333 4353 4373 layer 13 ir absorptive 4314 4334 4354 4374 layer 14 ir absorptive 4315 4335 4355 4375 layer 15 ir absorptive 4316 4336 4356 4376 layer 16 ir absorptive 4317 4337 4357 4377 layer 17 ir absorptive 4318 4338 4358 4378 layer 18 ir absorptive 4319 4339 4359 4379 layer 19 ir absorptive 4320 4340 4360 4380 layer 20 ______________________________________ table 75 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4401 4421 4441 4461 layer 1 ir absorptive 4402 4422 4442 4462 layer 2 ir absorptive 4403 4423 4443 4463 layer 3 ir absorptive 4404 4424 4444 4464 layer 4 ir absorptive 4405 4425 4445 4465 layer 5 ir absorptive 4406 4426 4446 4466 layer 6 ir absorptive 4407 4427 4447 4467 layer 7 ir absorptive 4408 4428 4448 4468 layer 8 ir absorptive 4409 4429 4449 4469 layer 9 ir absorptive 4410 4430 4450 4470 layer 10 ir absorptive 4411 4431 4451 4471 layer 11 ir absorptive 4412 4432 4452 4472 layer 12 ir absorptive 4413 4433 4453 4473 layer 13 ir absorptive 4414 4434 4454 4474 layer 14 ir absorptive 4415 4435 4455 4475 layer 15 ir absorptive 4416 4436 4456 4476 layer 16 ir absorptive 4417 4437 4457 4477 layer 17 ir absorptive 4418 4438 4458 4478 layer 18 ir absorptive 4419 4439 4459 4479 layer 19 ir absorptive 4420 4440 4460 4480 layer 20 ______________________________________ table 76 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4501 4521 4541 4561 layer 1 ir absorptive 4502 4522 4542 4562 layer 2 ir absorptive 4503 4523 4543 4563 layer 3 ir absorptive 4504 4524 4544 4564 layer 4 ir absorptive 4505 4525 4545 4565 layer 5 ir absorptive 4506 4526 4546 4566 layer 6 ir absorptive 4507 4527 4547 4567 layer 7 ir absorptive 4508 4528 4548 4568 layer 8 ir absorptive 4509 4529 4549 4569 layer 9 ir absorptive 4510 4530 4550 4570 layer 10 ir absorptive 4511 4531 4551 4571 layer 11 ir absorptive 4512 4532 4552 4572 layer 12 ir absorptive 4513 4533 4553 4573 layer 13 ir absorptive 4514 4534 4554 4574 layer 14 ir absorptive 4515 4535 4555 4575 layer 15 ir absorptive 4516 4536 4556 4576 layer 16 ir absorptive 4517 4537 4557 4577 layer 17 ir absorptive 4518 4538 4558 4578 layer 18 ir absorptive 4519 4539 4559 4579 layer 19 ir absorptive 4520 4540 4560 4580 layer 20 ______________________________________ table 77 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 4601 4621 4641 4661 layer 1 ir absorptive 4602 4622 4642 4662 layer 2 ir absorptive 4603 4623 4643 4663 layer 3 ir absorptive 4604 4624 4644 4664 layer 4 ir absorptive 4605 4625 4645 4665 layer 5 ir absorptive 4606 4626 4646 4666 layer 6 ir absorptive 4607 4627 4647 4667 layer 7 ir absorptive 4608 4628 4648 4668 layer 8 ir absorptive 4609 4629 4649 4669 layer 9 ir absorptive 4610 4630 4650 4670 layer 10 ir absorptive 4611 4631 4651 4671 layer 11 ir absorptive 4612 4632 4652 4672 layer 12 ir absorptive 4613 4633 4653 4673 layer 13 ir absorptive 4614 4634 4654 4674 layer 14 ir absorptive 4615 4635 4655 4675 layer 15 ir absorptive 4616 4636 4656 4676 layer 16 ir absorptive 4617 4637 4657 4677 layer 17 ir absorptive 4618 4638 4658 4678 layer 18 ir absorptive 4619 4639 4659 4679 layer 19 ir absorptive 4620 4640 4660 4680 layer 20 ______________________________________ table 78 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 350 0.35 20 conductive he 200 layer __________________________________________________________________________ table 79 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 4701 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 4702 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 h.sub.2 100 nh.sub.3 100 4703 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 bias voltage of 150 v the cylinder __________________________________________________________________________ table 80 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 350 0.35 20 conductive he 200 layer __________________________________________________________________________ table 81 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 4801 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 4802 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 h.sub.2 100 nh.sub.3 100 4803 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 bias voltage of -150 v the cylinder __________________________________________________________________________ table 82 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 350 0.35 20 conductive he 200 layer __________________________________________________________________________ table 83 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 4901 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 4902 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 h.sub.2 100 nh.sub.3 100 4903 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 nh.sub.3 100 bias voltage of -150 v the cylinder __________________________________________________________________________ table 84 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 85 ______________________________________ drum no. 5101 5102 5103 5104 5105 ______________________________________ a (.mu.m) 25 50 50 12 12 b (.mu.m) 0.8 2.5 0.8 1.5 0.3 ______________________________________ table 86 ______________________________________ drum no. 5201 5202 5203 5204 5205 ______________________________________ c (.mu.m) 50 100 100 30 30 d (.mu.m) 1.2 5 0.9 2.5 0.4 ______________________________________ talbe 87 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 88 ______________________________________ intial increase electri- fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ degree of degree of surface break down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 89 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer h.sub.2 100 nh.sub.3 300 __________________________________________________________________________ table 90 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 91 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 92 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 93 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 94 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 95 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 96 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 97 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break inter- degree of degree of surface down abrasion ference background residual abrasion voltage resistance fringe fogginess stress ______________________________________ .circle. .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 98 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 99 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circle. ______________________________________ .circleincircle.: excellent .circle. : good table 100 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 101 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break inter- degree of degree of surface down abrasion ference background residual abrasion voltage resistance fringe fogginess stress ______________________________________ .circle. .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 102 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 103 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of surface down abrasion background residual abrasion voltage resistance fogginess stress ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 104 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.3 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 105 __________________________________________________________________________ initial electrification residual defective image increase of efficiency voltage ghost image flow defective image __________________________________________________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ surface breakdown abrasion interference degree of background degree of abrasion voltage resistance fringe fogginess residual stress __________________________________________________________________________ .circle. .circle. .circle. .circle. .circleincircle. .circleincircle. __________________________________________________________________________ .circleincircle.: excellent .circle. : good table 106 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 6701 6706 6711 6716 6721 6726 6731 conductive layer 1 photo- 6702 6707 6712 6717 6722 6727 6732 conductive layer 2 photo- 6703 6708 6713 6718 6723 6728 6733 conductive layer 3 photo- 6704 6709 6714 6719 6724 6729 6734 conductive layer 5 photo- 6705 6710 6715 6720 6725 6730 6735 conductive layer 6 __________________________________________________________________________ table 107 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer h.sub.2 100 nh.sub.3 300 __________________________________________________________________________ table 108 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 6801 6807 6813 6819 6825 6831 6837 conductive layer 1 photo- 6802 6808 6814 6820 6826 6832 6838 conductive layer 2 photo- 6803 6809 6815 6821 6827 6833 6839 conductive layer 3 photo- 6804 6810 6816 6822 6828 6834 6840 conductive layer 4 photo- 6805 6811 6817 6823 6829 6835 6841 conductive layer 5 photo- 6806 6812 6818 6824 6830 6836 6842 conductive layer 6 __________________________________________________________________________ table 109 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 bias voltage of the cylinder +150 v __________________________________________________________________________ table 110 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 6901 6907 6913 6919 6925 6931 6937 conductive layer 1 photo- 6902 6908 6914 6920 6926 6932 6938 conductive layer 2 photo- 6903 6909 6915 6921 6927 6933 6939 conductive layer 3 photo- 6904 6910 6916 6922 6928 6934 6940 conductive layer 4 photo- 6905 6911 6917 6923 6929 6935 6941 conducitve layer 5 photo- 6906 6912 6918 6924 6930 6936 6942 conductive layer 6 __________________________________________________________________________ table 111 __________________________________________________________________________ photo- photo- photo- photo- photo- conduc- conduc- conduc- conduc- conduc- tive tive tive tive tive layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ drum 7001 7002 7003 7004 7005 no. __________________________________________________________________________ table 112 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 7101 7102 7103 7104 7105 7106 no. __________________________________________________________________________ table 113 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 7201 7202 7203 7204 7205 7206 no. __________________________________________________________________________ table 114 ______________________________________ drum no. ______________________________________ ir absorptive 7301 layer 1 ir absorptive 7302 layer 2 ir absorptive 7303 layer 3 ir absorptive 7304 layer 4 ir absorptive 7305 layer 5 ir absorptive 7306 layer 6 ir absorptive 7307 layer 7 ir absorptive 7308 layer 8 ir absorptive 7309 layer 9 ir absorptive 7310 layer 10 ir absorptive 7311 layer 11 ir absorptive 7312 layer 12 ir absorptive 7313 layer 13 ir absorptive 7314 layer 14 ir absorptive 7315 layer 15 ir absorptive 7316 layer 17 ir absorptive 7317 layer 18 ir absorptive 7318 layer 19 ir absorptive 7319 layer 20 ______________________________________ table 115 __________________________________________________________________________ photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ ir absorptive 7401 7421 7441 7461 7481 layer 1 ir absorptive 7402 7422 7442 7462 7482 layer 2 ir absorptive 7403 7423 7443 7463 7483 layer 3 ir absorptive 7404 7424 7444 7464 7484 layer 4 ir absorptive 7405 7425 7445 7465 7485 layer 5 ir absorptive 7406 7426 7446 7466 7486 layer 6 ir absorptive 7407 7427 7477 7467 7487 layer 7 ir absorptive 7408 7428 7448 7468 7488 layer 8 ir absorptive 7409 7429 7449 7469 7489 layer 9 ir absorptive 7410 7430 7450 7470 7490 layer 10 ir absorptive 7411 7431 7451 7471 7491 layer 11 ir absorptive 7412 7432 7452 7472 7492 layer 12 ir absorptive 7413 7433 7453 7473 7493 layer 13 ir absorptive 7414 7434 7454 7474 7494 layer 14 ir absorptive 7415 7435 7455 7475 7495 layer 15 ir absorptive 7416 7436 7456 7476 7496 layer 16 ir absorptive 7417 7437 7457 7477 7497 layer 17 ir absorptive 7418 7438 7458 7478 7498 layer 18 ir absorptive 7419 7439 7459 7479 7499 layer 19 ir absorptive 7420 7440 7460 7480 74100 layer 20 __________________________________________________________________________ table 116 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 7501 7521 7541 7561 7581 75101 layer 1 ir absorptive 7502 7522 7542 7562 7582 75102 layer 2 ir absorptive 7503 7523 7543 7563 7583 75103 layer 3 ir absorptive 7504 7524 7544 7564 7584 75104 layer 4 ir absorptive 7505 7525 7545 7565 7585 75105 layer 5 ir absorptive 7506 7526 7546 7566 7586 75106 layer 6 ir absorptive 7507 7527 7547 7567 7587 75107 layer 7 ir absorptive 7508 7528 7548 7568 7588 75108 layer 8 ir absorptive 7509 7529 7549 7569 7589 75109 layer 9 ir absorptive 7510 7530 7550 7570 7590 75110 layer 10 ir absorptive 7511 7531 7551 7571 7591 75111 layer 11 ir absorptive 7512 7532 7552 7572 7592 75112 layer 12 ir absorptive 7513 7533 7553 7573 7593 75113 layer 13 ir absorptive 7514 7534 7554 7574 7594 75114 layer 14 ir absorptive 7515 7535 7555 7575 7595 75115 layer 15 ir absorptive 7516 7536 7556 7576 7596 75116 layer 16 ir absorptive 7517 7537 7557 7577 7597 75117 layer 17 ir absorptive 7518 7538 7558 7578 7598 75118 layer 18 ir absorptive 7519 7539 7559 7579 7599 75119 layer 19 ir absorptive 7520 7540 7560 7580 75100 75120 layer 20 __________________________________________________________________________ table 117 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 7601 7621 7641 7661 7681 76101 layer 1 ir absorptive 7602 7622 7642 7662 7682 76102 layer 2 ir absorptive 7603 7623 7643 7663 7683 76103 layer 3 ir absorptive 7604 7624 7644 7664 7684 76104 layer 4 ir absorptive 7605 7625 7645 7665 7685 76105 layer 5 ir absorptive 7606 7626 7646 7666 7686 76106 layer 6 ir absorptive 7607 7627 7647 7667 7687 76107 layer 7 ir absorptive 7608 7628 7648 7668 7688 76108 layer 8 ir absorptive 7609 7629 7649 7669 7689 76109 layer 9 ir absorptive 7610 7630 7650 7670 7690 76110 layer 10 ir absorptive 7611 7631 7651 7671 7691 76111 layer 11 ir absorptive 7612 7632 7652 7672 7692 76112 layer 12 ir absorptive 7613 7633 7653 7673 7693 76113 layer 13 ir absorptive 7614 7634 7654 7674 7694 76114 layer 14 ir absorptive 7615 7635 7655 7675 7695 76115 layer 15 ir absorptive 7616 7636 7656 7676 7696 76116 layer 16 ir absorptive 7617 7637 7657 7677 7697 76117 layer 17 ir absorptive 7618 7638 7658 7678 7698 76118 layer 18 ir absorptive 7619 7639 7659 7679 7699 76119 layer 19 ir absorptive 7620 7640 7660 7680 76100 76120 layer 20 __________________________________________________________________________ table 118 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 7701 7702 7703 no. ______________________________________ table 119 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 7801 7807 7813 7819 conductive layer 1 photo- 7802 7808 7814 7820 conductive layer 2 photo- 7803 7809 7815 7821 conductive layer 3 photo- 7804 7810 7816 7822 conductive layer 4 photo- 7805 7811 7817 7823 conductive layer 5 photo- 7806 7812 7818 7824 conductive layer 6 ______________________________________ table 120 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 7901 7907 7913 7919 conductive layer 1 photo- 7902 7908 7914 7920 conductive layer 2 photo- 7903 7909 7915 7921 conductive layer 3 photo- 7904 7910 7916 7922 conductive layer 4 photo- 7905 7911 7917 7923 conductive layer 5 photo- 7906 7912 7918 7924 conductive layer 6 ______________________________________ table 121 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 8001 8007 8013 8019 conductive layer 1 photo- 8002 8008 8014 8020 conductive layer 2 photo- 8003 8009 8015 8021 conductive layer 3 photo- 8004 8010 8016 8022 conductive layer 4 photo- 8005 8011 8017 8023 conductive layer 5 photo- 8006 8012 8018 8024 conductive layer 6 ______________________________________ table 122 ______________________________________ drum no. ______________________________________ ir absorptive 8101 layer 1 ir absorptive 8102 layer 2 ir absorptive 8103 layer 3 ir absorptive 8104 layer 4 ir absorptive 8105 layer 5 ir absorptive 8106 layer 6 ir absorptive 8107 layer 7 ir absorptive 8108 layer 8 ir absorptive 8109 layer 9 ir absorptive 8110 layer 10 ir absorptive 8111 layer 11 ir absorptive 8112 layer 12 ir absorptive 8113 layer 13 ir absorptive 8114 layer 14 ir absorptive 8115 layer 15 ir absorptive 8117 layer 17 ir absorptive 8118 layer 18 ir absorptive 8119 layer 19 ir absorptive 8120 layer 20 ______________________________________ table 123 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5 layer 7 ______________________________________ ir absorptive 8201 8221 8241 layer 1 ir absorptive 8202 8222 8242 layer 2 ir absorptive 8203 8223 8243 layer 3 ir absorptive 8204 8224 8244 layer 4 ir absorptive 8205 8225 8245 layer 5 ir absorptive 8206 8226 8246 layer 6 ir absorptive 8207 8227 8247 layer 7 ir absorptive 8208 8228 8248 layer 8 ir absorptive 8209 8229 8249 layer 9 ir absorptive 8210 8230 8250 layer 10 ir absorptive 8211 8231 8251 layer 11 ir absorptive 8212 8232 8252 layer 12 ir absorptive 8213 8233 8253 layer 13 ir absorptive 8214 8234 8254 layer 14 ir absorptive 8215 8235 8255 layer 15 ir absorptive 8216 8236 8256 layer 16 ir absorptive 8217 8237 8257 layer 17 ir absorptive 8218 8238 8258 layer 18 ir absorptive 8219 8239 8259 layer 19 ir absorptive 8220 8240 8260 layer 20 ______________________________________ table 124 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 8301 8321 8341 8361 layer 1 ir absorptive 8302 8322 8342 8362 layer 2 ir absorptive 8303 8323 8343 8363 layer 3 ir absorptive 8304 8324 8344 8364 layer 4 ir absorptive 8305 8325 8345 8365 layer 5 ir absorptive 8306 8326 8346 8366 layer 6 ir absorptive 8307 8327 8347 8367 layer 7 ir absorptive 8308 8328 8348 8368 layer 8 ir absorptive 8309 8329 8349 8369 layer 9 ir absorptive 8310 8330 8350 8370 layer 10 ir absorptive 8311 8331 8351 8371 layer 11 ir absorptive 8312 8332 8352 8372 layer 12 ir absorptive 8313 8333 8353 8373 layer 13 ir absorptive 8314 8334 8354 8374 layer 14 ir absorptive 8315 8335 8355 8375 layer 15 ir absorptive 8316 8336 8356 8376 layer 16 ir absorptive 8317 8337 8357 8377 layer 17 ir absorptive 8318 8338 8358 8378 layer 18 ir absorptive 8319 8339 8359 8379 layer 19 ir absorptive 8320 8340 8360 8380 layer 20 ______________________________________ table 125 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 8401 8421 8441 8461 layer 1 ir absorptive 8402 8422 8442 8462 layer 2 ir absorptive 8403 8423 8443 8463 layer 3 ir absorptive 8404 8424 8444 8464 layer 4 ir absorptive 8405 8425 8445 8465 layer 5 ir absorptive 8406 8426 8446 8466 layer 6 ir absorptive 8407 8427 8447 8467 layer 7 ir absorptive 8408 8428 8448 8468 layer 8 ir absorptive 8409 8429 8449 8469 layer 9 ir absorptive 8410 8430 8450 8470 layer 10 ir absorptive 8411 8431 8451 8471 layer 11 ir absorptive 8412 8432 8452 8472 layer 12 ir absorptive 8413 8433 8453 8473 layer 13 ir absorptive 8414 8434 8454 8474 layer 14 ir absorptive 8415 8435 8455 8475 layer 15 ir absorptive 8416 8436 8456 8476 layer 16 ir absorptive 8417 8437 8457 8477 layer 17 ir absorptive 8418 8438 8458 8478 layer 18 ir absorptive 8419 8439 8459 8479 layer 19 ir absorptive 8420 8440 8460 8480 layer 20 ______________________________________ table 126 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 8501 8502 8503 8504 8505 8506 8507 no. __________________________________________________________________________ table 127 ______________________________________ charge charge charge charge charge charge injec- injec- injec- injec- injec- injec- tion tion tion tion tion tion inhibi- inhibi- inhibi- inhibi- inhibi- inhibi- drum tion tion tion tion tion tion no. layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 ______________________________________ contact 8601 8609 8617 8625 8633 8641 layer 1 contact 8602 8610 8618 8626 8634 8642 layer 2 contact 8603 8611 8619 8627 8635 8643 layer 3 contact 8604 8612 8620 8628 8636 8644 layer 4 contact 8605 8613 8621 8629 8637 8645 layer 5 contact 8606 8614 8622 8630 8638 8646 layer 6 contact 8607 8615 8623 8631 8639 8647 layer 7 contact 8608 8616 8624 8662 8640 8648 layer 8 ______________________________________ table 128 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 8701 8709 8717 8725 8733 8741 8749 layer 1 contact 8702 8710 8718 8726 8734 8742 8750 layer 2 contact 8703 8711 8719 8727 8735 8743 8751 layer 3 contact 8704 8712 8720 8728 8736 8744 8752 layer 4 contact 8705 8713 8721 8729 8737 8745 8753 layer 5 contact 8706 8714 8722 8730 8738 8746 8754 layer 6 contact 8707 8715 8723 8731 8739 8747 8755 layer 7 contact 8708 8716 8724 8732 8740 8748 8756 layer 8 __________________________________________________________________________ table 129 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 8801 8809 8817 8825 8833 8841 8849 layer 1 contact 8802 8810 8818 8826 8834 8842 8850 layer 2 contact 8803 8811 8819 8827 8835 8843 8851 layer 3 contact 8804 8812 8820 8828 8836 8844 8852 layer 4 contact 8805 8813 8821 8829 8837 8845 8853 layer 5 contact 8806 8814 8822 8830 8838 8846 8854 layer 6 contact 8807 8815 8823 8831 8839 8847 8855 layer 7 contact 8808 8816 8824 8832 8840 8848 8856 layer 8 __________________________________________________________________________ table 130 ______________________________________ charge charge charge injection injection injection inhibition inhibition inhibition layer 4 layer 6 layer 7 ______________________________________ drum 8901 8902 8903 no. ______________________________________ table 131 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 9001 9003 9005 9007 conductive layer 5 photo- 9002 9004 9006 9008 conductive layer 6 ______________________________________ table 132 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 9101 9104 9107 9110 conductive layer 4 photo- 9102 9105 9108 9111 conductive layer 5 photo- 9103 9106 9109 9112 conductive layer 6 ______________________________________ table 133 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 9201 9204 9207 9210 conductive layer 4 photo- 9202 9205 9208 9211 conductive layer 5 photo- 9203 9206 9209 9212 conductive layer 6 ______________________________________ table 134 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer 1 nh.sub.3 100 __________________________________________________________________________ table 135 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9301 9321 9341 9361 layer 1 ir absorptive 9302 9322 9342 9362 layer 2 ir absorptive 9303 9323 9343 9363 layer 3 ir absorptive 9304 9324 9344 9364 layer 4 ir absorptive 9305 9325 9345 9365 layer 5 ir absorptive 9306 9326 9346 9366 layer 6 ir absorptive 9307 9327 9347 9367 layer 7 ir absorptive 9308 9328 9348 9368 layer 8 ir absorptive 9309 9329 9349 9369 layer 9 ir absorptive 9310 9330 9350 9370 layer 10 ir absorptive 9311 9331 9351 9371 layer 11 ir absorptive 9312 9332 9352 9372 layer 12 ir absorptive 9313 9333 9353 9373 layer 13 ir absorptive 9314 9334 9354 9374 layer 14 ir absorptive 9315 9335 9355 9375 layer 15 ir absorptive 9316 9336 9356 9376 layer 16 ir absorptive 9317 9337 9357 9377 layer 17 ir absorptive 9318 9338 9358 9378 layer 18 ir absorptive 9319 9339 9359 9379 layer 19 ir absorptive 9320 9340 9360 9380 layer 20 ______________________________________ table 136 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9401 9421 9441 9461 layer 1 ir absorptive 9402 9422 9442 9462 layer 2 ir absorptive 9403 9423 9443 9463 layer 3 ir absorptive 9404 9424 9444 9464 layer 4 ir absorptive 9405 9425 9445 9465 layer 5 ir absorptive 9406 9426 9446 9466 layer 6 ir absorptive 9407 9427 9447 9467 layer 7 ir absorptive 9408 9428 9448 9468 layer 8 ir absorptive 9409 9429 9449 9469 layer 9 ir absorptive 9410 9430 9450 9470 layer 10 ir absorptive 9411 9431 9451 9471 layer 11 ir absorptive 9412 9432 9452 9472 layer 12 ir absorptive 9413 9433 9453 9473 layer 13 ir absorptive 9414 9434 9454 9474 layer 14 ir absorptive 9415 9435 9455 9475 layer 15 ir absorptive 9416 9436 9456 9476 layer 16 ir absorptive 9417 9437 9457 9477 layer 17 ir absorptive 9418 9438 9458 9478 layer 18 ir absorptive 9419 9439 9459 9479 layer 19 ir absorptive 9420 9440 9460 9480 layer 20 ______________________________________ table 137 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9501 9521 9541 9561 layer 1 ir absorptive 9502 9522 9542 9562 layer 2 ir absorptive 9503 9523 9543 9563 layer 3 ir absorptive 9504 9524 9544 9564 layer 4 ir absorptive 9505 9525 9545 9565 layer 5 ir absorptive 9506 9526 9546 9566 layer 6 ir absorptive 9507 9527 9547 9567 layer 7 ir absorptive 9508 9528 9548 9568 layer 8 ir absorptive 9509 9529 9549 9569 layer 9 ir absorptive 9510 9530 9550 9570 layer 10 ir absorptive 9511 9531 9551 9571 layer 11 ir absorptive 9512 9532 9552 9572 layer 12 ir absorptive 9513 9533 9553 9573 layer 13 ir absorptive 9514 9534 9554 9574 layer 14 ir absorptive 9515 9535 9555 9575 layer 15 ir absorptive 9516 9536 9556 9576 layer 16 ir absorptive 9517 9537 9557 9577 layer 17 ir absorptive 9518 9538 9558 9578 layer 18 ir absorptive 9519 9539 9559 9579 layer 19 ir absorptive 9520 9540 9560 9580 layer 20 ______________________________________ table 138 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9601 9621 9641 9661 layer 1 ir absorptive 9602 9622 9642 9662 layer 2 ir absorptive 9603 9623 9643 9663 layer 3 ir absorptive 9604 9624 9644 9664 layer 4 ir absorptive 9605 9625 9645 9665 layer 5 ir absorptive 9606 9626 9646 9666 layer 6 ir absorptive 9607 9627 9647 9667 layer 7 ir absorptive 9608 9628 9648 9668 layer 8 ir absorptive 9609 9629 9649 9669 layer 9 ir absorptive 9610 9630 9650 9670 layer 10 ir absorptive 9611 9631 9651 9671 layer 11 ir absorptive 9612 9632 9652 9672 layer 12 ir absorptive 9613 9633 9653 9673 layer 13 ir absorptive 9614 9634 9654 9674 layer 14 ir absorptive 9615 9635 9655 9675 layer 15 ir absorptive 9616 9636 9656 9676 layer 16 ir absorptive 9617 9637 9657 9677 layer 17 ir absorptive 9618 9638 9658 9678 layer 18 ir absorptive 9619 9639 9659 9679 layer 19 ir absorptive 9620 9640 9660 9680 layer 20 ______________________________________ table 139 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9701 9721 9741 9761 layer 1 ir absorptive 9702 9722 9742 9762 layer 2 ir absorptive 9703 9723 9743 9763 layer 3 ir absorptive 9704 9724 9744 9764 layer 4 ir absorptive 9705 9725 9745 9765 layer 5 ir absorptive 9706 9726 9746 9766 layer 6 ir absorptive 9707 9727 9747 9767 layer 7 ir absorptive 9708 9728 9748 9768 layer 8 ir absorptive 9709 9729 9749 9769 layer 9 ir absorptive 9710 9730 9750 9770 layer 10 ir absorptive 9711 9731 9751 9771 layer 11 ir absorptive 9712 9732 9752 9772 layer 12 ir absorptive 9713 9733 9753 9773 layer 13 ir absorptive 9714 9734 9754 9774 layer 14 ir absorptive 9715 9735 9755 9775 layer 15 ir absorptive 9716 9736 9756 9776 layer 16 ir absorptive 9717 9737 9757 9777 layer 17 ir absorptive 9718 9738 9758 9778 layer 18 ir absorptive 9719 9739 9759 9779 layer 19 ir absorptive 9720 9740 9760 9780 layer 20 ______________________________________ table 140 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 9801 9821 9841 9861 layer 1 ir absorptive 9802 9822 9842 9862 layer 2 ir absorptive 9803 9823 9843 9863 layer 3 ir absorptive 9804 9824 9844 9864 layer 4 ir absorptive 9805 9825 9845 9865 layer 5 ir absorptive 9806 9826 9846 9866 layer 6 ir absorptive 9807 9827 9847 9867 layer 7 ir absorptive 9808 9828 9848 9868 layer 8 ir absorptive 9809 9829 9849 9869 layer 9 ir absorptive 9810 9830 9850 9870 layer 10 ir absorptive 9811 9831 9851 9871 layer 11 ir absorptive 9812 9832 9852 9872 layer 12 ir absorptive 9813 9833 9853 9873 layer 13 ir absorptive 9814 9834 9854 9874 layer 14 ir absorptive 9815 9835 9855 9875 layer 15 ir absorptive 9816 9836 9856 9876 layer 16 ir absorptive 9817 9837 9857 9877 layer 17 ir absorptive 9818 9038 9858 9878 layer 18 ir absorptive 9819 9839 9859 9879 layer 19 ir absorptive 9820 9840 9860 9880 layer 20 ______________________________________ table 141 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 9901 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 9902 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 h.sub.2 100 nh.sub.3 300 9903 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 bias voltage of the cylinder +100 v __________________________________________________________________________ table 142 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 10001 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 10002 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 h.sub.2 100 nh.sub.3 300 10003 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 bias voltage of the cylinder +100 v __________________________________________________________________________ table 143 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 10101 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 10102 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 h.sub.2 100 nh.sub.3 300 10103 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 nh.sub.3 100 bias voltage of the cylinder +100 v __________________________________________________________________________ table 144 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) layer 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 __________________________________________________________________________ table 145 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) layer 100 ppm no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 146 ______________________________________ initial electri- fication residual defective image efficiency voltage ghost image flow ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of defective surface down abrasion background image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good .delta.: applicable for practical use x: poor table 147 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) layer 100 ppm no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer h.sub.2 100 (lower nh.sub.3 100 layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 layer h.sub.2 100 (upper nh.sub.3 300 layer) __________________________________________________________________________ table 148 ______________________________________ initial electri- fication residual defective image efficiency voltage ghost image flow ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of defective surface down abrasion background image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good .delta.: applicable for practical use x: poor table 149 ______________________________________ intial electrification residual defective image efficiency voltage ghost image flow ______________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ degree of increase of surface breakdown abrasion background defective image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. excellent .circle. good .delta. applicable for practical use x poor table 150 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) layer 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 151 ______________________________________ intial electrification residual defective image efficiency voltage ghost image flow ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ degree of increase of surface breakdown abrasion background defective image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. excellent .circle. good .delta. applicable for practical use x poor table 152 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 153 ______________________________________ intial electrification residual defective image efficiency voltage ghost image flow ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ degree of increase of surface breakdown abrasion background defective image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. excellent .circle. good .delta. applicable for practical use x poor table 154 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 155 __________________________________________________________________________ intial electrification residual defective image increase of efficiency voltage ghost image flow defective image __________________________________________________________________________ .circle. .circle. .circle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ surface breakdown abrasion interference degree of background abrasion voltage resistance fringe fogginess __________________________________________________________________________ .circle. .circleincircle. .circleincircle. .circle. .circleincircle. __________________________________________________________________________ .circleincircle. excellent .circle. good table 156 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 157 ______________________________________ intial electrification residual defective image efficiency voltage ghost image flow ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ degree of increase of surface breakdown abrasion background defective image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. excellent .circle. good .delta. applicable for practical use x poor table 158 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) layer 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 159 __________________________________________________________________________ intial electrification residual defective image increase of efficiency voltage ghost image flow defective image __________________________________________________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. __________________________________________________________________________ surface breakdown abrasion interference degree of background abrasion voltage resistance fringe fogginess __________________________________________________________________________ .circle. .circleincircle. .circleincircle. .circle. .circleincircle. __________________________________________________________________________ .circleincircle. excellent .circle. good table 160 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) layer 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 161 ______________________________________ intial electrification residual defective image efficiency voltage ghost image flow ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ degree of increase of surface breakdown abrasion background defective image abrasion voltage resistance fogginess ______________________________________ .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. excellent .circle. good .delta. applicable for practical use x poor table 162 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) layer 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 163 ______________________________________ initial increase electri- of fication residual defective image defective efficiency voltage ghost image flow image ______________________________________ .circleincircle. .circle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of surface down abrasion interference background abrasion voltage resistance fringe fogginess ______________________________________ .circle. .circleincircle. .circleincircle. .circle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 164 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 11901 11906 11911 11916 11921 11926 11931 conductive layer 1 photo- 11902 11907 11912 11917 11922 11927 11932 conductive layer 2 photo- 11903 11908 11913 11918 11923 11928 11933 conductive layer 3 photo- 11904 11909 11914 11919 11924 11929 11934 conductive layer 5 photo- 11905 11910 11915 11920 11925 11930 11935 conductive layer 6 __________________________________________________________________________ table 165 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer h.sub.2 100 (lower nh.sub.3 100 layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 layer h.sub.2 100 (upper nh.sub.3 300 layer) __________________________________________________________________________ table 166 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 12001 12007 12013 12019 12025 12031 12037 conductive layer 1 photo- 12002 12008 12014 12020 12026 12032 12038 conductive layer 2 photo- 12003 12009 12015 12021 12027 12033 12039 conductive layer 3 photo- 12004 12010 12016 12022 12028 12034 12040 conductive layer 4 photo- 12005 12011 12017 12023 12029 12035 12041 conductive layer 5 photo- 12006 12012 12018 12024 12030 12036 12042 conductive layer 6 __________________________________________________________________________ table 167 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower bias voltage of -150 v layer) the cylinder surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper bias voltage of +150 v layer) the cylinder __________________________________________________________________________ table 168 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ photo- 12101 12107 12113 12119 12125 12131 12137 conductive layer 1 photo- 12102 12108 12114 12120 12126 12132 12138 conductive layer 2 photo- 12103 12109 12115 12121 12127 12133 12139 conductive layer 3 photo- 12104 12110 12116 12122 12128 12134 12140 conductive layer 4 photo- 12105 12111 12117 12123 12129 12135 12141 conductive layer 5 photo- 12106 12112 12118 12124 12130 12136 12142 conductive layer 6 __________________________________________________________________________ table 169 ______________________________________ photo- photo- photo- photo- photo- con- con- con- con- con- ductive ductive ductive ductive ductive layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ drum 12201 12202 12203 12204 12205 no. ______________________________________ table 170 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 12301 12302 12303 12304 12305 12306 no. __________________________________________________________________________ table 171 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 12401 12402 12403 12404 12405 12406 no. __________________________________________________________________________ table 172 ______________________________________ drum no. ______________________________________ ir absorptive 12501 layer 1 ir absorptive 12502 layer 2 ir absorptive 12503 layer 3 ir absorptive 12504 layer 4 ir absorptive 12505 layer 5 ir absorptive 12506 layer 6 ir absorptive 12507 layer 7 ir absorptive 12508 layer 8 ir absorptive 12509 layer 9 ir absorptive 12510 layer 10 ir absorptive 12511 layer 11 ir absorptive 12512 layer 12 ir absorptive 12513 layer 13 ir absorptive 12514 layer 14 ir absorptive 12515 layer 15 ir absorptive 12516 layer 17 ir absorptive 12517 layer 18 ir absorptive 12518 layer 19 ir absorptive 12519 layer 20 ______________________________________ table 173 __________________________________________________________________________ photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ ir absorptive 12601 12621 12641 12661 12681 layer 1 ir absorptive 12602 12622 12642 12662 12682 layer 2 ir absorptive 12603 12623 12643 12663 12683 layer 3 ir absorptive 12604 12624 12644 12664 12684 layer 4 ir absorptive 12605 12625 12645 12665 12685 layer 5 ir absorptive 12606 12626 12646 12666 12686 layer 6 ir absorptive 12607 12627 12647 12667 12687 layer 7 ir absorptive 12608 12628 12648 12668 12688 layer 8 ir absorptive 12609 12629 12649 12669 12689 layer 9 ir absorptive 12610 12630 12650 12670 12690 layer 10 ir absorptive 12611 12631 12651 12671 12691 layer 11 ir absorptive 12612 12632 12652 12672 12692 layer 12 ir absorptive 12613 12633 12653 12673 12693 layer 13 ir absorptive 12614 12634 12654 12674 12694 layer 14 ir absorptive 12615 12635 12655 12675 12695 layer 15 ir absorptive 12616 12636 12656 12676 12696 layer 16 ir absorptive 12617 12637 12657 12677 12697 layer 17 ir absorptive 12618 12638 12658 12678 12698 layer 18 ir absorptive 12619 12639 12659 12979 12699 layer 19 ir absorptive 12620 12640 12660 12680 126100 layer 20 __________________________________________________________________________ table 174 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 12701 12721 12741 12761 12781 127101 layer 1 ir absorptive 12702 12722 12742 12762 12782 127102 layer 2 ir absorptive 12703 12723 12743 12763 12783 127103 layer 3 ir absorptive 12704 12724 12744 12764 12784 127104 layer 4 ir absorptive 12705 12725 12745 12765 12785 127105 layer 5 ir absorptive 12706 12726 12746 12766 12786 127106 layer 6 ir absorptive 12707 12727 12747 12767 12787 127107 layer 7 ir absorptive 12708 12728 12748 12768 12788 127108 layer 8 ir absorptive 12709 12729 12749 12769 12789 127109 layer 9 ir absorptive 12710 12730 12750 12770 12790 127110 layer 10 ir absorptive 12711 12731 12751 12771 12791 127111 layer 11 ir absorptive 12712 12732 12752 12772 12792 127112 layer 12 ir absorptive 12713 12733 12753 12773 12793 127113 layer 13 ir absorptive 12714 12734 12754 12774 12794 127114 layer 14 ir absorptive 12715 12735 12755 12775 12795 127115 layer 15 ir absorptive 12716 12736 12756 12776 12796 127116 layer 16 ir absorptive 12717 12737 12757 12777 12797 127117 layer 17 ir absorptive 12718 12738 12758 12778 12798 127118 layer 18 ir absorptive 12719 12739 12759 12779 12799 127119 layer 19 ir absorptive 12720 12740 12760 12780 12700 127120 layer 20 __________________________________________________________________________ table 175 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductve conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 12801 12821 18241 12861 12881 128101 layer 1 ir absorptive 12802 12822 12842 12862 12882 128102 layer 2 ir absorptive 12803 12823 12843 12863 12883 128103 layer 3 ir absorptive 12804 12824 12844 12864 12884 128104 layer 4 ir absorptive 12805 12825 12845 12865 12885 128105 layer 5 ir absorptive 12806 12826 12846 12866 12886 128106 layer 6 ir absorptive 12807 12827 12847 12867 12887 128107 layer 7 ir absorptive 12808 12828 12848 12868 12888 128108 layer 8 ir absorptive 12809 12829 12849 12869 12889 128109 layer 9 ir absorptive 12810 12830 12850 12870 12890 128110 layer 10 ir absorptive 12811 12831 12851 12871 12891 128111 layer 11 ir absorptive 12812 12832 12852 12872 12892 128112 layer 12 ir absorptive 12813 12833 12853 12873 12893 128113 layer 13 ir absorptive 12814 12834 12854 12874 12894 128114 layer 14 ir absorptive 12815 12835 12855 12875 12895 128115 layer 15 ir absorptive 12816 12836 12856 12876 12896 128116 layer 16 ir absorptive 12817 12837 12857 12877 12897 128117 layer 17 ir absorptive 12818 12838 12858 12878 12898 128118 layer 18 ir absorptive 12819 12839 12879 12879 12899 128119 layer 19 ir absorptive 12820 12840 12860 12880 128100 128120 layer 20 __________________________________________________________________________ table 176 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 12901 12902 12903 no. ______________________________________ table 177 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 13001 13007 13013 13019 conductive layer 1 photo- 13002 13008 13014 13020 conductive layer 2 photo- 13003 13009 13015 13021 conductive layer 3 photo- 13004 13010 13016 13022 conductive layer 4 photo- 13005 13011 13017 13023 conductive layer 5 photo- 13006 13012 13018 13024 conductive layer 6 ______________________________________ table 178 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 13101 13107 13113 13119 conductive layer 1 photo- 13102 13108 13114 13120 conductive layer 2 photo- 13103 13109 13115 13121 conductive layer 3 photo- 13104 13110 13116 13122 conductive layer 4 photo- 13105 13111 13117 13123 conductive layer 5 photo- 13106 13112 13118 13124 conductive layer 6 ______________________________________ table 179 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 13201 13207 13213 13219 conductive layer 1 photo- 13202 13208 13214 13220 conductive layer 2 photo- 13203 13209 13215 13221 conductive layer 3 photo- 13204 13210 13216 13222 conductive layer 4 photo- 13205 13211 13217 13223 conductive layer 5 photo- 13206 13212 13218 13224 conductive layer 6 ______________________________________ table 180 ______________________________________ drum no. ______________________________________ ir absorptive 13301 layer 1 ir absorptive 13302 layer 2 ir absorptive 13303 layer 3 ir absorptive 13304 layer 4 ir absorptive 13305 layer 5 ir absorptive 13306 layer 6 ir absorptive 13307 layer 7 ir absorptive 13308 layer 8 ir absorptive 13309 layer 9 ir absorptive 13310 layer 10 ir absorptive 13311 layer 11 ir absorptive 13312 layer 12 ir absorptive 13313 layer 13 ir absorptive 13314 layer 14 ir absorptive 13315 layer 15 ir absorptive 13317 layer 17 ir absorptive 13318 layer 18 ir absorptive 13319 layer 19 ir absorptive 13320 layer 20 ______________________________________ table 181 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5 layer 7 ______________________________________ ir absorptive 13401 13421 13441 layer 1 ir absorptive 13402 13422 13442 layer 2 ir absorptive 13403 13423 13443 layer 3 ir absorptive 13404 13424 13444 layer 4 ir absorptive 13405 13425 13445 layer 5 ir absorptive 13406 13426 13446 layer 6 ir absorptive 13407 13427 13447 layer 7 ir absorptive 13408 13428 13448 layer 8 ir absorptive 13409 13429 13449 layer 9 ir absorptive 13410 13430 13450 layer 10 ir absorptive 13411 13431 13451 layer 11 ir absorptive 13412 13432 13452 layer 12 ir absorptive 13413 13433 13453 layer 13 ir absorptive 13414 13434 13454 layer 14 ir absorptive 13415 13435 13455 layer 15 ir absorptive 13416 13436 13456 layer 16 ir absorptive 13417 13437 13457 layer 17 ir absorptive 13418 13438 13458 layer 18 ir absorptive 13419 13439 13459 layer 19 ir absorptive 13420 13440 13460 layer 20 ______________________________________ table 182 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 13501 13521 13541 13561 layer 1 ir absorptive 13502 13522 13542 13562 layer 2 ir absorptive 13503 13523 13543 13563 layer 3 ir absorptive 13504 13524 13544 13564 layer 4 ir absorptive 13505 13525 13545 13565 layer 5 ir absorptive 13506 13526 13546 13566 layer 6 ir absorptive 13507 13527 13547 13567 layer 7 ir absorptive 13508 13528 13548 13568 layer 8 ir absorptive 13509 13529 13549 13569 layer 9 ir absorptive 13510 13530 13550 13570 layer 10 ir absorptive 13511 13531 13551 13571 layer 11 ir absorptive 13512 13532 13552 13572 layer 12 ir absorptive 13513 13533 13553 13573 layer 13 ir absorptive 13514 13534 13554 13574 layer 14 ir absorptive 13515 13535 13555 13575 layer 15 ir absorptive 13516 13536 13556 13576 layer 16 ir absorptive 13517 13537 13557 13577 layer 17 ir absorptive 13518 13538 13558 13578 layer 18 ir absorptive 13519 13539 13559 13579 layer 19 ir absorptive 13520 13540 13560 13580 layer 20 ______________________________________ table 183 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 13601 13621 13641 13661 layer 1 ir absorptive 13602 13622 13642 13662 layer 2 ir absorptive 13603 13623 13643 13663 layer 3 ir absorptive 13604 13624 13644 13664 layer 4 ir absorptive 13605 13625 13645 13665 layer 5 ir absorptive 13606 13626 13646 13666 layer 6 ir absorptive 13607 13627 13647 13667 layer 7 ir absorptive 13608 13628 13648 13668 layer 8 ir absorptive 13609 13629 13649 13669 layer 9 ir absorptive 13610 13630 13650 13670 layer 10 ir absorptive 13611 13631 13651 13671 layer 11 ir absoprtive 13612 13632 13652 13672 layer 12 ir absorptive 13613 13633 13653 13673 layer 13 ir absorptive 13614 13634 13654 13674 layer 14 ir absorptive 13615 13635 13655 13675 layer 15 ir absorptive 13616 13636 13656 13676 layer 16 ir absorptive 13617 13637 13657 13677 layer 17 ir absorptive 13618 13638 13658 13678 layer 18 ir absorptive 13619 13639 13659 13679 layer 19 ir absorptive 13620 13640 13660 13680 layer 20 ______________________________________ table 184 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 13701 13702 13703 13704 13705 13706 13707 no. __________________________________________________________________________ table 185 __________________________________________________________________________ charge charge charge charge charge charge injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition no. layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 13801 13809 13817 13825 13833 13841 layer 1 contact 13802 13810 13818 13826 13834 13842 layer 2 contact 13803 13811 13819 13827 13835 13843 layer 3 contact 13804 13812 13820 13828 13836 13844 layer 4 contact 13805 13813 13821 13829 13837 13845 layer 5 contact 13806 13814 13822 13830 13838 13846 layer 6 contact 13807 13815 13823 13831 13839 13847 layer 7 contact 13808 13816 13824 13832 13840 13848 layer 8 __________________________________________________________________________ table 186 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 13901 13909 13917 13925 13933 13941 13949 layer 1 contact 13902 13910 13918 13926 13934 13942 13950 layer 2 contact 13903 13911 13919 13927 13935 13943 13951 layer 3 contact 13904 13912 13920 13928 13936 13944 13952 layer 4 contact 13905 13913 13921 13929 13937 13945 13953 layer 5 contact 13906 13914 13922 13930 13938 13946 13954 layer 6 contact 13907 13915 13923 13931 13939 13947 13955 layer 7 contact 13908 13916 13924 13932 13940 13948 13956 layer 8 __________________________________________________________________________ table 187 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 layer 7 __________________________________________________________________________ contact 14001 14009 14017 14025 14033 14041 14049 layer 1 contact 14002 14010 14018 14026 14034 14042 14050 layer 2 contact 14003 14011 14019 14027 14035 14043 14051 layer 3 contact 14004 14012 14020 14028 14036 14044 14052 layer 4 contact 14005 14013 14021 14029 14037 14045 14053 layer 5 contact 14006 14014 14022 14030 14038 14046 14054 layer 6 contact 14007 14015 14023 14031 14039 14047 14055 layer 7 contact 14008 14016 14024 14032 14040 14048 14056 layer 8 __________________________________________________________________________ table 188 ______________________________________ charge injection charge injection charge injection inhibition layer 4 inhibition layer 6 inhibition 7 drum 14101 14102 14103 no. ______________________________________ table 189 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 14201 14203 14205 14207 conductive layer 5 photo- 14202 14204 14206 14208 conductive layer 6 ______________________________________ table 190 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 14301 14304 14307 14310 conductive layer 4 photo- 14302 14305 14308 14311 conductive layer 5 photo- 14303 14306 14309 14312 conductive layer 6 ______________________________________ table 191 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6 layer 7 ______________________________________ photo- 14401 14404 14407 14410 conductive layer 4 photo- 14402 14405 14408 14411 conductive layer 5 photo- 14403 14406 14409 14412 conductive layer 6 ______________________________________ table 192 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sscm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 193 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 14501 14521 14541 14561 layer 1 ir absorptive 14502 14522 14542 14562 layer 2 ir absorptive 14503 14523 14543 14563 layer 3 ir absorptive 14504 14524 14544 14564 layer 4 ir absorptive 14505 14525 14545 14565 layer 5 ir absorptive 14506 14526 14546 14566 layer 6 ir absorptive 14507 14527 14547 14567 layer 7 ir absorptive 14508 14528 14548 14568 layer 8 ir absorptive 14509 14529 14549 14569 layer 9 ir absorptive 14510 14530 14550 14570 layer 10 ir absorptive 14511 14531 14551 14571 layer 11 ir absorptive 14512 14532 14552 14572 layer 12 ir absorptive 14513 14533 14553 14573 layer 13 ir absorptive 14514 14534 14554 14574 layer 14 ir absorptive 14515 14535 14555 14575 layer 15 ir absorptive 14516 14536 14556 14576 layer 16 ir absorptive 14517 14537 14557 14577 layer 17 ir absorptive 14518 14538 14558 14578 layer 18 ir absorptive 14519 14539 14559 14579 layer 19 ir absorptive 14520 14540 14560 14580 layer 20 ______________________________________ table 194 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 14601 14621 14641 14661 layer 1 ir absorptive 14602 14622 14642 14662 layer 2 ir absorptive 14603 14623 14643 14663 layer 3 ir absortive 14604 14624 14644 14664 layer 4 ir absorptive 14605 14625 14645 14665 layer 5 ir absorptive 14606 14626 14646 14666 layer 6 ir absorptive 14607 14627 14647 14667 layer 7 ir absorptive 14608 14628 14648 14668 layer 8 ir absorptive 14609 14629 14649 14669 layer 9 ir absorptive 14610 14630 14650 14670 layer 10 ir absorptive 14611 14631 14651 14671 layer 11 ir absorptive 14612 14632 14652 14672 layer 12 ir absorptive 14613 14633 14653 14673 layer 13 ir absorptive 14614 14634 14654 14674 layer 14 ir absorptive 14615 14635 14655 14675 layer 15 ir absorptive 14616 14636 14656 14676 layer 16 ir absorptive 14617 14637 14657 14677 layer 17 ir absorptive 14618 14638 14658 14678 layer 18 ir absorptive 14619 14639 14659 14679 layer 19 ir absorptive 14620 14640 14660 14680 layer 20 ______________________________________ table 195 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 14701 14721 14741 14761 layer 1 ir absorptive 14702 14722 14742 14762 layer 2 ir absorptive 14703 14723 14743 14763 layer 3 ir absorptive 14704 14724 14744 14764 layer 4 ir absorptive 14705 14725 14745 14765 layer 5 ir absorptive 14706 14726 14746 14766 layer 6 ir absorptive 14707 14727 14747 14767 layer 7 ir absorptive 14708 14728 14748 14768 layer 8 ir absorptive 14709 14729 14749 14769 layer 9 ir absorptive 14710 14730 14750 14770 layer 10 ir absorptive 14711 14731 14751 14771 layer 11 ir absorptive 14712 14732 14752 14772 layer 12 ir absorptive 14713 14733 14753 14773 layer 13 ir absorptive 14714 14734 14754 14774 layer 14 ir absorptive 14715 14735 14755 14775 layer 15 ir absorptive 14716 14736 14756 14776 layer 16 ir absorptive 14717 14737 14757 14777 layer 17 ir absorptive 14718 14738 14758 14778 layer 18 ir absorptive 14719 14739 14759 14779 layer 19 ir absorptive 14720 14740 14760 14780 layer 20 ______________________________________ table 196 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 14801 14821 14841 14861 layer 1 ir absorptive 14802 14822 14842 14862 layer 2 ir absorptive 14803 14823 14843 14863 layer 3 ir absorptive 14804 14824 14844 14864 layer 4 ir absorptive 14805 14825 14845 14865 layer 5 ir absorptive 14806 14826 14846 14866 layer 6 ir absorptive 14807 14827 14847 14867 layer 7 ir absorptive 14808 14828 14848 14868 layer 8 ir absorptive 14809 14829 14849 14869 layer 9 ir absorptive 14810 14830 14850 14870 layer 10 ir absorptive 14811 14831 14851 14871 layer 11 ir absorptive 14812 14832 14852 14872 layer 12 ir absorptive 14813 14833 14853 14873 layer 13 ir absorptive 14814 14834 14854 14874 layer 14 ir absorptive 14815 14835 14855 14875 layer 15 ir absorptive 14816 14836 14856 14876 layer 16 ir absorptive 14817 14837 14857 14877 layer 17 ir absorptive 14818 14838 14858 14878 layer 18 ir absorptive 14819 14839 14859 14879 layer 19 ir absorptive 14820 14840 14860 14880 layer 20 ______________________________________ table 197 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 14901 14921 14941 14961 layer 1 ir absorptive 14902 14922 14942 14962 layer 2 ir absorptive 14903 14923 14943 14963 layer 3 ir absorptive 14904 14924 14944 14964 layer 4 ir absorptive 14905 14925 14945 14965 layer 5 ir absorptive 14906 14926 14946 14966 layer 6 ir absorptive 14907 14927 14947 14967 layer 7 ir absorptive 14908 14928 14948 14968 layer 8 ir absorptive 14909 14929 14949 14969 layer 9 ir absorptive 14910 14990 14950 14970 layer 10 ir absorptive 14911 14931 14951 14971 layer 11 ir absorptive 14912 14932 14952 14972 layer 12 ir absorptive 14913 14933 14953 14973 layer 13 ir absorptive 14914 14934 14954 14974 layer 14 ir absorptive 14915 14935 14955 14975 layer 15 ir absorptive 14916 14936 14956 14996 layer 16 ir absorptive 14917 14937 14957 14977 layer 17 ir absorptive 14918 14938 14958 14978 layer 18 ir absorptive 14919 14939 14959 14979 layer 19 ir absorptive 14920 14940 14960 14980 layer 20 ______________________________________ table 198 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5 layer 7 ______________________________________ ir absorptive 15051 15021 15041 15061 layer 1 ir absorptive 15002 15022 15042 15062 layer 2 ir absorptive 15003 15023 15043 15063 layer 3 ir absorptive 15004 15024 15044 15064 layer 4 ir absorptive 15005 15025 15045 15065 layer 5 ir absorptive 15006 15026 15046 15066 layer 6 ir absorptive 15007 15027 15047 15067 layer 7 ir absorptive 15008 15028 15048 15068 layer 8 ir absorptive 15009 15029 15049 15069 layer 9 ir absorptive 15010 15030 15050 15070 layer 10 ir absorptive 15011 15031 15051 15071 layer 11 ir absorptive 15012 15032 15052 15072 layer 12 ir absorptive 15013 15033 15053 15073 layer 13 ir absorptive 15014 15034 15054 15074 layer 14 ir absorptive 15015 15035 15055 15075 layer 15 ir absorptive 15016 15036 15056 15076 layer 16 ir absorptive 15017 15037 15057 15077 layer 17 ir absorptive 15018 15038 15058 15078 layer 18 ir absorptive 15019 15039 15059 15079 layer 19 ir absorptive 15020 15040 15060 15080 layer 20 ______________________________________ table 199 __________________________________________________________________________ gas used and its substrate inner layer flow rate temperature rf power pressure thickness drum no. (sscm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 15101 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 15102 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 h.sub.2 100 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 nh.sub.3 300 15103 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 200 __________________________________________________________________________ gas used and its substrate inner layer flow rate temperature rf power pressure thickness drum no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 15201 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 15202 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 h.sub.2 100 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 nh.sub.3 300 15203 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 201 __________________________________________________________________________ gas used and its substrate inner layer flow rate temperature rf power pressure thickness drum no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 15301 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 15302 lower layer b.sub.2 h.sub.6 /ar (20%) 500 h.sub.2 100 250 200 0.40 0.3 nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 nh.sub.3 300 15303 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 202 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) __________________________________________________________________________ table 203 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 203 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 204 ______________________________________ intial drum electrification residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ drum increase of surface breakdown abrasion no. defective image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 205 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer h.sub.2 100 nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 205 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer h.sub.2 100 nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 206 ______________________________________ initial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 207 ______________________________________ initial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 208 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 208 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 209 ______________________________________ initial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 210 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 210 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 211 ______________________________________ initial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 212 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 212 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 213 ______________________________________ initial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion interference no. image abrasion voltage resistance fringe ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ .circleincircle.: excellent .circle. : good table 214 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 214 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 215 ______________________________________ initial drum electrification residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: exellent .circle. : good table 216 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 216 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 217 ______________________________________ initial drum electrification residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion interference no. image abrasion voltage resistence fringe ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ .circleincircle.: excellent .circle. : good table 218 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 218 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 219 ______________________________________ initial drum electrification residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ increase of break drum defective surface down abrasion no. image abrasion voltage resistance ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 220 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperatrue rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 220 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 221 ______________________________________ initial drum electrification residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ increase of break drum defective surface down abrasion interference no. image abrasion voltage resistance fringe ______________________________________ (a) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circleincircle. .circleincircle. .circle. ______________________________________ .circleincircle.: excellent .circle. : good table 222 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 16701 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16702 sif.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 16703 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16704 sih.sub.4 200 250 250 0.40 20 ar 200 16705 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 16706* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16707* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 16708* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16709* sih.sub.4 200 250 250 0.40 20 ar 200 16710* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 203 (b) markless case: followed table 203 (a) table 223 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 16801 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16802 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 16803 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16804 sih.sub.4 200 250 250 0.40 20 ar 200 16805 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 16806* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16807* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 16808* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16809* sih.sub.4 200 250 250 0.40 20 ar 200 16810* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 205 (b) markless case: followed table 205 (a) table 224 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 16901 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16902 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 16903 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16304 sih.sub.4 200 250 250 0.40 20 ar 200 16905 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 16906* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 16907* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub. 4) 100 ppm no 6 16908* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 16309* sih.sub.4 200 250 250 0.40 20 ar 200 16910* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 203 (b) markless case: followed table 203 (a) table 225 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 17001 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm geh.sub.4 10 no 10 17002 sih.sub.4 80 250 170 0.25 3 sif.sub.4 20 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm snh.sub.4 5 no 5 17003 sih.sub.4 100 250 130 0.25 3 b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 17004* sih.sub.4 100 250 150 0.35 3 h.sub.2 100 ph.sub.3 (against sih.sub.4) 800 ppm 17005* sih.sub.4 100 250 130 0.25 3 ph.sub.3 (against sih.sub.4) 800 ppm geh.sub.4 10 no 10 17006 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no** 10 no*** 10 .fwdarw. 0**** __________________________________________________________________________ *surface layer followed table 208(b) markless case: followed table 208(a) **substrate side 2 .mu.m ***surface layer side 1 .mu.m ****constantly changed table 226 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 17101 17106 17111 17116 17121 17126 17131 conductive layer 1 photo- 17102 17107 17112 17117 17122 17127 17132 conductive layer 2 photo- 17103 17108 17113 17118 17123 17128 17133 conductive layer 3 photo- 17104 17109 17114 17119 17124 17129 17134 conductive layer 5 photo- 17105 17110 17115 17120 17125 17130 17135 conductive layer 6 __________________________________________________________________________ *surface layer followed table 6 (b) markless case: followed table 6 (a) table 227 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer a h.sub.2 100 nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm surface* b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 layer b h.sub.2 100 nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ *each of the surface layers a and b is individually used in accordance with the kind of the lower layer table 228 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 17201 17207 17213 17219 17225 17231 17237 conductive layer 1 photo- 17202 17208 17214 17220 17226 17232 17238 conductive layer 2 photo- 17203 17209 17215 17221 17227 17233 17239 conductive layer 3 photo- 17204 17210 17216 17222 17228 17234 17240 conductive layer 4 photo- 17205 17211 17217 17223 17229 17235 17241 conductive layer 5 photo- 17206 17212 17218 17224 17230 17236 17242 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 229 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer a nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm bias voltage of -150 v the cylinder surface* b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer b nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm bias voltage of -150 v the cylinder __________________________________________________________________________ *each of the surface layers a and b is individually used in accordance with the kind of the lower layer table 230 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 17301 17307 17313 17319 17325 17331 17337 conductive layer 1 photo- 17302 17308 17314 17320 17326 17362 17338 conductive layer 2 photo- 17303 17309 17315 17321 17327 17333 17339 conductive layer 3 photo- 17304 17310 17316 17322 17328 17334 17340 conductive layer 4 photo- 17305 17311 17317 17323 17329 17335 17341 conductive layer 5 photo- 17306 17312 17318 17324 17330 17336 17342 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 231 ______________________________________ photo- photo- photo- con- photo- con- photo- con- ductive conductive ductive conductive ductive layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ drum 17401 17402 17403 17404 17405 no. 17406* 17407* 17408* 17409* 17410* ______________________________________ *surface layer followed table 210 (b) markless case: followed table 210 (a) table 232 ______________________________________ photo- photo- photo- photo- photo- photo- con- con- con- con- con- con- ductive ductive ductive ductive ductive ductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 ______________________________________ drum 17501 17502 17503 17504 17505 17506 no. 17507* 17508* 17509* 17510* 17511* 17512* ______________________________________ *surface layer b was used. markless case: surface layer a was used. table 233 ______________________________________ photo- photo- photo- photo- photo- photo- con- con- con- con- con- con- ductive ductive ductive ductive ductive ductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 ______________________________________ drum 17601 17602 17603 17604 17605 17606 no. 17607* 17608* 17609* 17610* 17611* 17612* ______________________________________ *surface layer b was used. *markless case: surface layer a was used. table 234 ______________________________________ drum no. ______________________________________ ir absorptive 17701 17720* layer 1 ir absorptive 17702 17721* layer 2 ir absorptive 17703 17722* layer 3 ir absorptive 17704 17723* layer 4 ir absorptive 17705 17724* layer 5 ir absorptive 17706 -- layer 6 ir absorptive 17707 -- layer 7 ir absorptive 17708 -- layer 8 ir absorptive 17709 -- layer 9 ir absorptive 17710 -- layer 10 ir absorptive 17711 -- layer 11 ir absorptive 17712 -- layer 12 ir absorptive 17713 -- layer 13 ir absorptive 17714 -- layer 14 ir absorptive 17715 -- layer 15 ir absorptive 17716 -- layer 17 ir absorptive 17717 17725* layer 18 ir absorptive 17718 17726* layer 19 ir absorptive 17719 17727* layer 20 ______________________________________ *:surface layer followed table 212(b) markless case:followed 212(a) table 235 __________________________________________________________________________ photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ ir absorptive 17801 17821 17841 17861 17881 layer 1 ir absorptive 17802 17822 17842 17862 17882 layer 2 ir absorptive 17803 17823 17843 17863 17883 layer 3 ir absorptive 17804 17824 17844 17864 17884 layer 4 ir absorptive 17805 17825 17845 17865 17885 layer 5 ir absorptive 17806 17826 17846 17866 17886 layer 6 ir absorptive 17807 17827 17847 17867 17887 layer 7 ir absorptive 17808 17828 17848 17868 17888 layer 8 ir absorptive 17809 17829 17849 17869 17889 layer 9 ir absorptive 17810 17830 17850 17870 17890 layer 10 ir absorptive 17811 17831 17851 17871 17891 layer 11* ir absorptive 17812 17832 17852 17872 17892 layer 12* ir absorptive 17813 17833 17853 17873 17893 layer 13* ir absorptive 17814 17834 17854 17874 17894 layer 14* ir absorptive 17815 17835 17855 17875 17895 layer 15* ir absorptive 17816 17836 17856 17876 17896 layer 16 ir absorptive 17817 17837 17857 17877 17897 layer 17* ir absorptive 17818 17838 17858 17878 17898 layer 18 ir absorptive 17819 17839 17859 17879 17899 layer 19 ir absorptive 17820 17840 17860 17880 178100 layer 20 __________________________________________________________________________ *: surface layer followed table 212(b) markless case: followed table 212(a) table 236 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 17901 17921 17941 17961 17981 179101 layer 1 ir absorptive 17902 17922 17942 17962 17982 179102 layer 2 ir absorptive 17903 17923 17943 17963 17983 179103 layer 3 ir absorptive 17904 17924 17944 17964 17984 179104 layer 4 ir absorptive 17905 17925 17945 17965 17985 179105 layer 5 ir absorptive 17906 17926 17946 17966 17986 179106 layer 6 ir absorptive 17907 17927 17947 17967 17987 179107 layer 7 ir absorptive 17908 17928 17948 17968 17988 179108 layer 8 ir absorptive 17909 17929 17949 17969 17989 179109 layer 9 ir absorptive 17910 17930 17950 17970 17990 179110 layer 10 ir absorptive 17911 17931 17951 17971 17991 179111 layer 11* ir absorptive 17912 17932 17952 17972 17992 179112 layer 12* ir absorptive 17913 17933 17953 17973 17993 179113 layer 13* ir absorptive 17914 17934 17954 17974 17994 179114 layer 14* ir absorptive 17915 17935 17955 17975 17995 179115 layer 15* ir absorptive 17916 17936 17956 17976 17996 179116 layer 16 ir absorptive 17917 17937 17957 17977 17997 179117 layer 17* ir absorptive 17918 17938 17958 17978 17998 179118 layer 18 ir absorptive 17919 17939 17959 17979 17999 179119 layer 19 ir absorptive 17920 17940 17960 17980 179100 179120 layer 20 __________________________________________________________________________ *: surface layer b was used markless case: surface layer a was used table 237 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 18001 18021 18041 18061 18081 180101 layer 1 ir absorptive 18002 18022 18042 18062 18082 180102 layer 2 ir absorptive 18003 18023 18043 18063 18083 180103 layer 3 ir absorptive 18004 18024 18044 18064 18084 180104 layer 4 ir absorptive 18005 18025 18045 18065 18085 180105 layer 5 ir absorptive 18006 18026 18046 18066 18086 180106 layer 6 ir absorptive 18007 18027 18047 18067 18087 180107 layer 7 ir absorptive 18008 18028 18048 18068 18088 180108 layer 8 ir absorptive 18009 18029 18049 18069 18089 180109 layer 9 ir absorptive 18010 18030 18050 18070 18090 180110 layer 10 ir absorptive 18011 18031 18051 18071 18091 180111 layer 11* ir absorptive 18012 18032 18052 18072 18092 180112 layer 12* ir absorptive 18013 18033 18053 18073 18093 180113 layer 13* ir absorptive 18014 18034 18054 18074 18094 180114 layer 14* ir absorptive 18015 18035 18055 18075 18095 180115 layer 15* ir absorptive 18016 18036 18056 18076 18096 180116 layer 16 ir absorptive 18017 18037 18057 18077 18097 180117 layer 17* ir absorptive 18018 18038 18058 18078 18098 180118 layer 18 ir absorptive 18019 18039 18059 18079 18099 180119 layer 19 ir absorptive 18020 18040 18060 18080 180100 180120 layer 20 __________________________________________________________________________ *: surface layer b was used markless case: surface layer a was used table 238 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 18101 18102 18103 no. 18104* 18105* 18106* ______________________________________ *surface layer followed table 214 (b) markless case: followed table 214 (a) table 239 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 18201 18207* 18213 18219 conductive layer 1 photo- 18202 18208 18214* 18220 conductive layer 2 photo- 18203* 18209 18215 18221 conductive layer 3 photo- 18204 18210 18216 18222* conductive layer 4 photo- 18205 18211 18217* 18223 conductive layer 5 photo- 18206 18212* 18218 18224 conductive layer 6 ______________________________________ *surface layer followed table 214 (b) markless case: followed table 214 (a) table 240 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 18301 18307 18313* 18319 conductive layer 1 photo- 18302 18308* 18314 18320 conductive layer 2 photo- 18303 18309 18315 18321* conductive layer 3 photo- 18304* 18310 18316 18322 conductive layer 4 photo- 18305 18311* 18317 18323 conductive layer 5 photo- 18306 18312 18318* 18324 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 241 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 18402* 18407 18413 18419 conductive layer 1 photo- 18402 18408 18414* 18420 conductive layer 2 photo- 18403 18409 18415 18421* conductive layer 3 photo- 18404 18410* 18416 18422 conductive layer 4 photo- 18405 18411 18417 18423* conductive layer 5 photo- 18406* 18412 18418 18424 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 242 ______________________________________ drum no. ______________________________________ ir absorptive 18501 18521 layer 1 * ir absorptive 18502 18522 layer 2 * ir absorptive 18503 18523 layer 3 * ir absorptive 18504 18524 layer 4 * ir absorptive 18505 18526 layer 5 * ir absorptive 18506 18526 layer 6 * ir absorptive 18507 18527 layer 7 * ir absorptive 18508 18528 layer 8 * ir absorptive 18509 18529 layer 9 * ir absorptive 18510 18530 layer 10 * ir absorptive 18511 18531 layer 11 * ir absorptive 18512 18532 layer 12 * ir absorptive 18513 18533 layer 13 * ir absorptive 18514 18534 layer 14 * ir absorptive 18515 18535 layer 15 * ir absorptive 18516 18536 layer 16 * ir absorptive 18517 18537 layer 17 * ir absorptive 18518 18538 layer 18 * ir absorptive 18519 18539 layer 19 * ir absorptive 18520 18540 layer 20 * ______________________________________ *charge injection inhibition layer and surface layer followed table 216(b) markless case: followed table 216(a) table 243 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5* layer 7 ______________________________________ ir absorptive 18601 18621 18641 layer 1 ir absorptive 18602 18622 18642 layer 2 ir absorptive 18603 18623 18643 layer 3 ir absorptive 18604 18624 18644 layer 4 ir absorptive 18605 18625 18645 layer 5 ir absorptive 18606 18626 18646 layer 6 ir absorptive 18607 18627 18647 layer 7 ir absorptive 18608 18628 18648 layer 8 ir absorptive 18609 18629 18649 layer 9 ir absorptive 18610 18630 18650 layer 10 ir absorptive 18611 18631 18651 layer 11 ir absorptive 18612 18632 18652 layer 12 ir absorptive 18613 18633 18653 layer 13 ir absorptive 18614 18634 18654 layer 14 ir absorptive 18615 18635 18655 layer 15 ir absorptive 18616 18636 18656 layer 16 ir absorptive 18617 18637 18657 layer 17 ir absorptive 18618 18638 18658 layer 18 ir absorptive 18619 18639 18659 layer 19 ir absorptive 18620 18640 18660 layer 20 ______________________________________ *surface layer followed table 216(b) markless case: followed table 216(a) table 244 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 18701 18721 18741 18761 layer 1 ir absorptive 18702 18722 18742 18762 layer 2 ir absorptive 18703 18723 18743 18763 layer 3 ir absorptive 18704 18724 18744 18764 layer 4 ir absorptive 18705 18725 18745 18765 layer 5 ir absorptive 18706 18726 18746 18766 layer 6 ir absorptive 18707 18727 18747 18767 layer 7 ir absorptive 18708 18728 18748 18768 layer 8 ir absorptive 18709 18729 18749 18769 layer 9 ir absorptive 18710 18730 18750 18770 layer 10 ir absorptive 18711 18731 18751 18771 layer 11 ir absorptive 18712 18732 18752 18772 layer 12 ir absorptive 18713 18733 18753 18773 layer 13 ir absorptive 18714 18734 18754 18774 layer 14 ir absorptive 18715 18735 18755 18775 layer 15 ir absorptive 18716 18736 18756 18776 layer 16 ir absorptive 18717 18737 18757 18777 layer 17 ir absorptive 18718 18738 18758 18778 layer 18 ir absorptive 18719 18739 18759 18779 layer 19 ir absorptive 18720 18740 18760 18780 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 245 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 18801 18821 18841 18861 layer 1 ir absorptive 18802 18822 18842 18862 layer 2 ir absorptive 18803 18823 18843 18863 layer 3 ir absorptive 18804 18824 18844 18864 layer 4 ir absorptive 18805 18825 18845 18865 layer 5 ir absorptive 18806 18826 18846 18866 layer 6 ir absorptive 18807 18827 18847 18867 layer 7 ir absorptive 18808 18828 18848 18868 layer 8 ir absorptive 18809 18829 18849 18869 layer 9 ir absorptive 18810 18830 18850 18870 layer 10 ir absorptive 18811 18831 18851 18871 layer 11 ir absorptive 18812 18832 18852 18872 layer 12 ir absorptive 18813 18833 18853 18873 layer 13 ir absorptive 18814 18834 18854 18874 layer 14 ir absorptive 18815 18835 18855 18875 layer 15 ir absorptive 18816 18836 18856 18876 layer 16 ir absorptive 18817 18837 18857 18877 layer 17 ir absorptive 18818 18838 18858 18878 layer 18 ir absorptive 18819 18839 18859 18879 layer 19 ir absorptive 18820 18840 18860 18880 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 246 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 18901 18902 18903 18904 18905 18906 18907 no. 18908* 18909* 18910* 18911* 18912* 18913* 18914* __________________________________________________________________________ *charge injection inhibition layer and surface layer followed table 218 (b) markless case: followed table 218 (a) table 247 __________________________________________________________________________ charge charge charge charge charge charge injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition no. layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 19001 19009 19017 19025 19033 19041 layer 1 contact 19002 19010 19018 19026 19034 19042 layer 2 contact 19003 19011 19019 19027 19035 19043 layer 3 contact 19004 19012 19020 19028 19036 19044 layer 4 contact 19005 19013 19021 19029 19037 19045 layer 5 contact 19006 19014 19022 19030 19038 19046 layer 6 contact 19007 19015 19023 19031 19039 19047 layer 7 contact 19008 19016 19024 19032 19040 19048 layer 8 __________________________________________________________________________ *surface layer followed table 218 (b) markless case: followed table 218 (a) table 248 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 19101 19109 19117 19125 19133 19141 19149 layer 1 contact 19102 19110 19118 19126 19134 19142 19150 layer 2 contact 19103 19111 19119 19127 19135 19143 19151 layer 3 contact 19104 19112 19120 19128 19136 19144 19152 layer 4 contact 19105 19113 19121 19129 19137 19145 19153 layer 5 contact 19106 19114 19122 19130 19138 19146 19154 layer 6 contact 19107 19115 19123 19131 19139 19147 19155 layer 7 contact 19108 19116 19124 19132 19140 19148 19156 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 249 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 19201 19209 19217 19225 19233 19241 19249 layer 1 contact 19202 19210 19218 19226 19234 19242 19250 layer 2 contact 19203 19211 19219 19227 19235 19243 19251 layer 3 contact 19204 19212 19220 19228 19236 19244 19252 layer 4 contact 19205 19213 19221 19229 19237 19245 19253 layer 5 contact 19206 19214 19222 19230 19238 19246 19254 layer 6 contact 19207 19215 19223 19231 19239 19247 19255 layer 7 contact 19208 19216 19224 19232 19240 19248 19256 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 250 ______________________________________ charge charge charge injection injection injection inhibition inhibition inhibition layer 4 layer 6* layer 7 ______________________________________ drum 19301 19302 19303 no. ______________________________________ *surface layer followed table 220 (b) markless case: followed table 220 (a) table 251 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 19401 19403 19405 19407 conductive layer 5 photo- 19402 19404 19406 19408 conductive layer 6 ______________________________________ *surface layer followed table 220 (b) markless case: followed table 220 (a) table 252 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 19501 19504 19507 19510 conductive layer 4 photo- 19502 19505 19508 19511 conductive layer 5 photo- 19503 19506 19509 19512 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 253 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 19601 19604 19607 19610 conductive layer 4 photo- 19602 19605 19608 19611 conductive layer 5 photo- 19603 19606 19609 19612 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 254 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer a nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer b nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 255 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 19701 19721 19741 19761 layer 1 ir absorptive 19702 19722 19742 19762 layer 2 ir absorptive 19703 19723 19743 19763 layer 3 ir absorptive 19704 19724 19744 19764 layer 4 ir absorptive 19705 19725 19745 19765 layer 5 ir absorptive 19706 19726 19746 19766 layer 6 ir absorptive 19707 19727 19747 19767 layer 7 ir absorptive 19708 19728 19748 19768 layer 8 ir absorptive 19709 19729 19749 19769 layer 9 ir absorptive 19710 19730 19750 19770 layer 10 ir absorptive 19711 19731 19751 19771 layer 11 ir absorptive 19712 19732 19752 19772 layer 12 ir absorptive 19713 19733 19753 19773 layer 13 ir absorptive 19714 19734 19754 19774 layer 14 ir absorptive 19715 19735 19755 19775 layer 15 ir absorptive 19716 19736 19756 19776 layer 16 ir absorptive 19717 19737 19757 19777 layer 17 ir absorptive 19718 19738 19758 19778 layer 18 ir absorptive 19719 19739 19759 19779 layer 19 ir absorptive 19720 19740 19760 19780 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 256 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 19801 19821 19841 19861 layer 1 ir absorptive 19802 19822 19842 19862 layer 2 ir absorptive 19803 19823 19843 19863 layer 3 ir absorptive 19804 19824 19844 19864 layer 4 ir absorptive 19805 19825 19845 19865 layer 5 ir absorptive 19806 19826 19846 19866 layer 6 ir absorptive 19807 19827 19847 19867 layer 7 ir absorptive 19808 19828 19848 19868 layer 8 ir absorptive 19809 19829 19849 19869 layer 9 ir absorptive 19810 19830 19850 19870 layer 10 ir absorptive 19811 19831 19851 19871 layer 11 ir absorptive 19812 19832 19852 19872 layer 12 ir absorptive 19813 19833 19853 19873 layer 13 ir absorptive 19814 19834 19854 19874 layer 14 ir absorptive 19815 19835 19855 19875 layer 15 ir absorptive 19816 19836 19856 19876 layer 16 ir absorptive 19817 19837 19857 19877 layer 17 ir absorptive 19818 19838 19858 19878 layer 18 ir absorptive 19819 19839 19859 19879 layer 19 ir absorptive 19820 19840 19860 19880 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 257 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 19901 19921 19941 19961 layer 1 ir absorptive 19902 19922 19942 19962 layer 2 ir absorptive 19903 19923 19943 19963 layer 3 ir absorptive 19904 19924 19944 19964 layer 4 ir absorptive 19905 19925 19945 19965 layer 5 ir absorptive 19906 19926 19946 19966 layer 6 ir absorptive 19907 19927 19947 19967 layer 7 ir absorptive 19908 19928 19948 19968 layer 8 ir absorptive 19909 19929 19949 19969 layer 9 ir absorptive 19910 19930 19950 19970 layer 10 ir absorptive 19911 19931 19951 19971 layer 11 ir absorptive 19912 19932 19952 19972 layer 12 ir absorptive 19913 19933 19953 19973 layer 13 ir absorptive 19914 19934 19954 19974 layer 14 ir absorptive 19915 19935 19955 19975 layer 15 ir absorptive 19916 19936 19956 19976 layer 16 ir absorptive 19917 19937 19957 19977 layer 17 ir absorptive 19918 19938 19958 19978 layer 18 ir absorptive 19919 19938 19959 19979 layer 19 ir absorptive 19920 19940 19960 19980 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 258 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 20001 20021 20041 20061 layer 1 ir absorptive 20002 20022 20042 20062 layer 2 ir absorptive 20003 20023 20043 20063 layer 3 ir absorptive 20004 20024 20044 20064 layer 4 ir absorptive 20005 20025 20045 20065 layer 5 ir absorptive 20006 20026 20046 20066 layer 6 ir absorptive 20007 20027 20047 20067 layer 7 ir absorptive 20008 20028 20048 20068 layer 8 ir absorptive 20009 20029 20049 20069 layer 9 ir absorptive 20010 20030 20050 20070 layer 10 ir absorptive 20011 20031 20051 20071 layer 11 ir absorptive 20012 20032 20052 20072 layer 12 ir absorptive 20013 20033 20053 20073 layer 13 ir absorptive 20014 20034 20054 20074 layer 14 ir absorptive 20015 20035 20055 20075 layer 15 ir absorptive 20016 20036 20056 20076 layer 16 ir absorptive 20017 20037 20057 20078 layer 17 ir absorptive 20018 20038 20058 20078 layer 18 ir absorptive 20019 20039 20059 20079 layer 19 ir absorptive 20020 20040 20060 20080 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 259 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 20101 20121 20141 20161 layer 1 ir absorptive 20102 20122 20142 20162 layer 2 ir absorptive 20103 20123 20143 20163 layer 3 ir absorptive 20104 20124 20144 20164 layer 4 ir absorptive 20105 20125 20145 20165 layer 5 ir absorptive 20106 20126 20146 20166 layer 6 ir absorptive 20107 20127 20147 20167 layer 7 ir absorptive 20108 20128 20148 20168 layer 8 ir absorptive 20109 20129 20149 20169 layer 9 ir absorptive 20110 20130 20150 20170 layer 10 ir absorptive 20111 20131 20151 20171 layer 11 ir absorptive 20112 20132 20152 20172 layer 12 ir absorptive 20113 20133 20153 20173 layer 13 ir absorptive 20114 20134 20154 20174 layer 14 ir absorptive 20115 20135 20155 20175 layer 15 ir absorptive 20116 20136 20156 20176 layer 16 ir absorptive 20117 20137 20157 20177 layer 17 ir absorptive 20118 20138 20158 20178 layer 18 ir absorptive 20119 20139 20159 20179 layer 19 ir absorptive 20120 20140 20160 20180 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 260 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 20201 20221 20241 20261 layer 1 ir absorptive 20202 20222 20242 20262 layer 2 ir absorptive 20203 20223 20243 20263 layer 3 ir absorptive 20204 20224 20244 20264 layer 4 ir absorptive 20205 20225 20245 20265 layer 5 ir absorptive 20206 20226 20246 20266 layer 6 ir absorptive 20207 20227 20247 20267 layer 7 ir absorptive 20208 20228 20248 20268 layer 8 ir absorptive 20209 20229 20249 20269 layer 9 ir absorptive 20210 20230 20250 20270 layer 10 ir absorptive 20211 20231 20251 20271 layer 11 ir absorptive 20212 20232 20252 20272 layer 12 ir absorptive 20213 20233 20253 20273 layer 13 ir absorptive 20214 20234 20254 20274 layer 14 ir absorptive 20215 20235 20255 20275 layer 15 ir absorptive 20216 20236 20256 20276 layer 16 ir absorptive 20217 20237 20257 20277 layer 17 ir absorptive 20218 20238 20258 20278 layer 18 ir absorptive 20219 20239 20259 20279 layer 19 ir absorptive 20220 20240 20260 20280 layer 20 ______________________________________ *surface layer b was used markless case: surface layer a was used table 261 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 20301 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 20302 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 100 20303 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder __________________________________________________________________________ table 262 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 20401 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 20402 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 100 20403 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder __________________________________________________________________________ table 263 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 20501 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 20502 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 100 20503 b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder __________________________________________________________________________ table 264 __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 265 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 265 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 266 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 267 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer h.sub.2 100 nh.sub.3 300 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 267 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer h.sub.2 100 nh.sub.3 300 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 268 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 269 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 270 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 270 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 271 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 272 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 272 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 273 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 274 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 274 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 275 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 276 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 276 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 277 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 278 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 278 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 279 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.:excellent .circle. :good table 280 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 280 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph 3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 281 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.:excellent .circle. :good table 282 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 282 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 283 ______________________________________ initial increase electri- defec- of drum fication residual tive image defective no. efficiency voltage ghost image flow image ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. .circle. ______________________________________ break degree of degree of drum surface down abrasion background residual no. abrasion voltage resistance fogginess stress ______________________________________ (a) .circle. .circle. .circle. .circleincircle. .circleincircle. (b) .circle. .circle. .circle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.:excellent .circle. :good table 284 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 21901 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 21902 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 21903 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 21904 sih.sub.4 200 250 250 0.40 20 ar 200 21905 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 21906* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 21907* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 21908* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 21909* sih.sub.4 200 250 250 0.40 20 ar 200 21910* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 265 (b) markless case: followed table 265 (a) table 285 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 22001 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 22002 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 22003 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 22004 sih.sub.4 200 250 250 0.40 20 ar 200 22005 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 22006* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 22007* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 22008* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 22009* sih.sub.4 200 250 250 0.40 20 ar 200 22010* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 267 (b) markless case: followed table 267 (a) table 286 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 22101 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 22102 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 22103 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 22104 sih.sub.4 200 250 250 0.40 20 ar 200 22105 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 22106* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 22107* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 22108* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 22109* sih.sub.4 200 250 250 0.40 20 ar 200 22110* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 265 (b) markless case: followed table 265 (a) table 287 __________________________________________________________________________ substrate inner layer drum gas used and its temperature rf power pressure thickness no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 22201 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm geh.sub.4 10 no 10 22202 sih.sub.4 80 250 170 0.25 3 sif.sub.4 20 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm snh.sub.4 5 no 5 22203 sih.sub.4 100 250 130 0.25 3 b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 22204* sih.sub.4 100 250 150 0.35 3 h.sub.2 100 ph.sub.3 (against sih.sub.4) 800 ppm 22205* sih.sub.4 100 250 130 0.25 3 ph.sub.3 (against sih.sub.4) 800 ppm geh.sub.4 10 no 10 22206 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no* 10 no** 10.fwdarw.0*** __________________________________________________________________________ *surface layer followed table 208(b) markless case: followed table 208(a) *substrate side 2 .mu.m **surface layer side 1 .mu.m ***constantly changed table 288 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 22301 22306 22311 22316 22321 22326 22331 conductive layer 1 photo- 22302 22307 22312 22317 22322 22327 22332 conductive layer 2 photo- 22303 22308 22313 22318 22323 22328 22233 conductive layer 3 photo- 22304 22309 22314 22319 22324 22329 22334 conductive layer 5 photo- 22305 22310 22315 22320 22325 22330 22335 conductive layer 6 __________________________________________________________________________ *surface layer followed table 6(b) markless case: followed table 6(a) table 289 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer a h.sub.2 100 nh.sub.3 300 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm surface* b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 layer b h.sub.2 100 nh.sub.3 300 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ *each of surface layers a and b is individually used in accordance with the kind of the lower layer table 290 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 22401 22407 22413 22419 22425 22431 22437 conductive layer 1 photo- 22402 22408 22414 22420 22426 22432 22438 conductive layer 2 photo- 22403 22409 22415 22421 22427 22433 22439 conductive layer 3 photo- 22404 22410 22416 22422 22428 22434 22440 conductive layer 4 photo- 22405 22411 22417 22423 22429 22435 22441 conductive layer 5 photo- 22406 22412 22418 22424 22430 22436 22442 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 291 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer a nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm bias voltage of +100 v the cylinder surface* b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer b nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm bias voltage of +100 v the cylinder __________________________________________________________________________ *each of surface layers a and b is individually used in accordance with the kind of the lower layer table 292 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 22501 22507 22513 22519 22525 22531 22537 conductive layer 1 photo- 22502 22508 22514 22520 22526 22532 22538 conductive layer 2 photo- 22503 22509 22515 22521 22527 22533 22539 conductive layer 3 photo- 22504 22510 22516 22522 22528 22534 22540 conductive layer 4 photo- 22505 22511 22517 22523 22529 22535 22541 conductive layer 5 photo- 22506 22512 22518 22524 22530 22536 22542 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 293 ______________________________________ photo- photo- photo- conduc- photo- conduc- photo- conduc- tive conductive tive conductive tive layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ drum 22601 22602 22603 22604 22605 no. 22606* 22607* 22608* 22609* 22610* ______________________________________ *surface layer followed table 272(b) markless case: followed table 272(a) table 294 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 22701 22702 22703 22704 22705 22706 no. 22707* 22708* 22709* 22710* 22711* 22712* __________________________________________________________________________ *surface layer b was used. markless case: surface layer a was used. table 295 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 22801 22802 22803 22804 22805 22806 no. 22807* 22808* 22809* 22810* 22811* 22812* __________________________________________________________________________ *surface layer b was used. markless case: surface layer a was used. table 296 ______________________________________ drum no. ______________________________________ ir absorptive 22901 22920* layer 1 ir absorptive 22902 22921* layer 2 ir absorptive 22903 22922* layer 3 ir absorptive 22904 22923* layer 4 ir absorptive 22905 22924* layer 5 ir absorptive 22906 -- layer 6 ir absorptive 22907 -- layer 7 ir absorptive 22908 -- layer 8 ir absorptive 22909 -- layer 9 ir absorptive 22910 -- layer 10 ir absorptive 22911 -- layer 11 ir absorptive 22912 -- layer 12 ir absorptive 22913 -- layer 13 ir absorptive 22914 -- layer 14 ir absorptive 22915 -- layer 15 ir absorptive 22916 -- layer 17 ir absorptive 22917 22925* layer 18 ir absorptive 22918 22926* layer 19 ir absorptive 22919 22927* layer 20 ______________________________________ *surface layer followed table 274(b) markless case: followed 274(a) table 297 __________________________________________________________________________ photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ ir aborptive 23001 23021 23041 23061 23081 layer 1 ir absorptive 23002 23022 23042 23062 23082 layer 2 ir absorptive 23003 23023 23043 23063 23083 layer 3 ir absorptive 23004 23024 23044 23064 23084 layer 4 ir absorptive 23005 23025 23045 23065 23085 layer 5 ir absorptive 23006 23026 23046 23066 23086 layer 6 ir absorptive 23007 23027 23047 23067 23087 layer 7 ir absorptive 23008 23028 23048 23068 23088 layer 8 ir absorptive 23009 23029 23049 23069 23089 layer 9 ir absorptive 23010 23030 23050 23070 23090 layer 10 ir absorptive 23011 23031 23051 23071 23091 layer 11* ir absorptive 23012 23032 23052 23072 23092 layer 12* ir absorptive 23013 23033 23053 23073 23093 layer 13* ir absorptive 23014 23034 23054 23074 23094 layer 14* ir absorptive 23015 23035 23055 23075 23095 layer 15* ir absorptive 23016 23036 23056 23076 23096 layer 16* ir absorptive 23017 23037 23057 23077 23097 layer 17* ir absorptive 23018 23038 23058 23078 23098 layer 18 ir absorptive 23019 23039 23059 23079 23099 layer 19 ir absorptive 23020 23040 23060 23080 230100 layer 20 __________________________________________________________________________ *surface layer followed table 274(b) markless case: followed table 274(a) table 298 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 23101 23121 23141 23161 23181 231101 layer 1 ir absorptive 23102 23122 23142 23162 23182 231102 layer 2 ir absorptive 23103 23123 23143 23163 23183 231103 layer 3 ir absorptive 23104 23124 23144 23164 23184 231104 layer 4 ir absorptive 23105 23125 23145 23165 23185 231105 layer 5 ir absorptive 23106 23126 23146 23166 23186 231106 layer 6 ir absorptive 23107 23127 23147 23167 23187 231107 layer 7 ir absorptive 23108 23128 23148 23168 23188 231108 layer 8 ir absorptive 23109 23129 23149 23169 23189 231109 layer 9 ir absorptive 23110 23130 23150 23170 23190 231110 layer 10 ir absorptive 23111 23131 23151 23171 23191 231111 layer 11* ir absorptive 23112 23132 23152 23172 23192 231112 layer 12* ir absorptive 23113 23133 23153 23173 23193 231113 layer 13* ir absorptive 23114 23134 23154 23174 23194 231114 layer 14* ir absorptive 23115 23135 23155 23175 23195 231115 layer 15* ir absorptive 23116 23136 23156 23176 23196 231116 layer 16 ir absorptive 23117 23137 23157 23177 23197 231117 layer 17* ir absorptive 23118 23138 23158 23178 23198 231118 layer 18 ir absorptive 23119 23139 23159 23179 23199 231119 layer 19 ir absorptive 23120 23140 23160 23180 231100 231120 layer 20 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 299 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 laeyr 6 __________________________________________________________________________ ir absorptive 23201 23221 23241 23261 23281 232101 layer 1 ir absorptive 23202 23222 23242 23262 23282 232102 layer 2 ir absorptive 23203 23223 23243 23263 23283 232103 layer 3 ir absorptive 23204 23224 23244 23264 23284 232104 layer 4 ir absorptive 23205 23225 23245 23265 23285 232105 layer 5 ir absorptive 23206 23226 23246 23266 23286 232106 layer 6 ir absorptive 23207 23227 23247 23267 23287 232107 layer 7 ir absorptive 23208 23228 23248 23268 23288 232108 layer 8 ir absorptive 23209 23229 23249 23269 23289 232109 layer 9 ir absorptive 23210 23230 23250 23270 23290 232110 layer 10 ir absorptive 23211 23231 23251 23271 23291 232111 layer 11* ir absorptive 23212 23232 23252 23272 23292 232112 layer 12* ir absorptive 23213 23233 23253 23273 23293 232113 layer 13* ir absorptive 23214 23234 23254 23274 23294 232114 layer 14* ir absorptive 23215 23235 23255 23275 23295 232115 layer 15* ir absorptive 23216 23236 23256 23276 23296 232116 layer 16* ir absorptive 23217 23237 23257 23277 23297 232117 layer 17* ir absorptive 23218 23238 23258 23278 23298 232118 layer 18 ir absorptive 23219 23239 23259 23279 23299 232119 layer 19 ir absorptive 23220 23240 23260 23280 232100 232120 layer 20 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 300 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 23301 23302 23303 no. 23304* 23305* 23306* ______________________________________ *surface layer followed table 276(b) markless case: followed table 276(a) table 301 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 23401 23407* 23413 23419 conductive layer 1 photo- 23402 23408 23414* 23420 conductive layer 2 photo- 23403* 23409 23415 23421 conductive layer 3 photo- 23404 23410 23416 23422* conductive layer 4 photo- 23405 23411 23417* 23423 conductive layer 5 photo- 23406 23412* 23418 23424 conductive layer 6 ______________________________________ *surface layer followed table 276(b) markless case: followed table 276(a) table 302 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 23501 23507 23513* 23519 conductive layer 1 photo- 23502 23508* 23514 23520 conductive layer 2 photo- 23503 23509 23515 23521* conductive layer 3 photo- 23504* 23510 23516 23522 conductive layer 4 photo- 23505 23511* 23517 23523 conductive layer 5 photo- 23506 23512 23518* 23524 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 303 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 23601* 23607 23613 23619 conductive layer 1 photo- 23602 23608 23614* 23620 conductive layer 2 photo- 23603 23609 23615 23621* conductive layer 3 photo- 23604 23610* 23616 23622 conductive layer 4 photo- 23605 23611 23617 23623* conductive layer 5 photo- 23606* 23612 23618 23624 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 304 ______________________________________ drum no. ______________________________________ ir absorptive 23701 23721 layer 1 * ir absorptive 23702 23722 layer 2 * ir absorptive 23703 23723 layer 3 * ir absorptive 23704 23724 layer 4 * ir absorptive 23705 23726 layer 5 * ir absorptive 23706 23726 layer 6 * ir absorptive 23707 23727 layer 7 * ir absorptive 23708 23728 layer 8 * ir absorptive 23709 23729 layer 9 * ir absorptive 23710 23730 layer 10 * ir absorptive 23711 23731 layer 11 * ir absorptive 23712 23732 layer 12 * ir absorptive 23713 23733 layer 13 * ir absorptive 23714 23734 layer 14 * ir absorptive 23715 23735 layer 15 * ir absorptive 23717 23737 layer 17 * ir absorptive 23718 23738 layer 18 * ir absorptive 23719 23739 layer 19 * ir absorptive 23720 23740 layer 20 * ______________________________________ *charge injection inhibition layer and surface layer followed table 278(b) markless case: followed table 178(a) table 305 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5* layer 7 ______________________________________ ir absorptive 23801 23821 23841 layer 1 ir absorptive 23802 23822 23842 layer 2 ir absorptive 23803 23823 23843 layer 3 ir absorptive 23804 23824 23844 layer 4 ir absorptive 23805 23825 23845 layer 5 ir absorptive 23806 23826 23846 layer 6 ir absorptive 23807 23827 23847 layer 7 ir absorptive 23808 23828 23848 layer 8 ir absorptive 23809 23829 23849 layer 9 ir absorptive 23810 23830 23840 layer 10 ir absorptive 23811 23831 23851 layer 11 ir absorptive 23812 23832 23852 layer 12 ir absorptive 23813 23833 23853 layer 13 ir absorptive 23814 23834 23854 layer 14 ir absorptive 23815 23835 23855 layer 15 ir absorptive 23816 23836 23856 layer 16 ir absorptive 23817 23837 23857 layer 17 ir absorptive 23818 23838 23858 layer 18 ir absorptive 23819 23839 23859 layer 19 ir absorptive 23820 23840 23860 layer 20 ______________________________________ *: surface layer followed table 278(b) markless case: followed table 278(a) table 306 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 23901 23921 23941 23961 layer 1 ir absorptive 23902 23922 23942 23962 layer 2 ir absorptive 23903 23923 23943 23963 layer 3 ir absorptive 23904 23924 23944 23964 layer 4 ir absorptive 23905 23925 23945 23965 layer 5 ir absorptive 23906 23926 23946 23966 layer 6 ir absorptive 23907 23927 23947 23967 layer 7 ir absorptive 23908 23928 23948 23968 layer 8 ir absorptive 23909 23929 23949 23969 layer 9 ir absorptive 23910 23930 23950 23970 layer 10 ir absorptive 23911 23931 23951 23971 layer 11 ir absorptive 23912 23932 23952 23972 layer 12 ir absorptive 23913 23933 23953 23973 layer 13 ir absorptive 23914 23934 23954 23974 layer 14 ir absorptive 23915 23935 23955 23975 layer 15 ir absorptive 23916 23936 23956 23976 layer 16 ir absorptive 23917 23937 23957 23977 layer 17 ir absorptive 23918 23938 23958 23978 layer 18 ir absorptive 23919 23939 23959 23979 layer 19 ir absorptive 23920 23940 23960 23980 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 307 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 24001 24021 24041 24061 layer 1 ir absorptive 24002 24022 24042 24062 layer 2 ir absorptive 24003 24023 24043 24063 layer 3 ir absorptive 24004 24024 24044 24064 layer 4 ir absorptive 24005 24025 24045 24065 layer 5 ir absorptive 24006 24026 24046 24066 layer 6 ir absorptive 24007 24027 24047 24067 layer 7 ir absorptive 24008 24028 24048 24068 layer 8 ir absorptive 24009 24029 24049 24069 layer 9 ir absorptive 24010 24030 24050 24070 layer 10 ir absorptive 24011 24031 24051 24071 layer 11 ir absorptive 24012 24032 24052 24072 layer 12 ir absorptive 24013 24033 24053 24073 layer 13 ir absorptive 24014 24034 24054 24074 layer 14 ir absorptive 24015 24035 24055 24075 layer 15 ir absorptive 24016 24036 24056 24076 layer 16 ir absorptive 24017 24037 24057 24077 layer 17 ir absorptive 24018 24038 24058 24078 layer 18 ir absorptive 24019 24039 24059 24079 layer 19 ir absorptive 24020 24040 24060 24080 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 308 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 24101 24102 24103 24104 24105 24106 24107 no. 24108* 24109* 24110* 24111* 24112* 24113* 24114* __________________________________________________________________________ *charge injection inhibition layer and surface layer followed table 280(b markless case: followed table 280(a) table 309 __________________________________________________________________________ charge charge charge charge charge charge injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition no. layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 24201 24209 24217 24225 24233 24241 layer 1 contact 24202 24210 24218 24226 24234 24242 layer 2 contact 24203 24211 24219 24227 24235 24243 layer 3 contact 24204 24212 24220 24228 24236 24244 layer 4 contact 24205 24213 24221 24229 24237 24245 layer 5 contact 24206 24214 24222 24230 24238 24246 layer 6 contact 24207 24215 24223 24231 24239 24247 layer 7 contact 24208 24216 24224 24232 24240 24248 layer 8 __________________________________________________________________________ *surface layer followed table 280(b) markless case: followed table 280(a) table 310 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibiton no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 24301 24309 24317 24325 24333 24341 24349 layer 1 contact 24302 24310 24318 24326 24334 24342 24350 layer 2 contact 24303 24311 24319 24327 24335 24343 24351 layer 3 contact 24304 24312 24320 24328 24336 24344 24352 layer 4 contact 24305 24313 24321 24329 24337 24345 24353 layer 5 contact 24306 24314 24322 24330 24338 24346 24354 layer 6 contact 24307 24315 24323 24331 24339 24347 24355 layer 7 contact 24308 24316 24324 24332 24340 24348 24356 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 311 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 24401 24409 24417 24425 24433 24441 24449 layer 1 contact 24402 24410 24418 24426 24434 24442 24450 layer 2 contact 24403 24411 24419 24427 24435 24443 24451 layer 3 contact 24404 24412 24420 24428 24436 24444 24452 layer 4 contact 24405 24413 24421 24429 24437 24445 24453 layer 5 contact 24406 24414 24422 24430 24438 24446 24454 layer 6 contact 24407 24415 24423 24431 24439 24447 24455 layer 7 contact 24408 24416 24424 24432 24440 24448 24456 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 312 ______________________________________ charge charge charge injection injection injection inhibition inhibition inhibition layer 4 layer 6* layer 7 ______________________________________ drum 24501 24502 24503 no. ______________________________________ *surface layer followed table 282 (b) markless case: followed table 282 (a) table 313 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 24601 24603 24605 24607 conductive layer 5 photo- 24602 24604 24606 24608 conductive layer 6 ______________________________________ *surface layer followed table 282 (b) markless case: followed table 282 (a) table 314 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 24701 24704 24707 24710 conductive layer 4 photo- 24702 24705 24708 24711 conductive layer 5 photo- 24703 24706 24709 24712 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 315 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 24801 24804 24807 24810 conductive layer 4 photo- 24802 24805 24808 24811 conductive layer 5 photo- 24803 24806 24809 24812 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 316 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer a nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer b nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 317 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 24901 24921 24941 24961 layer 1 ir absorptive 24902 24922 24942 24962 layer 2 ir absorptive 24903 24923 24943 24963 layer 3 ir absorptive 24904 24924 24944 24964 layer 4 ir absorptive 24905 24925 24945 24965 layer 5 ir absorptive 24906 24926 24946 24966 layer 6 ir absorptive 24907 24927 24947 24967 layer 7 ir absorptive 24908 24928 24948 24968 layer 8 ir absorptive 24909 24929 24949 24969 layer 9 ir absorptive 24910 24930 24950 24970 layer 10 ir absorptive 24911 24931 24951 24971 layer 11 ir absorptive 24912 24932 24952 24972 layer 12 ir absorptive 24913 24933 24953 24973 layer 13 ir absorptive 24914 24934 24954 24974 layer 14 ir absorptive 24915 24935 24955 24975 layer 15 ir absorptive 24916 24936 24956 24976 layer 16 ir absorptive 24917 24937 24957 24977 layer 17 ir absorptive 24918 24938 24958 24978 layer 18 ir absorptive 24919 24939 24959 24979 layer 19 ir absorptive 24920 24940 24960 24980 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 318 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 25001 25021 25041 25061 layer 1 ir absorptive 25002 25022 25042 25062 layer 2 ir absorptive 25003 25023 25043 25063 layer 3 ir absorptive 25004 25024 25044 25064 layer 4 ir absorptive 25005 25025 25045 25065 layer 5 ir absorptive 25006 25026 25046 25066 layer 6 ir absorptive 25007 25027 25047 25067 layer 7 ir absorptive 25008 25028 25048 25068 layer 8 ir absorptive 25009 25029 25049 25069 layer 9 ir absorptive 25010 25030 25050 25070 layer 10 ir absorptive 25011 25031 25051 25071 layer 11 ir absorptive 25012 25032 25052 25072 layer 12 ir absorptive 25013 25033 25053 25073 layer 13 ir absorptive 25014 25034 25054 25074 layer 14 ir absorptive 25015 25035 25055 25075 layer 15 ir absorptive 25016 25036 25056 25076 layer 16 ir absorptive 25017 25037 25057 25077 layer 17 ir absorptive 25018 25038 25058 25078 layer 18 ir absorptive 25019 25039 25059 25079 layer 19 ir absorptive 25020 25040 25060 25080 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 319 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 25101 25121 25141 25161 layer 1 ir absorptive 25102 25122 25142 25162 layer 2 ir absorptive 25103 25123 25143 25163 layer 3 ir absorptive 25104 25124 25144 25164 layer 4 ir absorptive 25105 25125 25145 25165 layer 5 ir absorptive 25106 25126 25146 25166 layer 6 ir absorptive 25107 25127 25147 25167 layer 7 ir absorptive 25108 25128 25148 25168 layer 8 ir absorptive 25109 25129 25149 25169 layer 9 ir absorptive 25110 25130 25150 25170 layer 10 ir absorptive 25111 25131 25151 25171 layer 11 ir absorptive 25112 25132 25152 25172 layer 12 ir absorptive 25113 25133 25153 25173 layer 13 ir absorptive 25114 25134 25154 25174 layer 14 ir absorptive 25115 25135 25155 25175 layer 15 ir absorptive 25116 25136 25156 25176 layer 16 ir absorptive 25117 25137 25157 25177 layer 17 ir absorptive 25118 25138 25158 25178 layer 18 ir absorptive 25119 25138 25159 25179 layer 19 ir absorptive 25120 25140 25160 25180 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 320 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 25201 25221 25241 25261 layer 1 ir absorptive 25202 25222 25242 25262 layer 2 ir absorptive 25203 25223 25243 25263 layer 3 ir absorptive 25204 25224 25244 25264 layer 4 ir absorptive 25205 25225 25245 25265 layer 5 ir absorptive 25206 25226 25246 25266 layer 6 ir absorptive 25207 25227 25247 25267 layer 7 ir absorptive 25208 25228 25248 25268 layer 8 ir absorptive 25209 25229 25249 25268 layer 9 ir absorptive 25210 25230 25250 25270 layer 10 ir absorptive 25211 25231 25251 25171 layer 11 ir absorptive 25212 25232 25252 25272 layer 12 ir absorptive 25213 25233 25253 25273 layer 13 ir absorptive 25214 25234 25254 25274 layer 14 ir absorptive 25215 25235 25255 25275 layer 15 ir absorptive 25216 25236 25256 25276 layer 16 ir absorptive 25217 25237 25257 25277 layer 17 ir absorptive 25218 25238 25258 25278 layer 18 ir absorptive 25219 25239 25259 25279 layer 19 ir absorptive 25220 25240 25260 25280 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 321 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 25301 25321 25341 25361 layer 1 ir absorptive 25302 25322 25342 25362 layer 2 ir absorptive 25303 25323 25343 25363 layer 3 ir absorptive 25304 25324 25344 25364 layer 4 ir absorptive 25305 25325 25345 25365 layer 5 ir absorptive 25306 25326 25346 25366 layer 6 ir absorptive 25307 25327 25347 25367 layer 7 ir absorptive 25308 25328 25348 25368 layer 8 ir absorptive 25309 25329 25349 25369 layer 9 ir absorptive 25310 25330 25350 25370 layer 10 ir absorptive 25311 25331 25351 25371 layer 11 ir absorptive 25312 25332 25352 25372 layer 12 ir absorptive 25313 25333 25353 25373 layer 13 ir absorptive 25314 25334 25354 25374 layer 14 ir absorptive 25315 25335 25355 25375 layer 15 ir absorptive 25316 25336 25356 25376 layer 16 ir absorptive 25317 25337 25357 25377 layer 17 ir absorptive 25318 25338 25358 25378 layer 18 ir absorptive 25319 25339 25359 25379 layer 19 ir absorptive 25320 25340 25360 25380 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 322 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 25401 25421 25441 25461 layer 1 ir absorptive 25402 25422 25442 25462 layer 2 ir absorptive 25403 25423 25443 25463 layer 3 ir absorptive 25404 25424 25444 25464 layer 4 ir absorptive 25405 25425 25445 25465 layer 5 ir absorptive 25406 25426 25446 25466 layer 6 ir absorptive 25407 25427 25447 25467 layer 7 ir absorptive 25408 25428 25448 25468 layer 8 ir absorptive 25409 25429 25449 25469 layer 9 ir absorptive 25410 25430 25450 25470 layer 10 ir absorptive 25411 25431 25451 25471 layer 11 ir absorptive 25412 25432 25452 25472 layer 12 ir absorptive 25413 25433 25453 25473 layer 13 ir absorptive 25414 25434 25454 25474 layer 14 ir absorptive 25415 25435 25455 25475 layer 15 ir absorptive 25416 25436 25456 25476 layer 16 ir absorptive 25417 25437 25457 25477 layer 17 ir absorptive 25418 25438 25458 25478 layer 18 ir absorptive 25419 25439 25459 25479 layer 19 ir absorptive 25420 25440 25460 25480 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 323 __________________________________________________________________________ substrate inner layer drum gas used and its temperature rf power pressure thickness no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 25501 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 25502 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 300 25503 b.sub.2 h.sub.6 /(20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 324 __________________________________________________________________________ substrate inner layer drum gas used and its temperature rf power pressure thickness no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 25601 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 25602 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 300 25603 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.3 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 325 __________________________________________________________________________ substrate inner layer drum gas used and its temperature rf power pressure thickness no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 25701 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 25702 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm h.sub.2 100 nh.sub.3 300 25703 b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 326 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.5 layer nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 327 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 327 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ table 328 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 329 (a) __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer h.sub.2 100 (lower layer) nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 layer h.sub.2 100 (upper layer) nh.sub.3 300 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 329 (b) __________________________________________________________________________ substrate inner layer name of gas used and its temperture rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 250 0.35 20 conductive b.sub.2 h.sub.6 (against sih.sub.4 ) 100 ppm layer no 4 surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer h.sub.2 100 (lower layer) nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm surface b.sub.2 h.sub.6 he (20%) 500 250 200 0.40 0.3 layer h.sub.2 100 (upper layer) nh.sub.3 300 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ table 330 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 331 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 332 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 332 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 333 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 334 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 +nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 334 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 335 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 336 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 336 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 337 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase sur- abra- of face break sion inter- degree of drum defective abra- down resis- ference background no. image sion voltage tance fringe fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. ______________________________________ .circleincircle. : excellent .circle. : good table 338(a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 338 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 100 0.25 0.5 layer n.sub.2 100 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 339 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 340 (a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 340 (b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 341 __________________________________________________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow __________________________________________________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. __________________________________________________________________________ increase of break degree of drum defective surface down abrasion interference background no. image abrasion voltage resistance fringe fogginess __________________________________________________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. __________________________________________________________________________ .circleincircle.: excellent .circle. : good table 342(a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh .sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 342(b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- si.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 343 ______________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow ______________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. ______________________________________ increase of break degree of drum defective surface down abrasion background no. image abrasion voltage resistance fogginess ______________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circleincircle. ______________________________________ .circleincircle.: excellent .circle. : good table 344(a) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive hz 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper sih.sub.4 (against b.sub.2 h.sub.6 +nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 344(b) __________________________________________________________________________ gas used and its substrate inner layer name of flow rate temperature rf power pressure thickness layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ contact sih.sub.4 20 250 50 0.05 0.5 layer n.sub.2 10 ir sih.sub.4 100 250 150 0.35 1 absorptive h.sub.2 100 layer geh.sub.4 50 ph.sub.3 (against sih.sub.4) 800 ppm no 10 charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition ph.sub.3 (against sih.sub.4) 800 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm layer) __________________________________________________________________________ table 345 __________________________________________________________________________ intial electri- drum fication residual defective image no. efficiency voltage ghost image flow __________________________________________________________________________ (a) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. (b) .circleincircle. .circleincircle. .circle. .circleincircle. .circleincircle. __________________________________________________________________________ increase of break degree of drum defective surface down abrasion interference background no. image abrasion voltage resistance fringe fogginess __________________________________________________________________________ (a) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. (b) .circle. .circle. .circleincircle. .circleincircle. .circle. .circleincircle. __________________________________________________________________________ .circleincircle.: excellent .circle. : good table 346 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 27101 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27102 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 27103 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27104 sih.sub.4 200 250 250 0.40 20 ar 200 27105 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 27106* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27107* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 27108* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27109* sih.sub.4 200 250 250 0.40 20 ar 200 27110* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 327(b) markless case: followed table 327(a) table 347 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 27201 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27202 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 27206 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27204 sih.sub.4 200 250 250 0.40 20 ar 200 27205 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 27206* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27207* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub. 4) 100 ppm no 6 27208* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27209* sih.sub.4 200 250 250 0.40 20 ar 200 27210* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 329(b) markless case: followed table 329(a) table 348 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 27301 sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27302 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 27303 sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27304 sih.sub.4 200 250 250 0.40 20 ar 200 27305 sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 27306* sih.sub.4 200 250 300 0.40 20 he 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 4 27307* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 b.sub.2 h.sub.6 (against sih.sub.4) 100 ppm no 6 27308* sih.sub.4 200 250 300 0.40 20 h.sub.2 200 27309* sih.sub.4 200 250 250 0.40 20 ar 200 27310* sih.sub.4 150 250 350 0.40 20 sif.sub.4 50 h.sub.2 200 __________________________________________________________________________ *surface layer followed table 327(b) markless case: followed table 327(a) table 349 __________________________________________________________________________ gas used and its substrate inner layer drum flow rate temperature rf power pressure thickness no. (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 27401 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm geh.sub.4 10 no 10 27402 sih.sub.4 80 250 170 0.25 3 sif.sub.4 20 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm snh.sub.4 5 no 5 27403 sih.sub.4 100 250 130 0.25 3 b.sub.2 h.sub.6 (against sih.sub.4) 800 ppm no 4 n.sub.2 4 ch.sub.4 6 27404* sih.sub.4 100 250 150 0.35 3 h.sub.2 100 ph.sub.3 (against sih.sub.4) 800 ppm 27405* sih.sub.4 100 250 130 0.25 3 ph.sub.3 (against sih.sub.4) 800 ppm geh.sub.4 10 no 10 27406 sih.sub.4 100 250 150 0.35 3 h.sub.2 100 b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm no** 10 no*** 10.fwdarw.0**** __________________________________________________________________________ *surface layer followed table 332(b) markless case: followed table 332(a) **substrate side 2 .mu.m ***surface layer side 1 .mu.m ****constantly changed table 350 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 27501 27506 27511 27516 27521 27526 27531 conductive layer 1 photo- 27502 27507 27512 27517 27522 27527 27532 conductive layer 2 photo- 27503 27508 28513 27518 27523 27528 27533 conductive layer 3 photo- 27504 27509 27514 27519 27524 27529 27534 conductive layer 5 photo- 27505 27510 27515 27520 27525 27530 27535 conductive layer 6 __________________________________________________________________________ *surface layer followed table 332(b) markless case: followed table 332(a) table 351 __________________________________________________________________________ gas used and its substrate inner layer flow rate temperature rf power pressure thickness name of layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer a h.sub.2 100 nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 nh.sub.3 300 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 layer b h.sub.2 100 nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 nh.sub. 3 300 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm __________________________________________________________________________ *each of the surface layers a and b is individually used in accordance with the kind of the lower layer table 352 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 27601 27607 27613 27619 27625 27631 27637 conductive layer 1 photo- 27602 27608 27614 27620 27626 27632 27638 conductive layer 2 photo- 27603 27609 27615 27621 27627 27633 27639 conductive layer 3 photo- 27604 27610 27616 27622 27628 27634 27640 conductive layer 4 photo- 27605 27611 27617 27623 27629 27635 27641 conductive layer 5 photo- 27606 27612 27618 27624 27630 27636 27642 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 353 __________________________________________________________________________ gas used and its substrate inner layer flow rate temperature rf power pressure thickness name of layer (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer a nh.sub.3 100 bias voltage of -150 v the cylinder sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 bias voltage of +100 v the cylinder sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer b nh.sub.3 100 bias voltage of -150 v the cylinder geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 bias voltage of +100 v the cylinder geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub. 100 ppm __________________________________________________________________________ *each of the surface layers a and b is individually used in accordance with the kind of the lower layer table 354 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ photo- 27701 27707 27713 27719 27725 27731 27737 conductive layer 1 photo- 27702 27708 27714 27720 27726 27732 27738 conductive layer 2 photo- 27703 27709 27715 27721 27727 27733 27739 conductive layer 3 photo- 27704 27710 27716 27722 27728 27734 27740 conductive layer 4 photo- 27705 27711 27717 27723 27729 27735 27741 conductive layer 5 photo- 27706 27712 27718 27724 27730 27736 27742 conductive layer 6 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 355 ______________________________________ photo- photo- photo- photo- conduc- conduc- conduc- photo- conductive tive tive tive conductive layer 1 layer 2 layer 3 layer 5 layer 6 ______________________________________ drum 27801 27802 27803 27804 24805 no. 27806* 27807* 27808* 27809* 27810* ______________________________________ *surface layer followed table 334(b) markless case: followed table 334(a) table 356 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 27901 27902 27903 27904 27905 27906 no. 27907* 27908* 27909* 27910* 27911* 27912* __________________________________________________________________________ *surface layer b was used. *markless case: surface layer a was used. table 357 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- conductive conductive conductive conductive conductive conductive layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ drum 28001 28002 28003 28004 28005 28006 no. 28007* 28008* 28009* 28010* 28011* 28012* __________________________________________________________________________ *surface layer b was used. markless case: surface layer a was used. table 358 ______________________________________ drum no. ______________________________________ ir absorptive 28101 28120* layer 1 ir absorptive 28102 28121* layer 2 ir absorptive 28103 28122* layer 3 ir absorptive 28104 28123* layer 4 ir absorptive 28105 28124* layer 5 ir absorptive 28106 -- layer 6 ir absorptive 28107 -- layer 7 ir absorptive 28108 -- layer 8 ir absorptive 28109 -- layer 9 ir absorptive 28110 -- layer 10 ir absorptive 28111 -- layer 11 ir absorptive 28112 -- layer 12 ir absorptive 22813 -- layer 13 ir absorptive 28114 -- layer 14 ir absorptive 28115 -- layer 15 ir absorptive 28116 -- layer 17 ir absorptive 28117 28125* layer 18 ir absorptive 28118 28126* layer 19 ir absorptive 28119 28127* layer 20 ______________________________________ *: surface layer followed table 336(b) markless case: followed 336(a) table 359 __________________________________________________________________________ photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 5 layer 6 __________________________________________________________________________ ir absorptive 28201 28221 28241 28261 28281 layer 1 ir absorptive 28202 28222 28242 28262 28282 layer 2 ir absorptive 28203 28223 28243 28263 28283 layer 3 ir absorptive 28204 28224 28244 28264 28284 layer 4 ir absorptive 28205 28225 28245 28265 28285 layer 5 ir absorptive 28206 28226 28246 28266 28286 layer 6 ir absorptive 28207 28227 28247 28267 28287 layer 7 ir absorptive 28208 28228 28248 28268 28288 layer 8 ir absorptive 28209 28229 28249 28269 28289 layer 9 ir absorptive 28210 28230 28250 28270 28290 layer 10 ir absorptive 28211 28231 28251 28271 28291 layer 11* ir absorptive 28212 28232 28252 28272 28292 layer 12* ir absorptive 28213 28233 28253 28273 28293 layer 13* ir absorptive 28214 28234 28254 28274 28294 layer 14* ir absorptive 28215 28235 28255 28275 28295 layer 15* ir absorptive 28216 28036 28256 28276 28296 layer 16 ir absorptive 28217 28237 28257 28277 28297 layer 17* ir absorptive 28218 28238 28258 28278 28298 layer 18 ir absorptive 28219 28239 28259 28279 28299 layer 19 ir absorptive 28220 28240 28260 28280 282100 layer 20 __________________________________________________________________________ *: surface layer followed table 336(b) markless case: followed table 336(a) table 360 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 28301 28321 28341 28361 28381 283101 layer 1 ir absorptive 28302 28322 28342 28362 28382 283102 layer 2 ir absorptive 28303 28323 28343 28363 28383 283103 layer 3 ir absorptive 28304 28324 28344 28364 28384 283104 layer 4 ir absorptive 28305 28325 28345 28365 28385 283105 layer 5 ir absorptive 28306 28326 28346 28366 28386 283106 layer 6 ir absorptive 28307 28327 28347 28367 28387 283107 layer 7 ir absorptive 28308 28328 28348 28368 28388 283108 layer 8 ir absorptive 28309 29329 29349 29369 28389 283109 layer 9 ir absorptive 29310 28330 28350 28370 28390 283110 layer 10 ir absorptive 28311 28331 28351 28371 28391 283111 layer 11* ir absorptive 28312 28332 28352 28372 28392 283112 layer 12* ir absorptive 28313 28333 28353 28373 28393 283113 layer 13* ir absorptive 28314 28334 28354 28374 28394 283114 layer 14* ir absorptive 28315 28335 28355 28375 28395 283115 layer 15* ir absorptive 28316 28336 28356 28376 28396 283116 layer 16 ir absorptive 28317 28337 28357 28377 28397 283117 layer 17* ir absorptive 28318 28338 28358 28378 28398 283118 layer 18 ir absorptive 28319 28339 28359 28379 28399 283119 layer 19 ir absorptive 28320 28340 28360 28380 283100 283120 layer 20 __________________________________________________________________________ *: surface layer b was used markless case: surface layer a was used table 361 __________________________________________________________________________ photo- photo- photo- photo- photo- photo- drum conductive conductive conductive conductive conductive conductive no. layer 1 layer 2 layer 3 layer 4 layer 5 layer 6 __________________________________________________________________________ ir absorptive 28401 28421 28441 28461 28481 284101 layer 1 ir absorptive 28402 28422 28442 28462 28482 284102 layer 2 ir absorptive 28403 28423 28443 28463 28483 284103 layer 3 ir absorptive 28404 28424 28444 28464 28484 284104 layer 4 ir absorptive 28405 28425 28445 28465 28485 284105 layer 5 ir absorptive 28406 28426 28446 28466 28486 284106 layer 6 ir absorptive 28407 28427 28447 28467 28487 284107 layer 7 ir absorptive 28408 28428 28448 28468 28488 284108 layer 8 ir absorptive 28409 29429 29449 29469 28489 284109 layer 9 ir absorptive 29410 28430 28450 28470 28490 284110 layer 10 ir absorptive 28411 28431 28451 28471 28491 284111 layer 11* ir absorptive 28412 28432 28452 28472 28492 284112 layer 12* ir absorptive 28413 28433 28453 28473 28493 284113 layer 13* ir absorptive 28414 28434 28454 28474 28494 284114 layer 14* ir absorptive 28415 28435 28455 28475 28495 284115 layer 15* ir absorptive 28416 28436 28456 28476 28496 284116 layer 16 ir absorptive 28417 28437 28457 28477 28497 284117 layer 17* ir absorptive 28418 28438 28458 28478 28498 284118 layer 18 ir absorptive 28419 28439 28459 28479 28499 284119 layer 19 ir absorptive 28420 28440 28460 28480 284100 284120 layer 20 __________________________________________________________________________ *: surface layer b was used markless case: surface layer a was used table 362 ______________________________________ contact contact contact layer 2 layer 3 layer 4 ______________________________________ drum 28501 28502 28503 no. 28504* 28405* 28506* ______________________________________ *surface layer followed table 338 (b) markless case: followed table 338 (a) table 363 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 28601 28607* 28613 28619 conductive layer 1 photo- 28602 28608 28614* 28620 conductive layer 2 photo- 28603* 28609 28615 28621 conductive layer 3 photo- 28604 28610 28616 28622* conductive layer 4 photo- 28605 28611 28617* 28623 conductive layer 5 photo- 28606 28612* 28618 28624 conductive layer 6 ______________________________________ *surface layer followed table 338 (b) markless case: followed table 338 (a) table 364 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 28701 28707 28713* 28719 conductive layer 1 photo- 28702 28708* 28714 28720 conductive layer 2 photo- 28703 28709 28715 28721* conductive layer 3 photo- 28704* 28710 28716 28722 conductive layer 4 photo- 28705 28711* 28717 28723 conductive layer 5 photo- 28706 28712 28718* 28724 conductive layer 6 ______________________________________ table 365 ______________________________________ drum contact contact contact contact no. layer 1 layer 2 layer 3 layer 4 ______________________________________ photo- 28801* 28807 28813 28819 conductive layer 1 photo- 28802 28808 28814* 28820 conductive layer 2 photo- 28803 28809 28815 28821* conductive layer 3 photo- 28804 28810* 28816 28822 conductive layer 4 photo- 28805 28811 28817 28823* conductive layer 5 photo- 28806* 28812 28818 28824 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 366 ______________________________________ drum no. ______________________________________ ir absorptive 28901 28921 layer 1 * ir absorptive 28902 28922 layer 2 * ir absorptive 28903 28923 layer 3 * ir absorptive 28904 28924 layer 4 * ir absorptive 28905 28925 layer 5 * ir absorptive 28906 28926 layer 6 * ir absorptive 28907 28927 layer 7 * ir absorptive 28908 28928 layer 8 * ir absorptive 28909 28929 layer 9 * ir absorptive 28910 28930 layer 10 * ir absorptive 28911 28931 layer 11 * ir absorptive 28912 28932 layer 12 * ir absorptive 28913 28933 layer 13 * ir absorptive 28914 28934 layer 14 * ir absorptive 28915 28935 layer 15 * ir absorptive 28916 28936 layer 16 * ir absorptive 28917 28937 layer 17 * ir absorptive 28918 28938 layer 18 * ir absorptive 28919 28939 layer 19 * ir absorptive 28920 28940 layer 20 * ______________________________________ *: charge injection inhibition layer and surface layer followed table 340(b) markless case: followed table 340(a) table 367 ______________________________________ photo- photo- photo- drum conductive conductive conductive no. layer 4 layer 5* layer 7 ______________________________________ ir absorptive 29001 29021 29041 layer 1 ir absorptive 29002 29022 29042 layer 2 ir absorptive 29003 29023 29043 layer 3 ir absorptive 29004 29024 29044 layer 4 ir absorptive 29005 29025 29045 layer 5 ir absorptive 29006 29026 29046 layer 6 ir absorptive 29007 29027 29047 layer 7 ir absorptive 29008 29028 29048 layer 8 ir absorptive 29009 29029 29049 layer 9 ir absorptive 29010 29030 29050 layer 10 ir absorptive 29011 29031 29051 layer 11 ir absorptive 29012 29032 29052 layer 12 ir absorptive 29013 29033 29053 layer 13 ir absorptive 29014 29034 29054 layer 14 ir absorptive 29015 29035 29055 layer 15 ir absorptive 29016 29036 29056 layer 16 ir absorptive 29017 29037 29057 layer 17 ir absorptive 29018 29038 29058 layer 18 ir absorptive 29019 29039 29059 layer 19 ir absorptive 29020 29040 29060 layer 20 ______________________________________ *: surface layer followed table 340(b) markless case: followed table 340(a) table 368 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 29101 29121 29141 29161 layer 1 ir absorptive 29102 29122 29142 29162 layer 2 ir absorptive 29103 29123 29143 29163 layer 3 ir absorptive 29104 29124 29144 29164 layer 4 ir absorptive 29105 29125 29145 29165 layer 5 ir absorptive 29106 29126 29146 29166 layer 6 ir absorptive 29107 29127 29147 29167 layer 7 ir absorptive 29108 29128 29148 29168 layer 8 ir absorptive 29109 29129 29149 29169 layer 9 ir absorptive 29110 29130 29150 29170 layer 10 ir absorptive 29111 29131 29151 29171 layer 11 ir absorptive 29112 29132 29152 29172 layer 12 ir absorptive 29113 29133 29153 29173 layer 13 ir absorptive 29114 29134 29154 29174 layer 14 ir absorptive 29115 29135 29155 29175 layer 15 ir absorptive 29116 29136 29156 29176 layer 16 ir absorptive 29117 29137 29157 29177 layer 17 ir absorptive 29118 29138 29158 29178 layer 18 ir absorptive 29119 29139 29159 29179 layer 19 ir absorptive 29120 29140 29160 29180 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 369 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 29201 29221 29241 29261 layer 1 ir absorptive 29202 29222 29242 29262 layer 2 ir absorptive 29203 29223 29243 29263 layer 3 ir absorptive 29204 29224 29244 29264 layer 4 ir absorptive 29205 29225 29245 29265 layer 5 ir absorptive 29206 29226 29246 29266 layer 6 ir absorptive 29207 29227 29247 29267 layer 7 ir absorptive 29208 29228 29248 29268 layer 8 ir absorptive 29209 29229 29249 29269 layer 9 ir absorptive 29210 29230 29250 29270 layer 10 ir absorptive 29211 29231 29251 29271 layer 11 ir absorptive 29212 29232 29252 29272 layer 12 ir absorptive 29213 29233 29253 29273 layer 13 ir absorptive 29214 29234 29254 29274 layer 14 ir absorptive 29215 29235 29255 29275 layer 15 ir absorptive 29216 29236 29256 29276 layer 16 ir absorptive 29217 29237 29257 29277 layer 17 ir absorptive 29218 29238 29258 29278 layer 18 ir absorptive 29219 29239 29259 29279 layer 19 ir absorptive 29220 29240 29260 29280 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 370 __________________________________________________________________________ contact contact contact contact contact contact contact layer 1 layer 2 layer 3 layer 4 layer 6 layer 7 layer 8 __________________________________________________________________________ drum 29301 29302 29303 29304 29305 29306 29307 no. 29308* 29309* 29310* 29311* 29312* 29313* 29314* __________________________________________________________________________ *charge injection inhibition layer andsurface layer followed table 342 (b markless case: followed table 342 (a) table 371 __________________________________________________________________________ charge charge charge charge charge charge injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition no. layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 29401 29409 29417 29425 29433 29441 layer 1 contact 29402 29410 29418 29426 29434 29442 layer 2 contact 29403 29411 29419 29427 29435 29443 layer 3 contact 29404 29412 29420 29428 29436 29444 layer 4 contact 29405 29413 29421 29429 29437 29445 layer 5 contact 29406 29414 29422 29430 29438 29446 layer 6 contact 29407 29415 29423 29431 29439 29447 layer 7 contact 29408 29416 29424 29432 29440 29448 layer 8 __________________________________________________________________________ *surface layer followed table 342 (b) markless case: followed table 342 (a) table 372 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 29501 29509 29517 29525 29533 29541 29549 layer 1 contact 29502 29510 29518 29526 29534 29542 29550 layer 2 contact 29503 29511 29519 29527 29535 29543 29551 layer 3 contact 29504 29512 29520 29528 29536 29544 29552 layer 4 contact 29505 29513 29521 29529 29537 29545 29553 layer 5 contact 29506 29514 29522 29530 29538 29546 29554 layer 6 contact 29507 29515 29523 29531 29539 29547 29555 layer 7 contact 29508 29516 29524 29532 29540 29548 29556 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 373 __________________________________________________________________________ charge charge charge charge charge charge charge injection injection injection injection injection injection injection drum inhibition inhibition inhibition inhibition inhibition inhibition inhibition no. layer 1 layer 2 layer 3 layer 4 layer 5* layer 6* layer 7 __________________________________________________________________________ contact 29601 29609 29617 29625 29633 29641 29649 layer 1 contact 29602 29610 29618 29626 29634 29642 29650 layer 2 contact 29603 29611 29619 29627 29635 29643 29651 layer 3 contact 29604 29612 29620 29628 29636 29644 29652 layer 4 contact 29605 29613 29621 29629 29637 29645 29653 layer 5 contact 29606 29614 29622 29630 29638 29646 29654 layer 6 contact 29607 29615 29623 29631 29639 29647 29655 layer 7 contact 29608 29616 29624 29632 29640 29648 29656 layer 8 __________________________________________________________________________ *surface layer b was used markless case: surface layer a was used table 374 ______________________________________ charge charge charge injection injection injection inhibition inhibition inhibition layer 4 layer 6* layer 7 ______________________________________ drum 29701 29702 29703 no. ______________________________________ *surface layer followed table 18 (b) markless case: followed table 18 (a) table 375 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 29801 29803 29805 29807 conductive layer 5 photo- 29802 29804 29806 29808 conductive layer 6 ______________________________________ *surface layer followed table 18 (b) markless case: followed table 18 (a) table 376 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 29901 29904 29907 29910 conductive layer 4 photo- 29902 29905 29908 29911 conductive layer 5 photo- 29903 29906 29909 29912 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 377 ______________________________________ charge charge charge charge injection injection injection injection drum inhibition inhibition inhibition inhibition no. layer 1 layer 4 layer 6* layer 7 ______________________________________ photo- 30001 30004 30007 30010 conductive layer 4 photo- 30002 30005 30008 30011 conductive layer 5 photo- 30003 30006 30009 30012 conductive layer 6 ______________________________________ *surface layer b was used markless case: surface layer a was used table 378 __________________________________________________________________________ substrate inner layer gas used and its temperature rf power pressure thickness name of layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer a nh.sub.3 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 300 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface* lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer b nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 nh.sub.3 100 geh.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________ *each of the surface layers a and b is individually used in accordance with the kind of the lower layer table 379 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30101 30121 30141 30161 layer 1 ir absorptive 30102 30122 30142 30162 layer 2 ir absorptive 30103 30123 30143 30163 layer 3 ir absorptive 30104 30124 30144 30164 layer 4 ir absorptive 30105 30125 30145 30165 layer 5 ir absorptive 30106 30126 30146 30166 layer 6 ir absorptive 30107 30127 30147 30167 layer 7 ir absorptive 30108 30128 30148 30168 layer 8 ir absorptive 30109 30129 30149 30169 layer 9 ir absorptive 30110 30130 30150 30170 layer 10 ir absorptive 30111 30131 30151 30171 layer 11 ir absorptive 30112 30132 30152 30172 layer 12 ir absorptive 30113 30133 30153 30173 layer 13 ir absorptive 30114 30134 30154 30174 layer 14 ir absorptive 30115 30135 30155 30175 layer 15 ir absorptive 30116 30136 30156 30176 layer 16 ir absorptive 30117 30137 30157 30177 layer 17 ir absorptive 30118 30138 30158 30178 layer 18 ir absorptive 30119 30139 30159 30179 layer 19 ir absorptive 30120 30140 30160 30180 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 380 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30201 30221 30241 30261 layer 1 ir absorptive 30202 30222 30242 30262 layer 2 ir absorptive 30203 30223 30243 30263 layer 3 ir absorptive 30204 30224 30244 30264 layer 4 ir absorptive 30205 30225 30245 30265 layer 5 ir absorptive 30206 30226 30246 30266 layer 6 ir absorptive 30207 30227 30247 30267 layer 7 ir absorptive 30208 30228 30248 30268 layer 8 ir absorptive 30209 30229 30249 30269 layer 9 ir absorptive 30210 30230 30250 30270 layer 10 ir absorptive 30211 30231 30251 30271 layer 11 ir absorptive 30212 30232 30252 30272 layer 12 ir absorptive 30213 30233 30253 30273 layer 13 ir absorptive 30214 30234 30254 30274 layer 14 ir absorptive 30215 30235 30255 30275 layer 15 ir absorptive 30216 30236 30256 30276 layer 16 ir absorptive 30217 30237 30257 30277 layer 17 ir absorptive 30218 30238 30258 30278 layer 18 ir absorptive 30219 30239 30259 30279 layer 19 ir absorptive 30220 30240 30260 30280 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 381 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30301 30321 30341 30361 layer 1 ir absorptive 30302 30322 30342 30362 layer 2 ir absorptive 30303 30323 30343 30363 layer 3 ir absorptive 30304 30324 30344 30364 layer 4 ir absorptive 30305 30325 30345 30365 layer 5 ir absorptive 30306 30326 30346 30366 layer 6 ir absorptive 30307 30327 30347 30367 layer 7 ir absorptive 30308 30328 30348 30368 layer 8 ir absorptive 30309 30329 30349 30369 layer 9 ir absorptive 30310 30330 30350 30370 layer 10 ir absorptive 30311 30331 30351 30371 layer 11 ir absorptive 30312 30332 30352 30372 layer 12 ir absorptive 30313 30333 30353 30373 layer 13 ir absorptive 30314 30334 30354 30374 layer 14 ir absorptive 30315 30335 30355 30375 layer 15 ir absorptive 30316 30336 30356 30376 layer 16 ir absorptive 30317 30337 30357 30377 layer 17 ir absorptive 30318 30338 30358 30378 layer 18 ir absorptive 30319 30339 30359 30379 layer 19 ir absorptive 30320 30340 30360 30380 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 382 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30401 30421 30441 30461 layer 1 ir absorptive 30402 30422 30442 30462 layer 2 ir absorptive 30403 30423 30443 30463 layer 3 ir absorptive 30404 30424 30444 30464 layer 4 ir absorptive 30405 30425 30445 30465 layer 5 ir absorptive 30406 30426 30446 30466 layer 6 ir absorptive 30407 30427 30447 30467 layer 7 ir absorptive 30408 30428 30448 30468 layer 8 ir absorptive 30409 30429 30449 30469 layer 9 ir absorptive 30410 30430 30450 30470 layer 10 ir absorptive 30411 30431 30451 30471 layer 11 ir absorptive 30412 30432 30452 30472 layer 12 ir absorptive 30413 30433 30453 30473 layer 13 ir absorptive 30414 30434 30454 30474 layer 14 ir absorptive 30415 30435 30455 30475 layer 15 ir absorptive 30416 30436 30456 30476 layer 16 ir absorptive 30417 30437 30457 30477 layer 17 ir absorptive 30418 30438 30458 30478 layer 18 ir absorptive 30419 30439 30459 30479 layer 19 ir absorptive 30420 30440 30460 30480 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 383 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30501 30521 30541 30561 layer 1 ir absorptive 30502 30522 30542 30562 layer 2 ir absorptive 30503 30523 30543 30563 layer 3 ir absorptive 30504 30524 30544 30564 layer 4 ir absorptive 30505 30525 30545 30565 layer 5 ir absorptive 30506 30526 30546 30566 layer 6 ir absorptive 30507 30527 30547 30567 layer 7 ir absorptive 30508 30528 30548 30568 layer 8 ir absorptive 30509 30529 30549 30569 layer 9 ir absorptive 30510 30530 30550 30570 layer 10 ir absorptive 30511 30531 30551 30571 layer 11 ir absorptive 30512 30532 30552 30572 layer 12 ir absorptive 30513 30533 30553 30573 layer 13 ir absorptive 30514 30534 30554 30574 layer 14 ir absorptive 30515 30535 30555 30575 layer 15 ir absorptive 30516 30536 30556 30576 layer 16 ir absorptive 30517 30537 30557 30577 layer 17 ir absorptive 30518 30538 30558 30578 layer 18 ir absorptive 30519 30539 30559 30579 layer 19 ir absorptive 30520 30540 30560 30580 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 384 ______________________________________ photo- photo- photo- photo- drum conductive conductive conductive conductive no. layer 1 layer 4 layer 5* layer 7 ______________________________________ ir absorptive 30601 30621 30641 30661 layer 1 ir absorptive 30602 30622 30642 30662 layer 2 ir absorptive 30603 30623 30643 30663 layer 3 ir absorptive 30604 30624 30644 30664 layer 4 ir absorptive 30605 30625 30645 30665 layer 5 ir absorptive 30606 30626 30646 30666 layer 6 ir absorptive 30607 30627 30647 30667 layer 7 ir absorptive 30608 30628 30648 30668 layer 8 ir absorptive 30609 30629 30649 30669 layer 9 ir absorptive 30610 30630 30650 30670 layer 10 ir absorptive 30611 30631 30651 30671 layer 11 ir absorptive 30612 30632 30652 30672 layer 12 ir absorptive 30613 30633 30653 30673 layer 13 ir absorptive 30614 30634 30654 30674 layer 14 ir absorptive 30615 30635 30655 30675 layer 15 ir absorptive 30616 30636 30656 30676 layer 16 ir absorptive 30617 30637 30657 30677 layer 17 ir absorptive 30618 30638 30658 30678 layer 18 ir absorptive 30619 30639 30659 30679 layer 19 ir absorptive 30620 30640 30660 30680 layer 20 ______________________________________ *: surface layer b was used markless case: surface layer a was used table 385 __________________________________________________________________________ substrate inner layer gas used and its temperature rf power pressure thickness drum no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 30701 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 30702 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 300 30703 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 386 __________________________________________________________________________ substrate inner layer gas used and its temperature rf power pressure thickness drum no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 30801 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 30802 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 300 30803 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 387 __________________________________________________________________________ substrate inner layer gas used and its temperature rf power pressure thickness drum no. flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ 30901 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 30902 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 100 upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.40 0.3 h.sub.2 100 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 50 ppm nh.sub.3 300 30903 lower layer b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of -150 v the cylinder upper layer b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm nh.sub.3 100 bias voltage of +100 v the cylinder __________________________________________________________________________ table 388 __________________________________________________________________________ substrate inner layer name of gas used and its temperature rf power pressure thickness layer flow rate (sccm) (.degree.c.) (w) (torr) (.mu.m) __________________________________________________________________________ charge sih.sub.4 100 250 150 0.35 3 injection h.sub.2 100 inhibition b.sub.2 h.sub.6 (against sih.sub.4) 1000 ppm layer no 10 photo- sih.sub.4 200 250 300 0.40 20 conductive h.sub.2 200 layer inter- sih.sub.4 10 250 150 0.35 0.3 mediate ch.sub.4 400 layer surface b.sub.2 h.sub.6 /ar (20%) 500 250 200 0.35 0.3 layer nh.sub.3 100 (lower layer) sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm surface b.sub.2 h.sub.6 /he (20%) 500 250 100 0.35 0.3 layer nh.sub.3 100 (upper layer) sih.sub.4 (against b.sub.2 h.sub.6 + nh.sub.3) 100 ppm __________________________________________________________________________
|
134-960-810-389-810
|
US
|
[
"US",
"EP",
"JP",
"CA",
"CN",
"WO",
"ES",
"AU",
"DE",
"BR",
"AT",
"MX"
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A61Q5/12,A61K8/34,A61K8/41,A61K8/42,A61K8/895,A61K8/898,A61K8/89,A61K8/58,A61Q5/00,A61K8/18,A61K8/00
| 2003-09-24T00:00:00 |
2003
|
[
"A61"
] |
conditioning composition comprising aminosilicone
|
a conditioning composition containing an aminosilicone having a viscosity of from about 1,000 cs to about 1,000,000 cs, and less than about 0.5% nitrogen by weight of the aminosilicone, a cationic surfactant, a high melting point fatty compound, and an aqueous carrier. these compositions may optionally comprise a low viscosity fluid. the present invention is further directed to a method of making the conditioning composition and a method of using the conditioning composition.
|
1. a hair conditioning composition comprising: (1) a terminal aminosilicone having chemical formula (r 1 ) a g 3-a —si(osig 2 ) n —(—osig b (r 1 ) 2-b ) m —o—sig 3-a wherein g is methyl, monovalent radical conforming to the formula c q h 2q l, a=1, b=2, n is from about 1500 to about 17000; m=0; q is 3; and l is —n (ch 3 ) 2 (2) from about 0.1% to about 10% of behenyl trimethyl ammonium chloride; (3) a high melting point fatty compound wherein said high melting fatty compound is selected from the group consisting of cetyl alcohol, stearyl alcohol and behenyl alcohol wherein said high melting fatty compound is present at a level of from about 0.1% to about 20%; (4) from about 0.1% to about 20% of low viscosity fluid, where in said low viscosity fluid comprises a non-polar, volatile hydrocarbon (5) an acid (6) from about 0.01% to about 5% polysorbate (7) from about 0.01% to about 10% polypropylene glycol and an aqueous carrier said terminal aminosilicone is present in the composition in an amount of from about 0.1% to about 20%. 2. the conditioning composition according to claim 1 wherein said aminosilicone is present in the composition in an amount of from about 0.5% to about 10%. 3. the conditioning composition according to claim 2 wherein said terminal aminosilicone is present in the composition in an amount of from about 1% to about 6%. 4. a method conditioning hair comprising the steps of applying said conditioning composition according to claim 1 to hair and rinsing.
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cross reference to related application(s) this application claims the benefit of u.s. provisional application nos. 60/505,726, filed sep. 24, 2003, and 60/543,219, filed feb. 10, 2004. field the present invention relates to conditioning compositions containing an aminosilicone, a cationic surfactant, a high melting point fatty compound, and an aqueous carrier. these compositions provide improved hair conditioning performance such as increasing hair shine, smoothness, and softness. background human hair becomes soiled due to its contact with the surrounding environment and from the sebum secreted by the scalp. the soiling of hair causes it to have a dirty feel and an unattractive appearance. the soiling of the hair necessitates shampooing with frequent regularity. shampooing cleans the hair by removing excess soil and sebum. however, shampooing can leave the hair in a wet, tangled, and generally unmanageable state. once the hair dries, it is often left in a dry, rough, lusterless, or frizzy condition due to removal of the hair's natural oils and other natural conditioning and moisturizing components. the hair can further be left with increased levels of static upon drying, which can interfere with the combing and result in a condition commonly referred to as “fly-away hair”, or contribute to an undesirable phenomenon of “split ends”. further, chemical treatments, such as perming, bleaching, or coloring hair, can also damage hair and leave it dry, rough, lusterless, and damaged. a variety of approaches have been developed to condition the hair. a common method of providing conditioning benefits to the hair is through the use of conditioning agents such as cationic surfactants and polymers, high melting point fatty compounds, low melting point oils, silicone compounds, and mixtures thereof. however, there still exists the opportunity to increase the conditioning benefits delivered through the conditioning compositions. there still exists a need for hair-conditioning compositions which provide improved silicone deposition and/or improved conditioning via friction reduction. particularly, a need still exists to provide a conditioning composition with enhanced benefits such as hair shine, softness, dry hair smoothness, hair strand alignment (e.g. minimize frizziness), and ease of combing. also, a need still exists for a conditioning composition that is effective for providing conditioning benefits to hair that is damaged by natural, environmental factors, as well as chemical hair treatments. summary the present invention can provide inherently more effective conditioning products, thus providing improved conditioning benefits such as hair shine, softness, dry hair smoothness, hair strand alignment (e.g., minimize frizziness), and ease of combing. further, the present invention can provide enhanced silicone deposition and/or improved conditioning via friction reduction. also, the present invention is effective for providing conditioning benefits to hair that is damaged by natural, environmental factors such as shampooing, as well as chemical hair treatments such as bleaching, coloring, or perming. the present invention is directed to a conditioning composition containing from about 0.1% to about 20% of an aminosilicone having a viscosity of from about 1,000 cs to about 1,000,000 cs, and less than about 0.5% nitrogen by weight of the aminosilicone; from about 0.1% to about 10% of a cationic surfactant; from about 0.1% to about 20% of a high melting point fatty compound; and an aqueous carrier. the present invention may optionally include a low viscosity fluid. the present invention is further directed to a method of using the conditioning composition. another embodiment of the invention relates to a method of making a conditioning composition comprising mixing together a previously formed blend of aminosilicone and a low viscosity fluid, wherein the aminosilicone has less than about 0.5% nitrogen by weight of the aminosilicone; a cationic surfactant; a high melting point fatty compound; and an aqueous carrier. detailed description the essential components of the conditioning composition are described below. also included is a nonexclusive description of various optional and preferred components useful in embodiments of the present invention. while the specification concludes with claims that particularly point out and distinctly claim the invention, it is believed that the present invention will be better understood from the following description. all percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. all such weights as they pertain to listed ingredients are based on the active level and, therefore do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. the term “weight percent” may be denoted as “wt. % herein. all molecular weights as used herein are weight average molecular weights expressed as grams/mole, unless otherwise specified. herein, “comprising” means that other steps and other ingredients which do not affect the end result can be added. this term encompasses the terms “consisting of” and “consisting essentially of”. the compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein. herein, “cs” means centistokes. the term “conditioning composition” as used herein, unless otherwise specified, refers to the compositions of the present invention, wherein the compositions are intended to include those compositions for topical application to the hair or scalp. the term “aminosilicone” as used herein, unless otherwise specified, refers to a silicone containing at least one primary amine, secondary amine, tertiary amine, or a quaternary ammonium group. the term “high melting point fatty compound” as used herein, unless otherwise specified, is a compound having the general formula r—x, wherein r is an aliphatic (e.g. fatty chain) and x is a functional group (e.g. alcohol, acid, or derivative), wherein the compounds have a melting point of 25° c. or higher. the compositions of the present invention preferably have a ph of from about 3 to about 8, preferably from about 4 to about 7 when measured on the neat product. a. aminosilicone the conditioning composition of the present invention includes an aminosilicone. an aminosilicone is a silicone containing at least one primary amine, secondary amine, tertiary amine, or a quaternary ammonium group. preferred aminosilicones may have less than about 0.5% nitrogen by weight of the aminosilicone, more preferably less than about 0.2%, more preferably still, less than about 0.1%. higher levels of nitrogen (amine functional groups) in the amino silicone tend to result in less friction reduction, and consequently less conditioning benefit from the aminosilicone. preferably the silicones used in the present invention have a particle size of less than about 50μ once incorporated into the final composition. the particle size measurement is taken from dispersed droplets in the final composition. particle size may be measured by means of a laser light scattering technique, using a horiba model la-910 laser scattering particle size distribution analyzer (horiba instruments, inc). in a preferred embodiment, the aminosilicone has a viscosity of from about 1,000 cs to about 1,000,000 cs, more preferably from about 10,000 cs to about 700,000 cs, more preferably from about 50,000 cs to about 500,000 cs, still more preferably from about 100,000 cs to about 400,000 cs. the viscosity of aminosilicones discussed herein is measured at 25° c. the aminosilicone is contained in the composition of the present invention at a level by weight of from about 0.1% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 6%. examples of preferred aminosilicones for use in embodiments of the subject invention include, but are not limited to, those which conform to the general formula (i): (r 1 ) a g 3-a —si—(—osig 2 ) n —(—osig b (r 1 ) 2-b ) m —o—sig 3-a (r 1 ) a wherein g is hydrogen, phenyl, hydroxy, or c 1 -c 8 alkyl, preferably methyl; a is 0 or an integer having a value from 1 to 3, preferably 1; b is 0, 1 or 2, preferably 1; wherein when a is 0, b is not 2; n is a number from 0 to 1,999; m is an integer from 0 to 1,999; the sum of n and m is a number from 1 to 2,000; a and m are not both 0; r 1 is a monovalent radical conforming to the general formula cqh 2q l, wherein q is an integer having a value from 2 to 8 and l is selected from the following groups: —n(r 2 )ch 2 —ch 2 —n(r 2 ) 2 ; —n(r 2 ) 2 ; —n(r 2 ) 3 a − ; —n(r 2 )ch 2 —ch 2 —nr 2 h 2 a − ; wherein r 2 is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, preferably an alkyl radical from about c 1 to about c 20 ; a − is a halide ion. a preferred amino silicone corresponding to formula (i) has m=0, a=1, q=3, g=methyl, n is preferably from about 1500 to about 1700, more preferably 1600; and l is —n(ch 3 ) 2 . this is an example of a terminal aminosilicone, as there is a nitrogen group on one or both ends of the silicone chain. a preferred aminosilicone corresponding to formula (i) is the polymer known as “trimethylsilylamodimethicone”, which is shown below in formula (ii): wherein n is a number from 1 to 1,999 and m is a number from 1 to 1,999. formula (ii) is an example of a graft amino silicone, as there is a nitrogen group pendant to the silicone chain, but it is not on an end of the chain. other aminosilicone polymers which may be used in the compositions of the present invention are represented by the general formula (iii): wherein r 3 is a monovalent hydrocarbon radical from c 1 to c 18 , preferably an alkyl or alkenyl radical, such as methyl; r 4 is a hydrocarbon radical, preferably a c 1 to c 18 alkylene radical or a c 10 to c 18 alkyleneoxy radical, more preferably a c 1 to c 8 alkyleneoxy radical; q − is a halide ion, preferably chloride; r is an average statistical value of from about 2 to about 20, preferably from about 2 to about 8; s is an average statistical value of from about 20 to about 200, preferably from about 20 to about 50, a preferred polymer of this class is known as ucare silicone ale 56™, available from union carbide. b. cationic surfactant the conditioning composition of the present invention comprises a cationic surfactant. the cationic surfactant is included in the composition at a level by weight of from about 0.1% to about 10%, preferably from about 1% to about 5%. cationic surfactants useful herein include, for example, those corresponding to the general formula (iv): wherein at least one of r 71 , r 72 , r 73 and r 74 is selected from an aliphatic group of from about 8 to about 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms, the remainder of r 71 , r 72 , r 73 and r 74 are independently selected from an aliphatic group of from about 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and x is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkyl sulfonate radicals. the aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether, ester, or amido linkages and other groups such as amino groups. the longer chain aliphatic groups, (e.g., those of about 12 carbons, or higher), can be saturated, unsaturated, or branched. preferred is when r 71 , r 72 , r 73 and r 74 are independently selected from c 1 to about c 22 alkyl. nonlimiting examples of cationic surfactants useful in the present invention include the materials having the following ctfa designations: quaternium-8, quaternium-14, quaternium-18, quaternium-18 methosulfate, quaternium-24, and mixtures thereof. among the cationic surfactants of general formula (iv), preferred are those containing in the molecule at least one alkyl chain having at least 16 carbons. nonlimiting examples of such preferred cationic surfactants include: behenyl trimethyl ammonium chloride available, for example, with tradename genamine kdmp from clariant, with tradename incroquat tmc-80 from croda, and with tradename econol tm22 from sanyo kasei; cetyl trimethyl ammonium chloride available, for example, with tradename ctac 30kc from kci, and with tradename ca-2350 from nikko chemicals; stearyl trimethyl ammonium chloride available, for example, with tradename genamine stacp from clariant; olealkonium chloride available, for example, with tradename incroquat o-50 from croda; hydrogenated tallow alkyl trimethyl ammonium chloride, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, di(behenyl/arachidyl) dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl propyleneglycol phosphate dimethyl ammonium chloride, stearoyl amidopropyl dimethyl benzyl ammonium chloride, stearoyl amidopropyl dimethyl (myristylacetate) ammonium chloride, and n-(stearoyl colamino formyl methyl) pyridinium chloride. also preferred are hydrophilically substituted cationic surfactants in which at least one of the substituents contains one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the r 71 -r 74 radicals contain one or more hydrophilic moieties selected from alkoxy (preferably c 1 -c 3 alkoxy), polyoxyalkylene (preferably c 1 -c 3 polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester, and combinations thereof. preferably, the hydrophilically substituted cationic conditioning surfactant contains from about 2 to about 10 nonionic hydrophile moieties located within the above stated ranges. highly preferred hydrophilically substituted cationic surfactants include dialkylamido ethyl hydroxyethylmonium salt, dialkylamidoethyl dimonium salt, dialkyloyl ethyl hydroxyethylmonium salt, dialkyloyl ethyldimonium salt, and mixtures thereof; for example, commercially available under the following tradenames; varisoft 110, varisoft 222, variquat k1215 and variquat 638 from witco chemical; mackpro klp, mackpro wlw, mackpro mlp, mackpro nsp, mackpro nlw, mackpro wwp, mackpro nlp, mackpro slp from mcintyre; ethoquad 18/25, ethoquad o/12pg, ethoquad c/25, ethoquad s/25, and ethoduoquad from akzo; dehyquat sp from henkel; and atlas g265 from ici americas. babassuamidopropalkonium chloride available from croda under the tradename incroquat ba-85 is also preferably used in the composition. amines are suitable as cationic surfactants. primary, secondary, and tertiary fatty amines are useful. particularly useful are tertiary amido amines having an alkyl group of from about 12 to about 22 carbons. exemplary tertiary amido amines include: stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethyl amine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachnidamidopropyldimethylamine, arachidamidopropyldiethylamine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, diethylaminoethylstearamide. also useful are dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, n-tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidylbehenylamine. useful amines in the present invention are disclosed in u.s. pat. no. 4,275,055. c. high melting point fatty compound the hair conditioning composition of the present invention comprises a high melting point fatty compound. the high melting point fatty compound is a compound having the general formula r—x, wherein r is an aliphatic (e.g. fatty chain) and x is a functional group (e.g. alcohol, acid, or derivative). the high melting point fatty compound, together with the above cationic surfactant and an aqueous carrier, provides a gel matrix which is suitable for providing various conditioning attributes such as slippery and slick feel on wet hair, and softness, moisturized feel, fly-away control on dry hair, dry hair smoothness, hair strand alignment (e.g., minimize frizziness), and ease of combing. suitable high melting point fatty compounds useful herein have a melting point of 25° c. or higher, and are selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. it is understood by the artisan that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, (e.g. some fatty alcohol derivatives can also be classified as fatty acid derivatives). however, a given classification is not intended to be a limitation on that particular compound, but is done so for convenience of classification and nomenclature. further, it is understood by the artisan that, depending on the number and position of double bonds and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than 25° c. such compounds of low melting point are not intended to be included in this section. nonlimiting examples of the high melting point compounds are found in international cosmetic ingredient dictionary, fifth edition, 1993, and ctfa cosmetic ingredient handbook, second edition, 1992. the high melting point fatty compound can be included in the composition at a level of from about 0.1% to about 20%, preferably from about 1% to about 10%, still more preferably from about 2% to about 9%, by weight of the composition. it is preferred that the high melting point fatty compound is included at a level so that the mole ratio of the cationic surfactant to the high melting fatty compound is from about 1:2 to about 1:8. the fatty alcohols useful herein are those having from about 14 to about 30 carbon atoms, preferably from about 16 to about 22 carbon atoms. these fatty alcohols are saturated and can be straight or branched chain alcohols. nonlimiting examples of fatty alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. the fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 25 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. these fatty acids are saturated and can be straight or branched chain acids. also included are diacids, triacids, and other multiple acids which meet the requirements herein. also included herein are salts of these fatty acids. nonlimiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof. the fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxy groups, hydroxy-substituted fatty acids, and mixtures thereof. nonlimiting examples of fatty alcohol derivatives and fatty acid derivatives include materials such as methyl stearyl ether; the ceteth series of compounds such as ceteth-1 through ceteth-45, which are ethylene glycol ethers of cetyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; the steareth series of compounds such as steareth-1 through steareth-10, which are ethylene glycol ethers of steareth alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; ceteareth 1 through ceteareth-10, which are the ethylene glycol ethers of ceteareth alcohol, (e.g. a mixture of fatty alcohols containing predominantly cetyl and stearyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present); c 1 -c 30 alkyl ethers of the ceteth, steareth, and ceteareth compounds just described; polyoxyethylene ethers of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, and mixtures thereof. high melting point fatty compounds of a single compound of high purity are preferred. single compounds of pure fatty alcohols selected from the group consisting of pure cetyl alcohol, stearyl alcohol, and behenyl alcohol are highly preferred. by “pure” herein, what is meant is that the compound has a purity of at least about 90%, preferably at least about 95%. these single compounds of high purity provide good rinsability from the hair when the consumer rinses off the composition. commercially available high melting point fatty compounds useful herein include: cetyl alcohol, stearyl alcohol, and behenyl alcohol having tradenames konol series available from shin nihon rika, and naa series available from nof; pure behenyl alcohol having tradename 1-docosanol available from wako, various fatty acids having tradenames neo-fat available from akzo, hystrene available from witco corp., and derma available from vevy. d. aqueous carrier the conditioning composition of the present invention comprises an aqueous carrier. the level and species of the carrier are selected according to the compatibility with other components and other desired characteristics of the product. the carrier useful in the present invention includes water and water solutions of lower alkyl alcohols and polyhydric alcohols. the lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, preferably ethanol and isopropanol. the polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propane diol. preferably, the aqueous carrier is substantially water. deionized water is preferably used. water from natural sources including mineral cations can also be used, depending on the desired characteristic of the product. generally, the compositions of the present invention comprise from about 20% to about 95%, preferably from about 30% to about 92%, and more preferably from about 50% to about 90% of an aqueous carrier. e. optional components 1. low viscosity fluid the compositions of the present invention may optionally comprise a low viscosity fluid to be mixed with the aminosilicone described above. the low viscosity fluid, when combined with the aminosilicone, serves to reduce the viscosity of the aminosilicone in order to facilitate the processing into the complete composition. concentrations of the low viscosity fluid in the conditioning compositions of the present invention will vary primarily with the type and amount of fluid and aminosilicone employed. preferred concentrations of the low viscosity fluid are from about 0.1% to about 20%, preferably from about 0.1% to about 10% by weight of the composition. preferred low viscosity fluids are partially or completely miscible with the amino silicone and are effective at reducing the viscosity of the blend. the low viscosity fluid or combination of fluids should be used in the composition so that there is the least amount of low viscosity fluid as possible. when the two materials are blended, the preferred viscosity range will be from about 500 cs to about 100,000 cs, more preferably from about 1,000 cs to about 50,000 cs. the low viscosity fluid for the aminosilicone is suitable for topical application to human hair and scalp. the low viscosity fluid is organic, silicone-containing or fluorine-containing, volatile or non-volatile, polar or non-polar, provided that the fluid is partially or completely miscible with the amino silicone and yields a mixture with the above stated viscosity. the low viscosity fluid preferably includes volatile, non-polar oils; non-volatile, relatively polar oils; non-volatile, non-polar oils; and non-volatile paraffinic hydrocarbon oils. the term “non-volatile” as used herein refers to materials which exhibit a vapor pressure of no more than about 0.2 mm hg at 25° c. at one atmosphere and/or to materials that have a boiling point at one atmosphere of at least about 300° c. the term “volatile” as used herein refers to all materials that are not “non-volatile” as previously defined herein. the phrase “relatively polar” as used herein means more polar than another material in terms of solubility parameter (e.g., the higher the solubility parameter the more polar the liquid). the term “non-polar” typically means that the material has a solubility parameter below about 6.5 (cal/cm 3 ) 0.5 . a. non-polar, volatile oils non-polar, volatile oils particularly useful in the present invention are selected from the group consisting of silicone oils, hydrocarbons, and mixtures thereof. such non-polar, volatile oils are disclosed, for example, in cosmetics, science, and technology, vol. 1, 27-104. the non-polar, volatile oils useful in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings. examples of preferred non-polar, volatile hydrocarbons include polydecanes such as isododecane and isodecane (e.g., permethyl-99a which is available from presperse inc.) and the c7-c8 through c12-c15 isoparaffins (such as the isopar series available from exxon chemicals). other isoparaffins include, for example, isozol series available from nippon petrochemicals co., ltd, such as isozol 200 (containing mainly c8 isoparaffin), isozol 300 (containing mainly c12 isoparaffin), and isozol 400 (containing mainly c14 isoparaffin). non-polar, volatile hydrocarbons, especially non-polar, volatile isoparaffins are highly preferred among a variety of low viscosity fluids, in view of reducing the viscosity of the aminosilicones and providing improved hair conditioning benefits such as reduced friction on dry hair. non-polar, volatile liquid silicone oils are disclosed in u.s. pat. no. 4,781,917. additionally, a description of various volatile silicones materials is found in todd et al., “volatile silicone fluids for cosmetics”, cosmetics and toiletries, 91:27-32 (1976). particularly preferred volatile silicone oils are selected from the group consisting of cyclic volatile silicones corresponding to the formula (v): wherein n is from about 3 to about 7; and linear volatile silicones corresponding to the formula (vi): (ch 3 ) 3 si—o—[si(ch 3 ) 2 —o] m —si(ch 3 ) 3 wherein m is from about 1 to about 7. linear volatile silicones generally have a viscosity of less than about 5 centistokes at 25° c., whereas the cyclic silicones have viscosities of less than about 10 centistokes at 25° c. highly preferred examples of volatile silicone oils include cyclomethicones of varying viscosities, e.g., dow corning 200, dow corning 244, dow corning 245, dow corning 344, and dow corning 345, (commercially available from dow corning corp.); sf-1204 and sf-1202 silicone fluids (commercially available from g.e. silicones), ge 7207 and 7158 (commercially available from general electric co.); and sws-03314 (commercially available from sws silicones corp.). b. relatively polar, non-volatile oils the non-volatile oil is “relatively polar” as compared to the non-polar, volatile oil discussed above. therefore, the non-volatile co-solvent is more polar (e.g., has a higher solubility parameter) than at least one of the non-polar, volatile oils. relatively polar, non-volatile oils potentially useful in the present invention are disclosed, for example, in cosmetics, science, and technology, vol. 1, 27-104 edited by balsam and sagarin, 1972; u.s. pat. nos. 4,202,879 and 4,816,261. relatively polar, non-volatile oils useful in the present invention are preferably selected from the group consisting of silicone oils; hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids with mono and polyhydric alcohols; polyoxyethylenes; polyoxypropylenes; mixtures of polyoxyethylene and polyoxypropylene ethers of fatty alcohols; and mixtures thereof. the relatively polar, non-volatile co-solvents useful in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings. more preferably, the relatively polar, non-volatile liquid co-solvents are selected from the group consisting of fatty alcohols having from about 12-26 carbon atoms; fatty acids having from about 12-26 carbon atoms; esters of monobasic carboxylic acids and alcohols having from about 14-30 carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about 5-26 carbon atoms; ethoxylated, propoxylated, and mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12-26 carbon atoms and a degree of ethoxylation and propoxylation of below about 50; and mixtures thereof. more preferred are propoxylated ethers of c14-c18 fatty alcohols having a degree of propoxylation below about 50, esters of c2-c8 alcohols and c12-c26 carboxylic acids (e.g. ethyl myristate, isopropyl palmitate), esters of c12-c26 alcohols and benzoic acid (e.g. finsolv tn supplied by finetex), diesters of c2-c8 alcohols and adipic, sebacic, and phthalic acids (e.g., diisopropyl sebacate, diisopropyl adipate, di-n-butyl phthalate), polyhydric alcohol esters of c6-c26 carboxylic acids (e.g., propylene glycol dicaprate/dicaprylate, propylene glycol isostearate); and mixtures thereof. even more preferred are branched-chain aliphatic fatty alcohols having from about 12-26 carbon atoms. even more preferred are isocetyl alcohol, octyldecanol, octyldodecanol and undecylpentadecanol; and even more preferred is octyldodecanol. c. non-polar, non-volatile oils in addition to the liquids discussed above, the low viscosity fluid may optionally include non-volatile, non-polar oils. typical non-volatile, non-polar oils are disclosed, for example, in cosmetics, science, and technology, vol. 1, 27-104 edited by balsam and sagarin, 1972; u.s. pat. nos. 4,202,879 and 4,816,261. the non-volatile oils useful in the present invention are essentially non-volatile polysiloxanes, paraffinic hydrocarbon oils, and mixtures thereof. the polysiloxanes useful in the present invention selected from the group consisting of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, poly-ethersiloxane copolymers, and mixtures thereof. examples of these include polydimethyl siloxanes having viscosities of from about 1 to about 100,000 centistokes at 25° c. among the preferred non-volatile silicone emollients useful in the present compositions are the polydimethyl siloxanes having viscosities of from about 2 to about 400 centistokes at 25° c. such polyalkylsiloxanes include the viscasil series (sold by general electric company) and the dow corning 200 series (sold by dow corning corp.). polyalkylarylsiloxanes include polymethylphenyl siloxanes having viscosities of from about 15 to about 65 centistokes at 25° c. these are available, for example, as sf 1075 methyl-phenyl fluid (sold by general electric company) and 556 cosmetic grade fluid (sold by dow corning corp.). useful polyethersiloxane copolymers include, for example, a polyoxyalkylene ether copolymer having a viscosity of from about 1200 to about 1500 centistokes at 25° c. such a fluid is available as sf1066 organosilicone surfactant (sold by general electric company). polysiloxane ethylene glycol ether copolymers are preferred copolymers for use in the present compositions. non-volatile paraffinic hydrocarbon oils useful in the present invention include mineral oils and certain branched-chain hydrocarbons. examples of these fluids are disclosed in u.s. pat. no. 5,019,375. preferred mineral oils have the following properties: (1) viscosity of from about 5 centistokes to about 70 centistokes at 40° c.; (2) density of from about 0.82 to about 0.89 g/cm 3 at 25° c.; (3) flash point of from about 138° c. to about 216° c.; and (4) carbon chain length of from about 14 to about 40 carbon atoms. preferred branched chain hydrocarbon oils have the following properties: (1) density of from about 0.79 to about 0.89 g/cm3 at 20° c.; (2) boiling point greater than about 250° c.; and (3) flash point of from about 110° c. to about 200° c. particularly preferred branched-chain hydrocarbons include permethyl 103 a, which contains an average of about 24 carbon atoms; permethyl 104a, which contains an average of about 68 carbon atoms; permethyl 102a, which contains an average of about 20 carbon atoms; all of which may be purchased from permethyl corporation; and ethylflo 364 which contains a mixture of 30 carbon atoms and 40 carbon atoms and may be purchased from ethyl corp. additional solvents useful herein are described in u.s. pat. no. 5,750,096. 2. acid the hair conditioning composition of the present invention may further comprise an acid selected from the group consisting of l-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, l-glutamic acid hydrochloride, tartaric acid, citric acid, and mixtures thereof; preferably l-glutamic acid, lactic acid, citric acid, and mixtures thereof. the amines herein are preferably partially neutralized with any of the acids at a molar ratio of the amine to the acid of from about 1:0.3 to about 1:2, more preferably from about 1:0.4 to about 1:1.3. 3. polysorbate the hair conditioning composition of the present invention preferably contains a polysorbate, in order to adjust rheology. preferred polysorbates useful herein include polysorbate-20, polysorbate-21, polysorbate-40, polysorbate-60, and mixtures thereof. highly preferred is polysorbate-20. the polysorbate can be contained in the composition at a level by weight of from about 0.01% to about 5%, preferably from about 0.05% to about 2%. 4. polypropylene glycol polypropylene glycols useful herein are those having a weight average molecular weight of from about 200 g/mol to about 100,000 g/mol, preferably from about 1,000 g/mol to about 60,000 g/mol. without intending to be limited by theory, it is believed that the polypropylene glycol herein deposits onto, or is absorbed into hair to act as a moisturizer buffer, and/or provides one or more other desirable hair conditioning benefits. the polypropylene glycol useful herein may be either water-soluble, water-insoluble, or may have a limited solubility in water, depending upon the degree of polymerization and whether other moieties are attached thereto. the desired solubility of the polypropylene glycol in water will depend in large part upon the form (e.g., leave-on, or rinse-off form) of the hair care composition. for example, in a rinse-off hair care composition, it is preferred that the polypropylene glycol herein has a solubility in water at 25° c. of less than about 1 g/100 g water, more preferably a solubility in water of less than about 0.5 g/100 g water, and even more preferably a solubility in water of less than about 0.1 g/100 g water. the polypropylene glycol can be included in the hair conditioning composition of the present invention at a level of from about 0.01% to about 10%, preferably from about 0.05% to about 6%, more preferably from about 0.1% to about 3% by weight of the composition. 5. low melting point oil low melting point oils useful herein are those having a melting point of less than 25° c. the low melting point oil useful herein is selected from the group consisting of: hydrocarbon having from about 10 to about 40 carbon atoms; unsaturated fatty alcohols having from about 10 to about 30 carbon atoms such as oleyl alcohol; unsaturated fatty acids having from about 10 to about 30 carbon atoms; fatty acid derivatives; fatty alcohol derivatives; ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, and glyceryl ester oils; poly α-olefin oils; and mixtures thereof. preferred low melting point oils herein are selected from the group consisting of: ester oils such as pentaerythritol ester oils, trimethylol ester oils, citrate ester oils, and glyceryl ester oils; poly α-olefin oils; and mixtures thereof, particularly useful pentaerythritol ester oils and trimethylol ester oils herein include pentaerythritol tetraisostearate, pentaerythritol tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate, and mixtures thereof. such compounds are available from kokyo alcohol with tradenames kakpti, kaktti, and shin-nihon rika with tradenames pto, enujerubu tp3so. particularly useful citrate ester oils herein include triisocetyl citrate with tradename citmol 316 available from bernel, triisostearyl citrate with tradename pelemol tisc available from phoenix, and trioctyldodecyl citrate with tradename citmol 320 available from bernel. particularly useful glyceryl ester oils herein include triisostearin with tradename sun espol g-318 available from taiyo kagaku, triolein with tradename cithrol gto available from croda surfactants ltd., trilinolein with tradename efaderma-f available from vevy, or tradename efa-glycerides from brooks. particularly useful poly α-olefin oils herein include polydecenes with tradenames puresyn 6 having a number average molecular weight of about 500 and puresyn 100 having a number average molecular weight of about 3000 and puresyn 300 having a number average molecular weight of about 6000 available from exxon mobil co. the low melting point oil can be included in the hair conditioning composition of the present invention at a level of from about 0.001% to about 10%, preferably up to about 5% by weight of the composition. 6. cationic polymer cationic polymers useful herein are those having an average molecular weight of at least about 5,000, typically from about 10,000 to about 10 million, preferably from about 100,000 to about 2 million. suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol. other suitable cationic polymers useful herein include, for example, cationic celluloses, cationic starches, and cationic guar gums. the cationic polymer can be included in the hair conditioning composition of the present invention at a level of from about 0.001% to about 10%, preferably up to about 5% by weight of the composition. 7. polyethylene glycol polyethylene glycol can also be used as an additional component. the polyethylene glycols useful herein correspond to the formula h(o—ch 2 —ch 2 ) n oh, wherein n is the number of ethoxy units. polyethylene glycols useful herein include peg-2m wherein n has an average value of about 2,000 (peg-2m is also known as polyox wsr® n-10 from union carbide and as peg-2,000); peg-5m wherein n has an average value of about 5,000 (peg-5m is also known as polyox wsr® n-35 and as polyox wsr® n-80, both from union carbide and as peg-5,000 and polyethylene glycol 300,000); peg-7m wherein n has an average value of about 7,000 (peg-7m is also known as polyox wsr® n-750 from union carbide); peg-9m wherein n has an average value of about 9,000 (peg-9m is also known as polyox wsr® n-3333 from union carbide); and peg-14m wherein n has an average value of about 14,000 (peg-14m is also known as polyox wsr® n-3000 from union carbide). the polyethylene glycol can be included in the hair conditioning composition of the present invention at a level of from about 0.001% to about 10%, preferably up to about 5% by weight of the composition. 8. additional components the composition of the present invention may include other additional components, which may be selected by the artisan according to the desired characteristics of the final product and which are suitable for rendering the composition more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. such other additional components generally are used individually at levels of from about 0.001% to about 10%, preferably up to about 5% by weight of the composition. a wide variety of other additional components can be formulated into the present compositions. these include: other conditioning agents such as hydrolysed collagen with tradename peptein 2000 available from hormel; vitamin e with tradename emix-d available from eisai; panthenol available from roche; panthenyl ethyl ether available from roche; hydrolysed keratin, proteins, plant extracts, and nutrients; emollients such as ppg-3 myristyl ether with tradename varonic apm available from goldschmidt; trimethyl pentanol hydroxyethyl ether; ppg-11 stearyl ether with tradename varonic aps available from goldschmidt; stearyl heptanoate with tradename tegosoft sh available from goldschmidt; lactil (mixture of sodium lactate, sodium pca, glycine, fructose, urea, niacinamide, inositol, sodium benzoate, and lactic acid) available from goldschmidt; ethyl hexyl palmitate with tradename saracos available from nishin seiyu and with tradename tegosoft op available from goldschmidt; hair-fixative polymers such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, and silicone grafted copolymers; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; ph adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the fd&c or d&c dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts; hair reducing agents such as the thioglycolates; perfumes; sequestering agents, such as disodium ethylenediamine tetra-acetate; ultraviolet and infrared screening and absorbing agents such as octyl salicylate; and antidandruff agents such as zinc pyrithione and salicylic acid. method of preparation the hair conditioning compositions of the following examples can be prepared by any conventional method well known in the art. they are suitably made as follows: deionized water is heated to 85° c. and cationic surfactants and high melting point fatty compounds are mixed in. the water is maintained at a temperature of about 85° c. until the components are homogenized, and no solids are observed. the mixture is then cooled to about 55° c. and maintained at this temperature, to form a gel matrix. aminosilicones, or a blend of aminosilicones and a low viscosity fluid, or an aqueous dispersion of an aminosilicione are added to the gel matrix. when included, poly α-olefin oils, polypropylene glycols, and/or polysorbates are also added to the gel matrix. the gel matrix is maintained at about 50° c. during this time with constant stirring to assure homogenization. after it is homogenized, it is cooled to room temperature. when included, other additional components such as perfumes and preservatives are added with agitation. a triblender and/or mill can be used in each step, if necessary to disperse the materials. method of use the conditioning compositions of the present invention are used in conventional ways to provide conditioning and other benefits. such method of use depends upon the type of composition employed but generally involves application of an effective amount of the product to the hair or scalp, which may then be rinsed from the hair or scalp (as in the case of hair rinses) or allowed to remain on the hair or scalp (as in the case of gels, lotions, creams, and sprays). “effective amount” means an amount sufficient enough to provide a dry conditioning benefit. in general, from about 1 g to about 50 g is applied to the hair or scalp. preferably, the composition is applied to wet or damp hair prior to drying of the hair. typically, the composition is used after shampooing the hair. the composition is distributed throughout the hair or scalp, typically by rubbing or massaging the hair or scalp. after such compositions are applied to the hair, the hair is dried and styled in accordance with the preference of the user. in the alternative, the composition is applied to dry hair, and the hair is then combed or styled in accordance with the preference of the user. non-limiting examples the compositions illustrated in the following examples exemplify specific embodiments of the compositions of the present invention, but are not intended to be limiting thereof. other modifications can be undertaken by the skilled artisan without departing from the spirit and scope of this invention. the compositions illustrated in the following examples are prepared by conventional formulation and mixing methods. all exemplified amounts are listed as weight percents and exclude minor materials such as diluents, preservatives, color solutions, imagery ingredients, botanicals, and so forth, unless otherwise specified. example i example i demonstrates the surprising discovery that aminosilicones below a certain percent nitrogen range will provide a superior level of reduced friction on treated hair. table 1 shows the relationship between friction and percent nitrogenfor amino functionalized silicone. herein, “ap” is aminopropyl;herein, “aeap” is aminoethylaminopropyl.aminecoef. ofpositiontypevisc% nfrictionnone—350,00000.390termap412,0000.0220.298termap312,0000.0260.290termap111,8750.0320.282termap87,0000.0350.300termap55,9500.0380.277termap31,0000.0510.282termap10,4500.0530.311termap22,9800.0600.294termap12,3380.0700.298graftaeap46,2000.0740.322termap8,3910.0760.292termap7,0290.0770.304termap5,1130.0870.282termaeap24,1600.1130.341termap2,0380.1260.307graftap191,8000.1640.426graftaeap1,000,000+0.1760.401graftaeap1,000,000+0.1820.386graftap53,4000.1820.390graftaeap78,4000.1960.338graftaeap558,0000.2110.354graftaeap1,000,000+0.5040.490graftaeap98,5000.6160.472graftap1,000,000+0.6160.520graftap143,5000.6370.509 for this study, the silicone is dissolved in a volatile solvent, hexamethyl disiloxane (mm), and applied to hair (20 gram flat switch) or 2 gram paper strip (3 inches by 9 inches (7.62 cm×22.86 cm)) at a level of 1,000 ppm of silicone to hair/paper weight. the solvent is allowed to evaporate and the hair/paper is allowed to equilibrate in a 50% relative humidity overnight. the friction of the coated hair/paper is then measured using an instron model 5542 (instron, inc.) to measure the force to drag a weighted sled (100 gms of weight) along the hair/paper in the with-cuticle direction. examples ii-vi ingredientiiiiiivvviglutamic acid (1)0.6400.6400.6400.6400.640stearamidopropyl dimethylamine (2)2.0002.0002.0002.000—behenamidopropyl dimethylamine (3)————2.300cetyl alcohol (4)2.5002.5002.5002.5002.500stearyl alochol (5)4.5004.5004.5004.5004.500dimethicone (6)3.0006.000——3.000amodimethicone (7)2.0004.0002.0002.0002.000dimethicone (8)——3.000——edta (9)0.1000.1000.1000.1000.100benzyl alcohol (10)0.4000.4000.4000.4000.400methylchloroisothiazolinone,0.00050.00050.00050.00050.0005methylisothiazolinone (11)panthenyl etheyl ether (12)0.0500.0500.0500.0500.050panthenol (13)0.0500.0500.0500.0500.050perfume0.3000.3000.3000.3000.300waterq.s.q.s.q.s.q.s.q.s.(1) l-glutamic acid, available from orsan/amylum(2) stearamidopropyldimethylamine (sapdma), available from saci(3) bapdma (incrominebb), available from croda(4) available from p&g brooksland(5) available from p&g brooksland(6) tsf-451-20a (20 cs straight oil), available from ge(7) terminal aminosilicone, ap type, available from ge; viscosity range from 220,000-245,000(8) dow corning 200 fluid, 10 cs(9) ethylene diamine tetraacetic acid (edta), available from basf(10) available from tessenderlo(11) kathon cg, available from rohm & haas(12) dl-pantyl, available from dow benelux(13) liquid dl-panthenol (56% active), available from dow benelux examples vii-x ingredientviiviiiixxstearamidopropyl———1.000dimethylamine (1)behentrimonium chloride/2.8743.4453.381—isopropyl alcohol (2)cetyl alcohol (3)1.9721.9722.3200.960stearyl alochol (4)3.5533.5534.1800.640dimethicone (5)3.0003.0003.0003.000amodimethicone (6)2.0002.0002.0002.000edta (7)———0.100disodium edta (8)0.1270.1270.127—benzyl alcohol (9)0.4000.4000.4000.400methylchloroisothiazolinone,0.00050.00050.00050.0005methylisothiazolinone (10)panthenyl etheyl ether (11)0.0500.0500.0500.050panthenol (12)———0.050panthenol (13)0.0500.0500.050—sodium hydroxide (14)0.0140.0140.014—isopropyl alcohol (15)0.7640.9160.899—citric acid (16)———0.130quaternium-18 (17)———0.750hydroxyethylcellulose (18)———0.250peg-2m (19)———0.500polysorbate 60, cetearyl———0.500alcohol (20)glyceryl stearate (21)———0.250oleyl alcohol (22)———0.250perfume0.3000.3000.3000.250waterq.s.q.s.q.s.q.s.(1) stearamidopropyldimethylamine (sapdma), available from saci(2) btmac/ipa (genamin kdmp), available from clariant(3) available from p&g brooksland(4) available from p&g brooksland(5) tsf-451-20a (20 cst straight oil), available from ge(6) terminal aminosilicone, ap type, available from ge; viscosity range from 220,000-245,000(7) ethylene diamine tetraacetic acid (edta), available from basf(8) disodium edta, available from scal(9) available from tessenderlo(10) kathon cg, available from rohm & haas(11) dl-pantyl, available from dow benelux(12) dl-panthenol (powder), available from dow benelux(13) liquid dl-panthenol (56% active), available from dow benelux(14) sodium hydroxide (naoh), available from kaneda(15) ipa (as solvent for btmac)(16) available from jungbunzlauer(17) distearyldimethylammonium chloride (dsdmac), available from goldschmidt(18) available from hercules/aqualon(19) peg-2m (polyox warn-10), available from amerchol(20) emulsifying wax (polawax nf), available from croda(21) glyceryl monostearate (gms), available from surfachem(22) available from njc/tomen examples xi-xv ingredientxixiixiiixivxvbehentrimonium chloride (1)2.2502.2503.3813.381—isopropyl alcohol (1)0.5980.5980.8990.899—stearamidopropyldimethylamine (2)————2.000l-glutamic acid (3)————0.640cetyl alcohol (4)1.8571.8572.3202.3202.500stearyl alochol (5)4.6424.6424.1804.1804.200amodimethicone (6)3.5003.5003.5003.5004.200isoparaffin (7)1.500—1.500—6.300disodium edta (8)0.1270.1270.1270.127—edta (9)————0.1benzyl alcohol (10)0.4000.4000.4000.4000.400methylchloroisothiazolinone,0.00050.00050.00050.00050.0005methylisothiazolinone (11)panthenyl etheyl ether (12)0.050——0.0500.050panthenol (13)0.050——0.0500.050sodium hydroxide (14)0.0140.0140.0140.014—perfume0.5000.5000.5000.5000.500waterq.s.q.s.q.s.q.s.q.s.(1) btmac/ipa (genamin kdmp), available from clariant(2) stearamidopropyldimethylamine, available from saci(3) l-glutamic acid, available from orsan/amylum(4) available from p&g brooksland(5) available from p&g brooksland(6) terminal aminosilicone, ap type, available from ge; viscosity range from 220,000-245,000(7) isozol 400 (a mixture of c11-c16 isoparaffins containing about 41% of c14 isoparaffin), available from nippon petrochemicals co., ltd.(8) available from scal(9) ethylene diamine tetraacetic acid (edta), available from basf(10) available from tessenderlo(11) kathon cg, available from rohm & haas(12) dl-pantyl, available from dow benelux(13) liquid dl-panthenol, available from dow benelux(14) sodium hydroxide (naoh), available from kaneda while particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. all documents cited in the background, summary of the invention, and detailed description of the invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
|
136-151-648-287-359
|
GB
|
[
"US",
"JP",
"KR",
"EP",
"GB",
"WO"
] |
G02F1/133,G09G3/20,G09G3/36,G09G5/10
| 2001-03-02T00:00:00 |
2001
|
[
"G02",
"G09"
] |
active matrix display device
|
a display has circuitry ( 50 ) which generates all possible pixel drive signal levels on separate signal level lines. a buffer ( 54 ) is associated with each signal level line. the outputs of the buffers are selectably switchable onto the columns. the signal levels for each column are stored in a memory ( 72 ) and the buffers are controlled in dependence on the stored signal levels. the response of the buffers is heavily dependent on the output load, and there is a very large variation in the output load of the buffers ( 54 ), as a function of the number of columns to which the buffer output is to be provided. the buffers are controlled in dependence on stored signal levels to ensure stability of the buffers for any output load.
|
1 . a display device comprising an array of liquid crystal pixels arranged in rows and columns, wherein: each column of pixels includes a column conductor to which pixel drive signals are provided to pixels in the column, column address circuitry is provided for generating the pixel drive signals, the column address circuitry comprising: circuitry for generating all defined drive signal levels on corresponding separate signal level lines, and a buffer associated with each signal level line, the outputs of the buffers being selectably switchable onto the columns as the pixel drive signals, the column address circuitry further comprises: a memory for storing values corresponding to the drive signal levels to be provided to each column, and the buffers are controlled in dependence on the stored values. 2 . a display device as claimed in claim 1 , wherein a bias current to each buffer is controlled in dependence on a quantity of columns to which the buffer output is to be switched. 3 . a display device as claimed in claim 1 , wherein each signal level line is associated with a plurality of buffers, each of the plurality of buffers being suitable for different output loads, and one of the plurality of buffers is selected in dependence on a quantity of columns to which the buffer output is to be switched. 4 . a display device as claimed in claim 3 , wherein each signal level line is associated with two buffers. 5 . a display device as claimed in claim 1 , wherein: each buffer has a plurality of selectable output stages, and the output stages selected is controlled in dependence on a quantity of columns to which the buffer output is to be switched. 6 - 7 . (canceled) 8 . a display device as claimed in claim 1 , wherein: each pixel comprises a thin film transistor switching device and a liquid crystal cell, each row of pixels includes a row conductor which connects to the gates of the thin film transistors of the pixels in the row, and row driver circuitry provides row address signals for controlling switching of the transistors of the pixels of the row. 9 . a method of providing pixel drive signals to a display device comprising an array of liquid crystal pixels arranged in rows and columns, the method comprising: generating all defined pixel drive signal levels; providing each pixel drive signal level to an associated buffer; storing values corresponding to required pixel drive signal levels for a row of pixels in a memory; calculating a quantity of pixels of the row to be addressed by each drive signal, based on the stored values; controlling the buffers in dependence on the calculated quantity of pixels; and switching the buffer outputs onto the columns during the row address period for the row to be addressed. 10 . a method as claimed in claim 9 , wherein controlling the buffers comprises applying an appropriate bias current to the buffers. 11 . a method as claimed in claim 9 , wherein controlling the buffers comprises selecting between alternative buffers for each pixel drive signal level. 12 . a method as claimed in claim 9 , wherein controlling the buffers comprises selecting a number of output stages to be connected to each buffer. 13 - 14 . (canceled) 15 . column address circuitry for driving columns of a liquid crystal display, each column having a column output that is configured to provide one of a plurality of defined drive signal levels to a plurality of pixels, comprising: circuitry for generating all of the defined drive signal levels on corresponding separate signal level lines, and a buffer associated with each signal level line, the outputs of the buffers being selectably switchable onto the column outputs, wherein: the column address circuitry further comprises a memory for storing values corresponding to the drive signal levels to be provided to each column, and the buffers are controlled in dependence on the stored values. 16 . the column address circuitry of claim 15 , wherein the buffers are controlled in dependence upon a histogram corresponding to the stored values. 17 . the column address circuitry of claim 15 , wherein each buffer is controlled to provide an output energy level that is dependent upon a quantity of columns that are selectively switched to the output of the buffer. 18 . the column address circuitry of claim 15 , wherein the output of each buffer is selectively switched to each column output based on the stored value corresponding to the drive signal level to be provided to the column. 19 . the column address circuitry of claim 15 , wherein each column includes an n:1 selector that is configured to select the output of the buffer corresponding to the stored value corresponding to the drive signal level to be provided to the column, and n corresponding to a quantity of the defined drive signal levels. 20 . the column address circuitry of claim 15 , wherein the defined drive signal levels correspond to grey-scale illumination values.
|
this invention relates to active matrix display devices, and relates in particular to the circuitry used for providing drive signals to the pixels of the display. active matrix display devices typically comprise an array of pixels arranged in rows and columns. each row of pixels shares a row conductor which connects to the gates of the thin film transistors of the pixels in the row. each column of pixels shares a column conductor, to which pixel drive signals are provided. the signal on the row conductor determines whether the transistor is turned on or off, and when the transistor is turned on, by a high voltage pulse on the row conductor, a signal from the column conductor is allowed to pass on to an area of liquid crystal material, thereby altering the light transmission characteristics of the material. an additional storage capacitor may be provided as part of the pixel configuration to enable a voltage to be maintained on the liquid crystal material even after removal of the row electrode pulse. u.s. pat. no. 5,130,829 discloses in more detail the design of an active matrix display device. the frame (field) period for active matrix display devices requires a row of pixels to be addressed in a short period of time, and this in turn imposes a requirement on the current driving capabilities of the transistor in order to charge or discharge the liquid crystal material to the desired voltage level. in order to meet these current requirements, the gate voltage supplied to the thin film transistor needs to fluctuate between values separated by approximately 30 volts. for example, the transistor may be turned off by applying a gate voltage of around 10 volts, or even lower, (with respect to the source) whereas a voltage of around 20 volts, or even higher, may be required to bias the transistor sufficiently to provide the required source-drain current to charge or discharge the liquid crystal material sufficiently rapidly. the requirement for large voltage swings in the row conductors requires the row driver circuitry to be implemented using high voltage components. the voltages provided on the column conductors typically vary by approximately 10 volts, which represents the difference between the drive signals required to drive the liquid crystal material between white and black states. various drive schemes have been proposed enabling the voltage swing on the column conductors to be reduced, so that lower voltage components may be used in the column driver circuitry. in the so-called common electrode drive scheme, the common electrode, connected to the full liquid crystal material layer, is driven to an oscillating voltage. the so-called four-level drive scheme uses more complicated row electrode waveforms in order to reduce the voltage swing on the column conductors, using capacitive coupling effects. these drive schemes enable lower voltage components to be used forthe column driver circuitry. however, there is still a significant amount of complexity and power inefficiency in the column driver circuits. each row is addressed in turn, and during the row address period of any one row, pixel signals are provided to each column. in the past, each column would be provided with a buffer for holding a pixel in the column to a drive signal level for the full duration of the row address period. this large number of buffers results in high power consumption. there have been proposals to provide a multiplexing scheme, in which a buffer is shared between a group of columns. the output of the buffer is switched in turn to the columns of the group. when the buffer is providing a signal to one column, it is isolated from the other columns by a switch. multiplexing is possible because the line time of the display is significantly greater than the time required to charge a column to the required voltage. in small displays for mobile applications, the line time may be in excess of 150 s whereas the time required to charge a column is typically less than 10 s. once the column has been charged to the required voltage, and after the end of the application of the required voltage to the column, charge transfer takes place between the charged column capacitance and the pixel capacitance. the column capacitance may be around 30 times larger than the column capacitance, so that the charge transfer to the pixel results in only a small voltage change. however, this charge transfer enables the pixel to be charged using a short column address pulse, despite the longer time constant of the pixel (resulting from the high tft resistance). a problem with this multiplexing approach is that there is cross talk between the columns within the group, particularly as all but one of the columns of the group are effectively floating at any point in time, and are therefore susceptible to signal level fluctuations. during the row address period, the tfts of all pixels in the row are switched on (and indeed this enables the charge transfer to take place between the column capacitance and the pixel), so that any signal fluctuations on the column conductors as a result of cross talk are passed onto the pixels. the invention provides an alternative approach for reducing the number of buffers required by the column driver circuitry. according to a first aspect of the invention, there is provided a display device comprising an array of liquid crystal pixels arranged in rows and columns, wherein each column of pixels shares a column conductor to which pixel drive signals are provided, wherein column address circuitry is provided for generating the pixel drive signals, the column address circuitry comprising circuitry for generating all possible drive signal levels on separate signal level lines and a buffer associated with each signal level line, the outputs of the buffers being selectably switchable onto the columns, wherein the column address circuitry further comprises a memory for storing the signal levels to be provided to each column, and wherein the buffers are controlled in dependence on the stored signal levels. the invention provides an alternative approach by which a grey level generation circuit is provided with a buffer for each possible grey level output. the response of the buffers is heavily dependent on the output load, and such buffers are typically designed to be suitable for specific ranges of output loads. as a result of the large number columns in a display, there is a very large variation in the output load of the buffers, as a function of the number of columns to which the buffer output is to be provided. therefore, the buffers are controlled in dependence on stored signal levels to ensure stability of the buffers for any output load. in one example, a bias current to each buffer is controlled in dependence on the number of columns to which the buffer output is to be switched. in another example, each signal level line is associated with a plurality of buffers, each of the plurality of buffers being suitable for different output loads, wherein one of the plurality of buffers is selected in dependence on the number of columns to which the buffer output is to be switched. each signal level line may be associated with two buffers. in another example, each buffer has a plurality of output stages, and wherein the number of output stages used is controlled in dependence on the number of columns to which the buffer output is to be switched. in a further example, an additional buffer is provided and the additional buffer is used when the number of columns to which an individual buffer output is to be switched exceeds half the total number of columns. these examples each provide arrangements which enable the output load required of each buffer to be used to provide control of the buffer configuration, in order to ensure stability of the buffer arrangements. the number of grey levels will typically be much smaller than the number of columns, so that the arrangement of the invention reduces the number of buffers required. preferably, each pixel comprises a thin film transistor switching device and a liquid crystal cell, wherein each row of pixels share a row conductor which connects to the gates of the thin film transistors of the pixels in the row, and wherein row driver circuitry provides row address signals for controlling the switching of the transistors of the pixels of the row. according to a second aspect of the invention, there is provided a method of providing pixel drive signals to a display device comprising an array of liquid crystal pixels arranged in rows and columns, the method comprising: generating all possible pixel drive signal levels; providing each pixel drive signal level to an associated buffer; storing the required pixel drive signals for a row of pixels in a memory; calculating the required number of pixels of the row to be addressed by each drive signal; controlling the buffers in dependence on the calculated number of pixels; and switching the buffer outputs onto the columns during the row address period for the row to be addressed. the step of controlling the buffers may comprise applying an appropriate bias current to the buffers, selecting between alternative buffers for each pixel drive signal level or selecting a number of output stages to be connected to each buffer. the invention also provides column address circuitry for driving the columns of a liquid crystal display, comprising circuitry for generating all possible drive signal levels on separate signal level lines and a buffer associated with each signal level line, the outputs of the buffers being selectably switchable onto the column outputs, wherein the column address circuitry further comprises a memory for storing the signal levels to be provided to each column, and wherein the buffers are controlled in dependence on the stored signal levels. examples of the invention will now be described in detail with reference to the accompanying drawings, in which: fig. 1 shows one example of a known pixel configuration for an active matrix liquid crystal display; fig. 2 shows a display device including row and column driver circuitry; fig. 3 shows a conventional column driver circuit; fig. 4 shows a column driver circuit according to the invention; fig. 5 shows in greater detail the memory in the circuit of fig. 4 ; fig. 6 shows in greater detail part of the memory of fig. 5 ; fig. 7 shows one buffer configuration for use in the column driver circuit of the invention; fig. 8 shows another buffer configuration for use in the column driver circuit of the invention; and fig. 9 shows a further buffer configuration for use in the column driver circuit of the invention. fig. 1 shows a conventional pixel configuration for an active matrix liquid crystal display. the display is arranged as an array of pixels in rows and columns. each row of pixels shares a common row conductor 10 , and each column of pixels shares a common column conductor 12 . each pixel comprises a thin film transistor 14 and a liquid crystal cell 16 arranged in series between the column conductor 12 and a common potential 18 . the transistor 14 is switched on and off by a signal provided on the row conductor 10 . the row conductor 10 is thus connected to the gate 14 a of each transistor 14 of the associated row of pixels. each pixel may additionally comprise a storage capacitor 20 which is connected at one end 22 to the next row electrode, to the preceding row electrode, or to a separate capacitor electrode. this capacitor 20 helps to maintain the drive voltage across the liquid crystal cell 16 after the transistor 14 has been turned off. a higher total pixel capacitance is also desirable to reduce various effects, such as kickback, and to reduce the grey-level dependence of the pixel capacitance. in order to drive the liquid crystal cell 16 to a desired voltage to obtain a required grey level, an appropriate signal is provided on the column conductor 12 in synchronism with a row address pulse on the row conductor 10 . this row address pulse turns on the thin film transistor 14 , thereby allowing the column conductor 12 to charge the liquid crystal cell 16 to the desired voltage, and also to charge the storage capacitor 20 to the same voltage. at the end of the row address pulse, the transistor 14 is turned off. the storage capacitor 20 reduces the effect of liquid crystal leakage and reduces the percentage variation in the pixel capacitance caused by the voltage dependency of the liquid crystal cell capacitance. the rows are addressed sequentially so that all rows are addressed in one frame period, and refreshed in subsequent frame periods. as shown in fig. 2 , the row address signals are provided by row driver circuitry 30 , and the pixel drive signals are provided by column address circuitry 32 , to the array 34 of display pixels. in order to enable a sufficient current to be driven through the thin film transistor 14 , which is implemented as an amorphous silicon thin film device, a high gate voltage must be used. in particular, the period during which the transistor is turned on is approximately equal to the total frame period within which the display must be refreshed, divided by the number of rows. it is well known that the gate voltage for the on-state and the off-state differ by approximately 30 volts in order to provide the required small leakage current in the off-state, and sufficient current flow in the on-state to charge or discharge the liquid crystal cell 16 within the available time. as a result, the row driver circuitry 30 uses high voltage components. there are various known addressing schemes for driving the display of fig. 1 , and these will not be described in detail in this text. some of the known operational techniques are described in greater detail, for example in u.s. pat. no. 5,130,829 and wo 99/52012, and these documents are incorporated herein by way of reference material. the invention is applicable to any particular drive scheme, and for this reason, no further explanation will be given of the precise operation of any particular drive scheme. this will be well known to those skilled in the art. fig. 3 shows a conventional column driver circuit. the number n of different pixel drive signal levels are generated by a grey level generator 40 , for example a resistor array. a switching matrix 42 controls the switching of the required level to each column and comprises an array of converters 43 for selecting one of the n grey levels based on a digital input from a latch 44 . the digital input is derived from a ram storing the required image data 45 . each column is provided with a buffer 46 for holding a pixel in the column to the required drive signal level for the full duration of the row address period. this large number of buffers 46 results in high power consumption. to reduce power in a low power chipset to drive the active matrix lcd, the total number of buffers needs to be reduced. this also enables less area to be occupied. in accordance with the invention, the grey level voltages are generated and then switched through an associated buffer to the relevant column, as shown in fig. 4 . the grey level generation circuit 50 comprises a resistor array between maximum and minimum voltages, with each tap 52 being provided to an associated buffer 54 . there are n buffers in total, providing the n grey scale levels. the n signal levels are provided to a switching matrix 56 which enables one of the n levels to be switched to each column, based on the image data 58 provided from a ram. each column is associated with a 1 of n selector 57 . in the example of fig. 4 , the required pixel data is defined by a six bit word, giving a total number of grey scale levels, n, of 64 . the number of columns that any one buffer 54 is driving will depend on the number of pixels in the addressed row which have the same pixel data. this means that each buffer has a possible maximum to minimum load ratio of 500 to 1 for a display with 500 columns. this load range is too large and results in unstable or extremely large buffers. to overcome this, the invention provides an architecture by which the number of columns is known, and hence the load seen by each buffer can be determined. a histogram is constructed in ram of the pixel data for the row. this enables the number of columns each buffer will be driving to be determined, and therefore enables the load to be calculated. the buffers are then controlled in dependence on the stored pixel data, as represented schematically by arrow 60 in fig. 4 , which represents the ram histogram data. fig. 5 shows the architecture of the ram for storage of the histogram data. in conventional manner, image data is received from a host at the input 70 . this is written into an image data storage section 72 of the memory using a line store 74 . the invention can be implemented using an additional area of ram 76 , which is reserved for storing the histogram data for each row in the image. the histogram data is obtained using counters 78 . the organisation of the histogram part 76 of the memory for one row is shown in detail in fig. 6 . the number of pixels in a row having each of the n signal levels v1, v2 . . . vn, is stored, as number n _{vn} . image data is written from the host to the area 72 of the ram and is then piped from the area 72 to the column driver switching matrix 56 , whenever the latter needs to be refreshed. during the period when data is being written to the area 72 of ram via the line store 74 , the series of counters 78 build up the histogram data and, when all of the row data has arrived, stores the histogram at the appropriate location 76 in the ram. in this way, the histogram only needs to be calculated once when the data arrives. the alternative is to calculate the histogram data when it is being read out from the ram as the display is being updated. however, in this latter case the histograms will be calculated up to frame rate times per second for each row and this will cost power. there are various ways to use this histogram data to control the configuration of the buffers, so that the buffers are stable at the required output load. fig. 7 shows a first example in which the histogram data is used to vary the capacitive drive capability of simple 2-stage amplifier. a conventional 2-stage circuit 80 is extended by adding extra output stages 82 in parallel. these additional output stages 82 are enabled under control from the histogram information (ho, h 1 , h 2 and h 3 ). thus, a number of output stages can be switched into operation as a function of the required output load. this enables a low power consumption to be maintained when there is low output demand, but enables a high output demand to be tolerated by increasing the currents flowing through the buffer. in this way, the second stage can be controlled to match the load capacitance, thereby giving similar settling characteristics for the different loads. for example, the output impedance, slew rate and stability margin can be controlled by switching in selected output stages. in the illustrated circuit, the resolution of the output stage switching is four columns, so that each configuration of the amplifier needs to be capable of driving a capacitive load that varies from a lowest value to a highest value a factor of 4 greater than the lowest value. in the example shown, one output configuration is for 1 to 4 columns, the next configuration is for 5 to 16 columns, and so on. this method of adjusting the output stages of the amplifier effectively adjusts the output impedance of the buffer to maintain stability for the required output load. unused buffers can be powered down, again to reduce the total power. there are of course other schemes for varying the buffer configuration in dependence on the desired output load. for example, the buffers may have a bias current input. the bias current may then be altered as a function of the output load, to provide the desired matching. alternatively, the buffer may be provided with a buffer loading capacitor. as the output load is increased, the buffer loading capacitor can be switched out of circuit, so that the overall load capacitance (the buffer loading capacitance and the output load capacitance) remains fairly constant. fig. 8 shows an arrangement in which each signal level line is associated with two buffers 54 a and 54 b . each of the two of buffers is suitable for different output loads. one of the two buffers is selected in dependence on the number of columns to which the buffer output is to be switched. thus, the histogram data at input 60 controls switches 62 arranged in complementary pairs. this enables the maximum output load variation to be halved. each signal level line may of course be associated with a greater number of buffers. in the example of fig. 9 , an additional buffer 92 is provided and the additional buffer 92 is used when the number of columns to which an individual buffer output is to be switched exceeds half the total number of columns. thus, if buffer 540 in fig. 9 is to supply more than half the pixels of a row (as determined from the histogram data 60 ), a switching matrix 94 routes the corresponding signal level v1 from the grey level generator 50 to the additional buffer 92 . the output of buffer 92 is used to drive some columns whereas the output of buffer 540 is used to drive others. the switching matrix 56 then receives n1 signal levels, and the histogram data 60 is used to control the switching matrix 56 so that when one signal level is required for more than half of the pixels of the row, this load is shared between the buffer for that signal level and the additional buffer. there may be two or more additional buffers, which enables the required output load range of the individual buffers to be reduced further. the terms row and column are somewhat arbitrary in the description and claims. these terms are intended to clarify that there is an array of elements with orthogonal lines of elements sharing common connections. although a row is normally considered to run from side to side of a display and a column to run from top to bottom, the use of these terms is not intended to be limiting in this respect. the column circuit may be implemented as an integrated circuit, and the invention also relates to the column circuits for implementing the display architecture described above. other features of the invention will be apparent to those skilled in the art.
|
136-681-939-860-213
|
US
|
[
"US"
] |
F21S8/02,F21V21/30,F21V31/03
| 2002-02-20T00:00:00 |
2002
|
[
"F21"
] |
light system
|
a lighting fixture is provided wherein the lighting fixture comprises a lamp and a positioning assembly. the positioning assembly is configured to allow translational, and rotational positioning of the lamp relative to a housing. the positioning assembly is also configured to be received by a housing.
|
1 . a lighting fixture, comprising: a housing; a lamp fixture; and a positioning assembly supported by the housing and positioning the lamp fixture, wherein the positioning assembly is configured to allow linear and rotational positioning of the lamp fixture. 2 . the lighting fixture of claim 1 , wherein the housing comprises a cylindrical structure. 3 . the lighting fixture of claim 2 , wherein the positioning assembly is further configured to facilitate rotation of the lamp fixture about an axis through the radial center of the cylindrical structure. 4 . the lighting fixture of claim 1 , wherein the positioning assembly further comprises: a substantially planar lid configured to engage the housing; and a linkage assembly connected to the lid and supporting the lamp fixture. 5 . the lighting fixture of claim 4 , wherein the lid further comprises a window. 6 . the lighting fixture of claim 5 , wherein the window comprises a glass covering configured to be recessed relative to a top surface of the lid of the positioning assembly, wherein the lid comprises a weep hole, and wherein the lid is configured to drain water off the surface of the glass covering through the weep hole. 7 . the lighting fixture of claim 4 , wherein the lid further comprises ventilation holes. 8 . the lighting fixture of claim 4 , wherein the linkage assembly further comprises an elongated member defining a slotted groove, wherein the slotted groove is configured to receive a thumb-bolt assembly for slideably adjusting and fixing the distance between the lamp fixture and the lid of the positioning assembly. 9 . the lighting fixture of claim 8 , wherein the slotted groove and thumb-bolt assembly are further configured for rotatably adjusting and fixing the pitch of the lamp fixture relative to the lid of the positioning assembly. 10 . the lighting fixture of claim 1 , wherein the housing further comprises a collar configured to be fixably attached to a cylinder. 11 . the lighting fixture of claim 10 , wherein the collar is configured to attach to the housing on both the outer and inner surfaces of a first end of the cylinder. 12 . the lighting fixture of claim 1 , wherein the housing has an open end. 13 . the lighting fixture of claim 1 , wherein the positioning assembly is removable from the housing. 14 . the lighting fixture of claim 1 , wherein the rotational positioning of the lamp fixture comprises both a pitch rotation direction and a yaw rotation direction. 15 . the lighting fixture of claim 1 , wherein the lamp fixture further comprises: a lamp fixture body; a lamp; and a reflector, wherein the reflector is configured to reflect light from the lamp and wherein the lamp fixture body is configured with a support shelf for supporting the reflector. 16 . the lighting fixture of claim 15 , wherein the lamp fixture body is further configured to support a filter lens. 17 . the lighting fixture of claim 15 , wherein the lamp fixture body further comprises a lamp fixture cap and a lamp fixture base, wherein the lamp fixture cap and lamp fixture base are configured to slideably connect to each other with at least one o-ring between the lamp fixture cap and lamp fixture base. 18 . a lighting fixture comprising: a lamp fixture; and a positioning assembly, wherein the positioning assembly is configured to allow translational and rotational positioning of the lamp fixture, and wherein the positioning assembly is configured to be received by a housing. 19 . the lighting fixture of claim 18 , wherein the housing comprises a cylindrical structure. 20 . the lighting fixture of claim 18 , wherein the positioning assembly is further configured to facilitate rotation of the lamp fixture about an axis through the radial center of the cylindrical structure. 21 . the lighting fixture of claim 18 , wherein the positioning assembly further comprises: a substantially planar lid; and a linkage assembly connected to the lid and supporting the lamp fixture. 22 . the lighting fixture of claim 21 , wherein the lid further comprises a window. 23 . the lighting fixture of claim 22 , wherein the window comprises a glass covering configured to be recessed relative to a top surface of the lid of the positioning assembly, wherein the lid comprises a weep hole, and wherein the lid is configured to drain water off the surface of the glass covering through the weep hole. 24 . the lighting fixture of claim 22 , wherein the lid further comprises ventilation holes. 25 . the lighting fixture of claim 21 , wherein the linkage assembly further comprises an elongated member defining a slotted groove, wherein the slotted groove is configured to receive a thumb-bolt assembly for slideably adjusting and fixing the distance between the lamp fixture and the lid of the positioning assembly. 26 . the lighting fixture of claim 25 , wherein the slotted groove and thumb-bolt assembly are further configured for rotatably adjusting and fixing the pitch of the lamp fixture relative to the lid of the positioning assembly. 27 . the lighting fixture of claim 18 , wherein the housing further comprises a collar configured to be fixably attached to a cylinder. 28 . the lighting fixture of claim 27 , wherein the collar is configured to attach to the housing on both the outer and inner surfaces of a first end of the cylinder. 29 . the lighting fixture of claim 18 , wherein the housing has an open end. 30 . the lighting fixture of claim 18 , wherein the positioning assembly is removable from the housing. 31 . the lighting fixture of claim 18 , wherein the rotational positioning of the lamp fixture comprises both a pitch rotation direction and a yaw rotation direction. 32 . the lighting fixture of claim 18 , wherein the lamp fixture further comprises: a lamp fixture body; a lamp; and a reflector, wherein the reflector is configured to reflect light from the lamp and wherein the lamp fixture body is configured with a support shelf for supporting the reflector. 33 . the lighting fixture of claim 32 , wherein the lamp fixture body is further configured to support a filter lens. 34 . the lighting fixture of claim 32 , wherein the lamp fixture body further comprises a lamp fixture cap and a lamp fixture base, wherein the lamp fixture cap and lamp fixture base are configured to slideably connect to each other with at least one o-ring between the lamp fixture cap and lamp fixture base. 35 . the lighting fixture of claim 28 , wherein the collar is a pour collar. 36 . the lighting fixture of claim 26 , wherein the lamp fixture further comprises: a lamp fixture body, wherein the lamp fixture body further comprises at least one positioning assembly connection point configured to receive the thumb bolt; a lamp; and a reflector, wherein the reflector is configured to reflect light from the lamp and wherein the lamp fixture body is configured with a support shelf for supporting the reflector. 37 . a method for using a lighting fixture comprising the steps of: positioning a housing; adjusting the elevation of a lamp fixture relative to a top surface of a positioning assembly; adjusting the pitch of the lamp fixture relative to the top surface of the positioning assembly; placing the positioning assembly onto the housing; and adjusting the yaw of the lamp fixture relative to a vertical line perpendicular to the top surface of the positioning assembly.
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field of invention the present invention relates, generally, to lighting systems. background of the invention lighting fixtures serve a wide variety of applications. for example, lighting fixtures are used in interior applications, such as lighting the lobby of an office building. lighting fixtures are also used in exterior applications, such as on the grounds of buildings, in parks, and in a multitude of locations generally requiring illumination. in general, well light fixtures advantageously provide illumination while hiding and/or protecting the lighting fixture components. enclosing lighting fixture components within a well can improve safety and aesthetics. in addition, well lights can serve to protect the components from tampering, for example by vandals, and from damage by lawn mowers, trimming machines, and animals. in particular, well light fixtures are often used in below grade installations. these below grade installations can be found in walkways, turf, planters, and other hardscape settings involving concrete, asphalt, gravel, pave stones, tile, and the like. some well light fixtures include a collar. collars can be used, for example, to affix the perimeter of the lighting fixture to the surrounding environment. however, some well light collars can cause undesirable deflections in the lighting housing, and allow weeds, grass, soil and debris to infiltrate the lighting fixture. in general, present day well lights are time consuming to install. installations typically require numerous adjustments to direct the illumination in the right direction or to provide a desired lighting effect on an object. to make these adjustments, the well light installer must often use several tools, and the use of these tools further slows the installation. furthermore, large numbers of well light fixtures are often installed on a single project, thus tending to increase the value of well lights that are more flexible and faster to install. in addition, well lights are typically limited in the range of motion available for the lighting fixture. summary of the invention in accordance with various exemplary embodiments of the present invention, a lighting fixture comprises a lamp fixture and a positioning assembly. the lighting fixture may also comprise a housing. in an exemplary embodiment, the positioning assembly is configured to be received by the housing. in another exemplary embodiment of the present invention, the positioning assembly is configured to allow translational and rotational positioning of the lamp fixture. brief description of the drawing the subject matter of the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification. the invention, however, both as to structure and method of operation, may be understood by reference to the following description taken in conjunction with the claims and the accompanying drawing figures, in which like parts may be referred to by like numerals: fig. 1 is an exploded side view of a lighting fixture according to various aspects of the present invention; figs. 2 and 3 are perspective views of a lighting fixture according to various embodiments of the present invention; fig. 4 is an side view of a lighting fixture as installed according to various aspects of the present invention; fig. 5 is an exploded view of a lighting fixture according to various embodiments of the present invention; fig. 6 is an side cross-sectional view of a collar in a lighting fixture according to various aspects of the present invention; fig. 7 is a side cross-sectional view of a lamp fixture of a lighting fixture according to various aspects of the present invention; fig. 8 is an exploded side view of a lighting fixture according to various aspects of the present invention; figs. 9 and 10 are detailed views of the inner and outer faces of a lid of a lighting fixture, respectively; and fig. 11 is a side cross-sectional view of a lid of a lighting fixture according to various embodiments of the present invention. detailed description an apparatus and method in accordance with various aspects of the present invention provide an improved lighting system for illumination of objects. in this regard, the present invention may be described in terms of functional block components and various processing steps. such functional blocks and steps may be realized by any number of devices and techniques configured to perform the specified functions. for example, a light system, according to various aspects of the present invention, may employ various mechanical joining devices, e.g., bolts, screws, adhesive, thumb screws, and the like. in accordance with various aspects of the present invention, a lighting system may facilitate, among other things, lamp range of motion, installation and repair time, and fixture integrity. a lamp fixture may be suitably supported by a positioning assembly, and may be positioned, for example, with both rotational and linear movement allowing illumination adjustments. the rotational movement may include yaw and/or pitch rotational movements. the lighting fixture may be configured for tool-less adjustment and access. the fixture may further include an integrated collar on a housing, thus enhancing fixture integrity. furthermore, the lamp fixture may provide a sealed environment for protecting lamp components from water. in accordance with an exemplary embodiment of the present invention, and with reference now to fig. 1, a lighting fixture 100 includes a housing 110 , a lamp fixture 120 , and a positioning assembly 130 . the housing 110 may be configured to support the positioning assembly 130 , which may be configured to support the lamp fixture 120 . the positioning assembly 130 is suitably further configured to allow translational and rotational positioning of the lamp fixture 120 . the lighting fixture 100 may be configured such that the housing 110 contains the lamp fixture 120 and portions of the positioning assembly 130 . in accordance with various aspects of the present invention, the housing 110 is configured to contain the lamp fixture 120 and/or to protect portions of the lighting fixture 100 . the housing 110 may also be configured to support the positioning assembly 130 . the housing 110 may include housings of various shapes and sizes. the housing 110 may include any suitable object capable of protecting and/or supporting the lamp fixture 120 . the housing 110 may include a side(s) 107 , a top end 109 and a bottom end 108 . the ends 108 , 109 may be completely or partially open or closed to facilitate access to the housing, drainage, power supply, ventilation, or other utility. in the present embodiment, for example, the top end 109 is open and configured to receive the positioning assembly 130 . the bottom end 108 may be configured to be open or closed. in an exemplary embodiment of the present invention, the bottom end 108 is open to allow moisture present in the housing to drain. to further this drainage, the soil or other material below the housing 110 may be prepared to facilitate such draining. for example, gravel may be placed under a ground installed housing 110 . furthermore, when the housing 110 is configured with the bottom end 108 open, power supplying cable may enter through the bottom end 108 . in embodiments in which the bottom of housing 110 is closed, power cables may enter through conduit couplings in the bottom or side of the housing 110 . in accordance with various exemplary embodiments of the present invention, and with reference to figs. 2 and 3 , the housing 110 may be configured in any suitable shape and configuration, including any cylindrical configuration such as a circular cylinder, rectangular cylinder, oval cylinder, triangular cylinder, or other cylindrical structure. although the exemplary embodiments include right cylindrical structures, the cylindrical structure may suitably be formed at angles to the top 109 and bottom 108 ends of the housing. in accordance with one exemplary embodiment of the present invention, the housing 110 is substantially a right circular cylinder 210 . the housing 110 may also, for example, be substantially a right rectangular cylinder 310 . a right circular cylinder may be described as a structure made of circular sections, wherein the center of each circular section forms a line substantially perpendicular to the top 109 and bottom 108 ends. the term cylinder refers to the lateral sides of the object, whatever the shape, and excluding any top and/or bottom caps. in general, the housing 110 may be configured to suitably support the positioning assembly 130 and/or to facilitate yaw rotation. for example, with reference now to fig. 2 , the right circular cylinder 210 is configured to facilitate yaw rotation with a circular collar 211 which has a circular receiving surface (not shown). the collar is suitably configured to mate with a circular lid 231 of the positioning assembly 130 . therefore, the circular lid 231 is free to rotate within the circular collar. in other embodiments, and with reference to fig. 3 , square or other shaped cylinders can be configured to facilitate yaw rotation of the positioning assembly. for example, a right square cylinder 310 may be configured with a square collar 311 which is adapted to receive the circular lid 231 . for example, the square collar 311 may be configured with a circular receiving surface in the square top end 309 of the square cylinder lighting fixture 300 . therefore, the circular lid 231 is free to rotate within the square top collar 311 . in these various embodiments, the lamp fixture 120 can be positioned throughout the 360 rotation relative to circular cylinder. although the present lighting fixture 100 has yaw and pitch rotational positioning movement capabilities, in various embodiments, one or the other may be omitted from the present invention. for example, if yaw rotation is omitted, square or other shaped lids may be used. the housing 110 may be constructed of any suitable material selected for any suitable purpose. for example, the housing 110 may be made of a corrosion resistant material such as, but not limited to polyvinyl chloride (pvc), glass reinforced composites, and the like. as another example, an exposed housing 110 may be made of stainless steel for architectural effect. also, the housing 110 may further be constructed by any suitable construction technique, such as, extrusion and/or injection molding, casting, machining, stamping, or the like. in another exemplary embodiment of the present invention, the housing 110 may be made of standard pvc pipe. the housing 110 may further be suitably coated, for example to prevent rusting, corrosion, patina process, etc. furthermore, the housing 110 may be painted or otherwise colored to enhance reflectivity, or achieve other illumination effects. in accordance with various embodiments of the present invention, the housing 110 is configured to be installed in either above grade or below grade installations in a wide variety of environments. for example, the housing 110 may be configured to be installed substantially below grade with primarily a top portion of the housing 110 visible and with the surface of a top portion of the positioning assembly 130 installed substantially flush with the surface of the terrain within which the lighting fixture is installed. while the present lighting fixture may be suitably installed within a landscape in a hole prepared in the ground, the lighting fixture may also be installed in other architectural environments, such as in walkways, vehicular drives, steps, columns, building facades, or other structures. furthermore, the housing 110 is not limited to hidden or below grade installations and can be installed with the housing exposed. in various embodiments of the present invention, the housing 110 is configured to have a selected height. the height may be selected based on any appropriate criteria. for example, the height may be selected to reduce the depth of the hole or receptacle that is prepared to receive the housing 110 . for example, the housing 110 height is suitably configured to be about 12 inches, although any appropriate height may be used. in various embodiments of the present invention, the housing 110 is configured to have a selected diameter. the diameter may be selected based on any suitable criteria. for example, the diameter may be selected to accommodate the lamp fixture 120 size and movement. in one exemplary embodiment of the present invention, the housing 110 diameter is suitably configured to be approximately 7 inches, although any suitable diameter may be used. in accordance with various aspects of the present invention, the housing 110 may be configured to support the positioning assembly 130 with or without the use of a collar. with reference now to fig. 4, a second housing 410 according to various aspects of the present invention may be further configured to include a pour collar 411 mated to a top end 409 of a cylinder 401 . the pour collar 411 is suitably configured to support and/or facilitate rotation of the positioning assembly 130 . the pour collar 411 may further be configured for mating with concrete, tile, turf, gravel, pave stones, or the like. for example, the top surface 433 of concrete 430 may be poured substantially flush with a top surface 413 , and adjacent to a side surface 412 , of the pour collar 411 . as noted above, however, the second housing 410 may also be installed in situations where the top surface 413 is not flush with any surroundings, such as in exposed or partially exposed installations. the pour collar 411 may further be configured to allow the positioning assembly 130 to be inserted and removed from the second housing 410 . the positioning assembly 130 may be physically maintained in contact with the second housing 410 through a variety of mechanisms. for example, in one embodiment of the present invention, the positioning assembly 130 may be held in contact with the second housing 410 by gravity. in this embodiment, the second housing 410 is physically positioned with the axis 440 of the cylinder 401 oriented in a substantially vertical direction. other orientations, however, including horizontal orientations and downward orientations may be utilized. in such orientations, the positioning assembly 130 may be fastened to the second housing 410 , such as by set screws, clips, or other restraining devices (not shown). referring now to fig. 5, a circular collar 511 may be configured such that a second positioning assembly 530 is removable, even after pouring concrete or other material up to the circular collar 511 and thus fixing the circular collar 511 relative to the surrounding environment. removability of the second positioning assembly 530 facilitates adjusting the positioning of a second lamp fixture 520 , replacing components, and removing any debris from the interior of the well light. furthermore, in one exemplary embodiment of the present invention, a circular lid 531 mates with a circular collar 511 having a circular receiving surface (not shown) allowing the positioning assembly 530 full 360 rotation and further facilitating positioning of the light. a collar, in accordance with various embodiments of the present invention, may be configured to receive the positioning assembly in any suitable manner. for example, with reference to fig. 6 , an exemplary integral collar 611 may include a receiving surface 614 for supporting or mating with the positioning assembly 130 . in one exemplary embodiment of the present invention, the receiving surface 614 is configured to be recessed from or lower than a top side surface 613 such that the positioning assembly 130 mounts flush with the top side surface 613 . in such a configuration, the positioning assembly 130 may be rotated and/or inserted and removed from mating with the collar 611 even when the collar 611 is fixed relative to a surrounding material. in an exemplary embodiment of the present invention, the positioning assembly 130 can be turned while seated on the collar 611 . rotation of the positioning assembly 130 within the collar 611 facilitates a first rotational degree of freedom, or yaw, for positioning the lamp fixture 120 . this lamp fixture 120 positioning can, for example, be performed while the lighting fixture is fully assembled, and without tools, thus facilitating quick positioning adjustments of the lamp fixture 120 . a collar 611 , in accordance with various embodiments of the present invention, may be configured to be attached to a second cylinder 601 by any appropriate material or mechanism. for example, attachment to the second cylinder 601 may be made by an adhesive such as an elastomeric silicone product or other suitable bonding agent. attaching the collar 611 to the second cylinder 601 by adhesive tends to maintain the shape of the second cylinder 601 and/or collar 611 . deformation of, for example, either the second cylinder 601 or the collar 611 , may prohibit the free rotation of the positioning assembly 130 and otherwise detract from the overall mating of the positioning assembly 130 to a third housing 610 . in other embodiments of the present invention, the collar may be attached to the second cylinder 601 by set screws, and the like. in various exemplary embodiments of the present invention, the collar 611 is suitably formed as an integral part of a third housing 610 , for example, by forming a single piece through injection molding. in another exemplary embodiment of the present invention, the collar 611 is suitably integrally attached to the second cylinder 601 . for example, the collar 611 may be configured to have an outer lip 632 and an inner lip 634 which are configured for receiving the second cylinder 601 between the outer lip 632 and the inner lip 634 . in this manner, the collar 611 is attached to both the outer surface 633 and inner surface 636 of the top end 609 of the second cylinder 601 . integral attachment or formation of the collar 611 and the second cylinder 601 may substantially prevent grass, weeds, soil, and debris from growing or otherwise coming between the collar 611 and the second cylinder 601 . the elimination of element penetration facilitates mating of the positioning assembly 130 to the third housing 610 and tends to provide enhanced overall appearance and durability. with reference now to fig. 7, a third lamp fixture 720 may include a lamp fixture body 721 , a reflector 750 , and a lamp 752 . the lamp fixture body 721 may be configured to support the reflector 750 and/or the lamp 752 . the reflector 750 is suitably configured to reflect the light from the lamp 752 , which provides illumination. the lamp fixture body 721 may further be configured to include one or more parts for, among other things, supporting and protecting the components within the lamp fixture. in accordance with an exemplary embodiment of the present invention, the lamp fixture body 721 comprises a lamp fixture base 722 and a lamp fixture cap 760 . the lamp fixture cap 760 may be removably attached to the lamp fixture base 722 by any suitable mechanism, such as screw-on lamp fixture caps, snap-on lamp fixture caps, or the like. the removable lamp fixture cap 760 allows access for replacing lamps, lenses, and/or socket and wiring components. in an exemplary embodiment of the present invention, the lamp fixture cap 760 is attached to the lamp fixture base 722 by a friction fit against one or more o-rings 761 , thus facilitating access to the inside of the lamp fixture body 721 . the lamp fixture base 722 , in accordance with an exemplary embodiment of the present invention, includes one or more circular machined surface notches 723 , for receiving the one or more o-rings 761 . the o-ring(s) 761 may be suitably configured to create an air/water tight seal and prevent outside elements from reaching the components within the lamp fixture body 721 . by preventing air from escaping the lamp fixture body 721 , substantial water resistance is facilitated even when the lamp fixture body 721 is submerged in water. a double o-ring 761 may provide increased water resistance as well as stability and strength of attachment for the lamp fixture cap 760 . in addition, the o-ring 761 configuration may facilitate simple and tool-less removal and replacement of the lamp fixture cap 760 . the lamp fixture body 721 may be suitably configured to support the lamp 752 and/or the reflector 750 . for example, the lamp fixture base 722 may include a support shelf 724 for maintaining the position of the reflector 750 of the lamp 752 , lens(es) 770 , and the like. the support shelf 724 may be suitably recessed below the top most surface 726 of the lamp fixture base 722 to facilitate holding the reflector 750 and one or more lenses 770 while allowing the lamp fixture cap 760 to be fully seated. although the support shelf 724 may be half an inch below the top most surface 726 in one embodiment of the present invention, other dimensions may suitably be used. in accordance with various aspects of the present invention, the third lamp fixture 720 may be configured to a permit selective inclusion of one or more cover and/or filter lenses 770 . for example, a cover lens 771 may be provided in the third lamp fixture 720 for, among other things, protecting the lamp 752 . the cover lens 771 may be either loose within or fixedly attached to the lamp fixture body 721 . for example, the cover lens 771 may be fixedly attached, by any mechanism, to lamp fixture cap 760 . in one exemplary embodiment of the present invention, an adhesive is used to attach the cover lens 771 to the lamp fixture cap 760 . in another exemplary embodiment of the present invention, the third lamp fixture 720 may be configured without lenses. in one exemplary embodiment of the present invention, one or more filter lens(es) 772 may be included between the reflector 750 and the lamp fixture cap 760 . the filter lens 772 may, for example, be held in place between the reflector 750 and the cover lens 771 . in various embodiments, the filter lens 772 may be clear in color and appearance. in other embodiments, the filter lens 772 may be configured in any suitable manner to filter light. the filter lens 772 may be suitably configured to generate colored lighting effects or to cause other lighting effects such as reduction of glare and/or enhanced lamp beam spread. the filter lens may also be replaced with a substantially colorless or otherwise optically inactive lens to maintain the relative positions of the reflector 750 and the lamp fixture cap 760 . the lamp 752 and reflector 750 may be any light emitting source, for example, an mr-16 or mr-11 halogen type low voltage lamp. furthermore, the lamp 752 may suitably include other light emitting elements such as fiber optics, micro electronics, and the like. in one exemplary embodiment of the present invention, the lamp 752 is powered by low voltage, e.g., 12 volt power. in other embodiments, the lamp 752 can be powered by more or less than 12 volts, for example 120 volts. electrical conductors (not shown) may provide power to the third lamp fixture 720 via a strain relief apparatus 770 which is flexibly attached, e.g., snapped on, to a receiving port of the lamp fixture base 722 . the electrical conductors may enter the third lamp fixture 720 via a strain relief apparatus 770 which generally protects the integrity of the terminal connection of the electrical conductors. the strain relief apparatus 770 may include thermal plastic elastomer or other plastics, rubber or similar flexible material. the lamp fixture base 722 may be further configured to have one or more positioning assembly connection points 728 for movably connecting with the positioning assembly 130 . the positioning assembly connection points 728 may be configured to receive any suitable connection mechanism facilitating adjusting and fixing the position of the lamp. in various embodiments, screws, bolts and the like with a variety of heads, such as allen wrench type heads, and others may be used. in one exemplary embodiment of the present invention, the positioning assembly connection points 728 may be configured to each receive a bolt. the bolt receiving positioning assembly connection points may be co-linear creating an axis of rotation about a line 729 and providing another rotational movement degree of freedom (pitch) for the third lamp fixture 720 . in one exemplary embodiment of the present invention, the bolts used to attach the third lamp fixture 720 to the positioning assembly 130 further comprise thumb knob bolts 527 , for facilitating tool-less adjustment of the height and rotational setting of the third lamp fixture 720 . in accordance with another aspect of the present invention, and with reference again to fig. 1 , any suitable positioning assembly 130 may be used which facilitates rotational and/or translational movement of the lamp fixture 120 with respect to the housing 110 . in one embodiment of the present invention, positioning assembly 130 includes a lid 131 and a linkage assembly 132 . in this embodiment of the present invention, the lid 131 is connected to the linkage assembly 132 , and the linkage assembly 132 is connected to the lamp fixture 120 . referring now to figs. 6 and 8 , the lid 831 may include a relatively planar top surface 801 , for example, for substantially flush mounting with the surrounding surface and with the top 813 of the collar 811 . the lid 831 may further include a surface 814 for mating with a receiving surface 614 of the collar 811 . the lid 831 is configured to mate with the collar 811 , for example with a lid diameter 860 of about 6 inches, and is configured to be somewhat, e.g. {fraction (1/32)} inches, smaller in diameter than an outer diameter 661 of the receiving surface 614 . any appropriate dimensions, however, may be used for the cylinder, collar and lid. the lid 831 may be configured with a suitable support structure 820 for providing added rigidity and stability. with reference to fig. 9 , an exemplary support structure 920 embodiment comprises multiple ribs formed in the bottom surface of the lid 831 . any suitable support structure, however, may be used to provide appropriate rigidity and stability. the support structure 920 may be configured to meet particular loading specifications. for example, a lid 931 often may support the weight of a human, a bike, or a car passing over the lighting fixture. with reference now to figs. 9 and 10 , the lid 931 and support structure 920 according to various aspects of the present invention include a window 1090 and ventilation holes 1080 . the window 1090 includes an opening in a lid 1031 which allows light from within the housing 110 to illuminate objects outside of the housing 110 . the window 1090 is suitably oblong, though any suitable shape and size of window may be used. the window 1090 may suitably be covered or may be an open window. in various exemplary embodiments of the present invention, a covering may also be a partial covering such as a grate, mesh, slat, or other suitable covering. furthermore, any suitable covering that allows some light to pass through the covering may be used. for example, the covering may be translucent or transparent, and may include materials such as glass, plastic, or other suitably transmissive material. in an exemplary embodiment of the present invention, a glass plate 991 is provided for the window 1090 . the glass plate 991 is, for example, large enough to cover the entire window 1090 . the glass plate 991 may be attached to the lid 1031 by any suitable mechanism. for example, mechanical clamps, brackets, slots, groves, pins, and the like may be used for attachment purposes. in the present embodiment, an adhesive is used to attach the glass plate 991 to the lid 1031 . with reference now to fig. 11 , the glass plate 1191 may be suitably recessed, for example, {fraction (1/32)} inches below the surface 1101 of the lid 1131 to provide protection to the glass plate 1191 . other dimensions may suitably be used for recessing the glass plate 1191 . in this manner, the full weight of a passing object is not placed squarely on the glass, thus reducing the likelihood of breaking the glass plate 1191 . in accordance with one aspect of the present invention, the lid 1131 may be configured to drain water off of the glass plate 1191 . for example, the lid 1131 may be configured such that the glass plate 1191 slopes toward a weep hole 1192 when the lid 1131 is installed in a level position. the slope of the glass plate 1191 may, for example, be created by placing one or more spacers 1103 near the weep hole 1192 . the lid 1131 and glass plate 1191 may include various other configurations for causing moisture to drain to the weep hole 1192 . for example, the lid 1131 can be manufactured with varying thickness such that the glass plate 1191 slopes from one side of the window 1190 to a weep hole 1192 on the other side of the window 1190 . the weep hole 1192 may be cut into the lid 1131 at the low end of the glass plate 1191 . in another example, the glass plate 1191 may be manufactured with a variable thickness, having one side thicker than the other to generate a slope for facilitating draining. the glass plate 1191 may be secured to the lid 1131 with an adhesive, by mechanical mechanism, or other suitable attachment mechanism. with reference again to figs. 9 and 10 , the ventilation holes 1080 allow moisture that may have been introduced into the housing 110 to evaporate. thus, fog and water droplets that might otherwise cloud the window 1090 tend to be reduced and illumination performance tends to increase. furthermore, the size and number of ventilation holes may be restricted to reduce the opportunity for leaves and other debris to fall into the housing 110 . also, small ventilation holes tend to reduce potential tampering, as the smaller holes may provide relatively little gripping surface for removing the positioning assembly 130 . the ventilation holes 980 of the present embodiment comprise seven oval ventilation holes in one quadrant of the lid 931 , though any other numbers and patterns of ventilation holes may also be used. similarly, although the ventilation holes 980 have approximately a -inch width, other dimensions may also be used. with reference again to fig. 5 , the positioning assembly 530 may comprise a linkage assembly 570 suitably configured for facilitating translational and rotational motion of the second lamp fixture 520 relative to the housing 110 . various linkage assemblies may be used for adjustably raising/lowering and/or rotatably setting the position of the second lamp fixture 520 . for example, the elongated members 572 may have notches or holes which can be selectively chosen for placing the lamp at a specified height. in one exemplary embodiment of the present invention, the linkage assembly 570 includes two elongated members 572 , each having a slot 575 along the vertical length of the elongated member. the elongated members 572 may, for example, be metal strips or other suitable material. each slot 575 is configured to receive a bolt or other similar object from the second lamp fixture 520 . in an exemplary embodiment, a thumb knob bolt 527 is positioned in the slot 575 and attached to the second lamp fixture 520 , for example at the positioning assembly connection points 528 . each slot 575 is configured to allow the thumb knob bolt 527 to slide linearly in slot 575 and/or to rotate with a pitch rotation. the second lamp fixture 520 is connected to the linkage assembly 570 such that the linear position and/or pitch rotation can be fixed in a set condition. for example, the thumb knob bolts 527 can be turned and tightened to hold the linear position and rotation of the second lamp fixture 520 . the thumb knob bolts 527 may then be loosened, and the second lamp fixture 520 rotated and raised or lowered to adjust the positioning of the second lamp fixture 520 which is then set by re-tightening the thumb knob bolts 527 . other bolt heads may also be used in the place of thumb knob bolts 527 . the linkage assembly 570 may be connected by any suitable mechanism to the lid 531 , for example, via bolts 571 . alternatively, the linkage assembly 570 may be riveted to the lid 531 or attached in any other suitable manner. raising and lowering the lamp fixture 120 within the housing 110 facilitates allowing more or less light to be emitted from the lighting fixture 100 . this may be advantageous where less glare is desired, for example, where people are walking directly over the fixture, or to achieve soft lighting or other illumination effects. although the invention has been described herein in conjunction with the appended drawings, the scope of the invention is not so limited. modifications in the selection, design, and arrangement of the various components and steps discussed herein may be made without departing from the scope of the invention as set forth in the appended claims.
|
137-364-994-903-738
|
KR
|
[
"CN",
"KR",
"TW",
"US"
] |
G06F3/038,G06F3/033,G09G5/08
| 2004-09-14T00:00:00 |
2004
|
[
"G06",
"G09"
] |
optical mouse and control method thereof
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an optical pointing device and a control method thereof are provided. the optical pointing device includes: an illumination unit for illuminating light on a working surface, and generating light in a predetermined code in response to a code signal; a control unit for detecting an image on the working surface to calculate a movement value, outputting movement information in response to an input signal inputted from the outside and the calculated movement value, intermittently outputting a code generation signal, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to a determination signal; and a determination unit for outputting the code signal in response to the code generation signal, detecting light in the predetermined code to thus determine whether or not the optical pointing device is separated from the working surface, and outputting the determination signal depending on the determination result. therefore, a glaring phenomenon generated when the optical pointing device is turned upside down can be prevented, and unnecessary power consumption can also be prevented.
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1. an optical pointing device comprising: an illumination unit for illuminating light on a working surface in response to an illumination signal during a calculation period, and generating light in a predetermined code in response to a code signal during a determination period, wherein the code signal repetitively turns on or off the illumination unit depending on a certain code value during the determination period; a control unit for outputting the illumination signal to detect an image on the working surface, detecting the image on the working surface to calculate a movement value, and outputting movement information in response to an input signal inputted from the outside and the calculated movement value during the calculation period, intermittently outputting a code generation signal to determine whether or not the optical pointing device is separated from the working surface during the determination period, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to a determination signal; and a determination unit for outputting the code signal to determine whether or not the optical pointing device is separated from the working surface in response to the code generation signal, detecting the light, determining whether a code of the detected light matches the predetermined code to thus determine whether or not the optical pointing device is separated from the working surface, and outputting the determination signal depending on the determination result during the determination period, wherein the determination period does not overlap with the calculation period, and the light generated during the determination period is different from the light illuminated during the calculation period. 2. the optical pointing device according to claim 1 , wherein the control unit comprises: an image information output unit for detecting an image on the working surface, and outputting image information on the detected image; a movement value calculation unit for outputting the illumination signal and calculating the movement value from the image information during the calculation period, intermittently outputting the code generation signal during the determination period, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to the determination signal; and a communication unit for outputting the movement information in response to the calculated movement value and the input signal. 3. the optical pointing device according to claim 2 , wherein the control unit has an active state in which the movement value is calculated while the illumination unit remains on for most of the time of the calculation period, and the code generation signal is intermittently output, an inactive state in which a determination is made whether or not the optical pointing device moves by intermittently turning on the illumination unit while the illumination unit remains off for most of the time of the calculation period and the code generation signal is intermittently output, and a glaring prevention state in which the code generation signal is intermittently output while the illumination unit remains off during the calculation period; and wherein the optical pointing device converts the active or inactive state into the glaring prevention state when the determination is made that the optical pointing device is separated from the working surface. 4. the optical pointing device according to claim 3 , wherein the control unit further has an idle state in which the illumination unit remains off; and wherein the control unit further serves to convert into the idle state when the glaring prevention state continues for a predetermined time. 5. the optical pointing device according to claim 1 , wherein the determination unit comprises: a code generator for outputting the code signal to turn on or off the illumination unit in response to the code generation signal; a detection sensor for receiving light generated from the illumination unit to output a detection signal; and a code interpreter for interpreting the detection signal and determining a code of the detection signal matches the predetermined code to determine whether or not the optical pointing device is on the working surface, and outputting the determination signal depending on the determination result. 6. the optical pointing device according to claim 5 , wherein the code generator outputs the code signal to turn on the illumination unit for a short time enough for a visually very weak signal to be detected. 7. the optical pointing device according to claim 5 , wherein the code generator outputs the code signal to turn on the illumination unit for a visually very weak signal to be detected and the code signal is a pulse signal and a duty cycle of the pulse signal is larger than 50% or smaller than 50%. 8. a method of controlling an optical pointing device, comprising: an illumination step that turns on or off an illumination unit to illuminate light on a work surface during a calculation period; a calculation step that detects an image on the working surface to calculate a movement value, and outputs movement information during the calculation period, intermittently outputting a code generation signal to determine whether or not the optical pointing device is separated from the working surface during the determination step; a code generation step that turns on or off the illumination unit to generate light in a predetermined code in response to a code signal during a determination period, wherein the code signal repetitively turns on or off the illumination unit depending on a certain code value during the determination period; a determination step that outputs the code signal to determine whether or not the optical pointing device is separated from the working surface in response to the code generation signal, detects light output from the illumination unit to analyze a code included in the light and determines whether the code included in the light matches the predetermined code, to thus determine whether or not the optical pointing device is separated from the working surface and outputs a determination signal depending on the determination result during the determination period; and a glaring prevention step that turns off the illumination unit when the optical pointing device is separated from the working surface in response to the determination signal, wherein the determination period does not overlap with the calculation period, and the light generated during the determination period is different from the light illuminated during the calculation period. 9. the method according to claim 8 , wherein the code generation step turns on the illumination unit for a short time enough for a visually very weak signal to be detected. 10. the method according to claim 8 , wherein the determination step comprises: a detection step that receives light generated from the illumination unit to output a detection signal; and an interpretation step that interprets the detection signal and determines a code of the detection signal matches the predetermined code to determine whether or not the optical pointing device is on the working surface, and outputs the determination signal depending on the determination result. 11. the method according to claim 8 , wherein the glaring prevention step converts an active state in which the movement value is calculated while the illumination unit remains on for most of the time of the calculation period and the code generation signal is output during the determination period, or an inactive state in which a determination is made whether or not the optical pointing device moves by intermittently turning on the illumination unit while the illumination unit remains off for most of the time of the calculation period and the code generation signal is output during the determination period, into a glaring prevention state in which the code generation signal is output during the determination period while the illumination unit remains off during the calculation period, when the optical pointing device is separated from the working surface, wherein the code generation step turns on or off the illumination unit during the determination period, and wherein the determination step detects light and determines whether the code included in the light matches the predetermined code during the determination period. 12. the method according to claim 11 , wherein the glaring prevention step further comprises converting into an idle state in which the illumination unit remains off until a button or a scroll device of the optical pointing device is controlled when the glaring prevention state continues for a predetermined time.
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cross-reference to related application this application claims the priority of korean patent application no. 2004-73545, filed sep. 14, 2004, the disclosure of which is incorporated herein in its entirety by reference. background of the invention 1. field of the invention the present invention relates to an optical pointing device, and more specifically, to an optical pointing device and control method thereof capable of preventing light from glaring out from an illumination unit when the optical pointing device is separated from working surface. 2. description of the related art an optical mouse is a peripheral input/output device of a computer that radiates light onto a surface across which it moves and receives light reflected from the surface to output movement information of the optical mouse. in general, the optical mouse is used on top of a flat working surface facing downward so that light radiated from the optical mouse is not directly visible to a user, but when the optical mouse is turned upside down, light output from the optical mouse is directly visible to the user and a glaring phenomenon may occur. fig. 1 is a block diagram of a conventional optical mouse, including a control unit 10 , an input unit 20 , and an illumination unit 30 . the control unit 10 includes an image information output unit 11 including an image sensor 11 - 1 and a converter 11 - 2 , a movement value calculation unit 12 , and a communication unit 13 . a lens of fig. 1 refers to an optical structure that transmits light reflected from the working surface under the mouse to the image sensor. in addition, a dotted line of fig. 1 indicates a direction in which light radiated from the illumination unit 30 is inputted to the image sensor 11 - 1 . a function of each block shown in fig. 1 will be described below. the control unit 10 detects an image on the working surface to calculate a movement value, receives signals from the input unit 20 , and outputs of the calculated movement value and the input unit signals to an external device such as a computer. the image information output unit 11 detects the image on the working surface and outputs image information on the detected image. the image sensor 11 - 1 receives light reflected from the working surface through the lens to detect image data and output an analog signal corresponding to the detected image data. the converter 11 - 2 converts the analog signal of the image sensor 11 - 1 into image information that is digital data and outputs the converted information. the movement value calculation unit 12 calculates and outputs the movement value using the image information inputted from the converter 11 - 2 and outputs a control signal for controlling the illumination unit 30 in response to a state of the optical mouse 1 and a signal inputted from the communication unit 13 . the communication unit 13 receives signals corresponding to information inputted through the input unit 20 (e.g., an operation state of a button or a movement of a scroll device) and outputs the input unit signals and signals from an external device such as a computer to the movement value calculation unit 12 , and outputs the movement information and the input unit signals to the external device such as a computer in response to the movement value inputted from the movement value calculation unit 12 and the input signal inputted from the input unit 20 . the input unit 20 , which may include buttons or scroll devices, outputs the input signal in response to manipulation by a user. the illumination unit 30 turns on or off in response to an illumination signal inputted from the movement value calculation unit 12 and radiates light onto the working surface when turned on. the illumination unit 30 , which is used as a light source, may include a light emitting diode and a driving circuit to turn on or off the light emitting diode. fig. 2 is a state diagram for explaining operation of the conventional optical mouse shown in fig. 1 . operation of the conventional optical mouse shown in fig. 1 will be described below with reference to fig. 2 . the conventional optical mouse has an active state in which the illumination unit 30 is turned on for most of the time and a movement value is calculated depending on the operation state of the optical mouse, an inactive state in which the light source is turned off for most of the time and turned on periodically to determine whether or not the optical mouse moves, and an idle state in which the light source remains in the off state. as long as the optical mouse moves in the active state, it remains the active state (s 1 ). however, when there is no movement of the optical mouse for a predetermined time in the active state, the optical mouse converts into the inactive state (s 2 ). when there is no movement of the optical mouse in the inactive state, the optical mouse remains in the inactive state (s 3 ). however, when movement of the optical mouse is detected, the optical mouse converts into the active state (s 4 ). when there is no movement of the optical mouse for a predetermined time in the inactive state, the optical mouse converts into the idle state (s 5 ). in the idle state, movement of the optical mouse is not detected, however when the input signal is generated by manipulation of the input unit, such as buttons, i.e., the input unit 20 , the optical mouse converts into the active state (s 6 ). fig. 3 is a diagram for explaining a method of controlling the illumination unit 30 in the conventional mouse shown in fig. 1 , in which figs. 3a and 3b show methods of controlling the illumination unit 30 in an active unit and in an inactive unit, respectively. a method of controlling the illumination unit 30 in the conventional optical mouse will be described below with reference to fig. 3 . in the active state ( fig. 3a ), the illumination unit 30 turns on periodically with a predetermined first period t 1 . in the inactive state ( fig. 3b ), the illumination unit 30 turns on periodically with a predetermined second period t 2 . the second period t 2 is set to be longer than the first period t 1 . in other words, the optical mouse calculates the movement value while turning the light source on relatively frequently in the active state ( fig. 3a ), and determines whether or not the optical mouse moves while turning on the optical mouse relatively infrequently in the inactive state ( fig. 3b ). however, for the conventional optical mouse shown in fig. 1 , while the optical mouse is in the active state ( fig. 3a ) or the inactive state ( fig. 3b ), when the user turns the optical mouse upside down, light may glare out from the illumination unit 30 . in addition, since the illumination unit 30 is unnecessarily turned on, power is unnecessarily consumed. fig. 4 is a block diagram of an embodiment of a conventional optical mouse with which the glaring phenomenon can be prevented, including a control unit 10 , an input unit 20 , an illumination unit 31 , and a detection unit 40 . the control unit 10 includes an information output unit 11 including an image sensor 11 - 1 and a converter 11 - 2 , a movement value calculation unit 12 , and a communication unit 13 , and the detection unit 40 includes a sensor and a light emitting diode (led). in fig. 4 , a dotted line indicates a direction in which light radiated from the illumination unit 31 is inputted to the image sensor 11 - 1 . a function of each block shown in fig. 4 will be described below. functions of the control unit 10 and the input unit 20 are the same as described in fig. 1 . the detection unit 40 radiates light using the light emitting diode (led) and detects the light using the sensor to determine whether or not the optical mouse is separated from the working surface, and outputs a detection signal depending on the determination result. in other words, when the optical mouse is on the working surface, light radiated from the light emitting diode (led) is reflected and detected with the sensor, and when the optical mouse is separated from the working surface, light radiated from the light emitting diode (led) is not detected. therefore, whether or not the optical mouse is separated from the working surface can be determined by whether or not light is detected with the sensor. the illumination unit 31 turns on or off in response to the illumination signal inputted from the movement value calculation unit 12 of the control unit 10 and the detection signal inputted from the detection unit 40 . fig. 5 is a block diagram for explaining operation of the illumination unit 31 of the conventional optical mouse shown in fig. 4 , including a resistor r 1 , a light emitting diode (led), and two driving circuits dr 1 and dr 2 which may include a resistor r 2 and a transistor tr 1 and a resistor r 3 and a transistor tr 2 , respectively. a function and operation of each block shown in fig. 5 is described below. the driving circuits dr 1 and dr 2 turn on or off, respectively, in response to an illumination signal inputted from the movement value calculation unit 12 or a detection signal inputted from the sensor of the detection unit 40 , to thus turn the light emitting diode (led) on or off. the two driving circuits dr 1 and dr 2 are connected in series so that if one of them turns off, the light emitting diode (led) turns off. in other words, when the optical mouse is on the working surface, the sensor of the detection unit 40 outputs the detection signal with a high level, to thus turn on the driving circuit dr 2 . the light emitting diode led then turns on or off in response to the illumination signal inputted from the movement value calculation unit 12 . however, when the optical mouse is separated from the working surface, the sensor of the detection unit 40 outputs a detection signal with a low level, to thus turn off the driving circuit dr 2 . the light emitting diode (led) then turns off, irrespective of operation of the movement value calculation unit 12 . however, for the conventional optical mouse shown in fig. 4 , if the optical mouse is turned upside down and light which is not radiated from the light emitting diode (led) is inputted from the outside of the optical mouse to the sensor, it can be mistakenly determined that the optical mouse is on the working surface. in addition, since a separate light emitting diode (led) is added to the detection unit 40 together with the illumination unit 31 for the control unit 10 , power consumption is increased and extra parts are required. in addition, with two driving circuits as shown in fig. 5 , cost is further increased and a circuit is complicated. summary of the invention it is, therefore, an object of the present invention to provide an optical pointing device capable of preventing a glaring phenomenon that may occur when the optical pointing device is separated from a working surface. it is another object of the present invention to provide a method of controlling the optical pointing device. in an exemplary embodiment according to the present invention, an optical pointing device includes: an illumination unit for illuminating light on a working surface, and generating light in a predetermined code in response to a code signal; a control unit for detecting an image on the working surface to calculate a movement value, outputting movement information in response to an input signal inputted from the outside and the calculated movement value, intermittently outputting a code generation signal, and turning off the illumination unit when the optical mouse is separated from the working surface in response to a determination signal; and a determination unit for outputting the code signal in response to the code generation signal, detecting light in the predetermined code to thus determine whether or not the optical mouse is separated from the working surface, and outputting the determination signal depending on a determination result. in the optical pointing device according to the exemplary embodiment of the present invention, the control unit may include: an image information output unit for detecting an image on the working surface, and outputting image information on the detected image; a movement value calculation unit for calculating a movement value from the image information, intermittently outputting the code generation signal, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to the determination signal; and a communication unit for outputting the movement information in response to the calculated movement value and the input signal. in the optical pointing device according to the exemplary embodiment of the present invention, the determination unit may include: a code generator for outputting the code signal to turn on or off the illumination unit in response to the code generation signal; a detection sensor for receiving light generated from the illumination unit to thus output a detection signal; and a code interpreter for interpreting the detection signal to determine whether or not the optical pointing device is on the working surface, and outputting the determination signal depending on the determination result. in the optical pointing device according to the exemplary embodiment of the present invention, the code generator may output the code signal to turn on the illumination unit for a short time enough for a visually very weak signal to be detected. in the optical pointing device according to the exemplary embodiment of the present invention, the code generator may output the code signal to repetitively turn on or off the illumination unit depending on a certain code value. in the optical pointing device according to the exemplary embodiment of the present invention, the code generator outputs the code signal to turn on the illumination unit for a visually very weak signal to be detected and the code signal is a pulse signal and a duty cycle of the pulse signal is larger than 50% or smaller than 50%. in the optical pointing device according to the exemplary embodiment of the present invention, the control unit may have an active state in which the movement value is calculated while the illumination unit remains on for most of the time, and the code generation signal is intermittently output, an inactive state in which a determination is made whether or not the pointing device moves by intermittently turning on the illumination unit while the illumination unit remains off for most of the time, and the code generation signal is intermittently output, and a glaring prevention state in which the code generation signal is intermittently output while the illumination unit remains off for most of the time; and the control pointing device may serve to convert the active state or the inactive state into the glaring prevention state when the determination is made that the optical pointing device is separated from the working surface. in the optical pointing device according to the exemplary embodiment of the present invention, the control unit may further have an idle state in which the illumination unit remains off; and the control unit may further serve to convert into the idle state when the glaring prevention state continues for a predetermined time. in another exemplary embodiment according to the present invention, an optical pointing device includes: an illumination unit for illuminating light on a working surface; a detection unit for determining whether or not the optical pointing device is on the working surface to thus output a detection signal; and a control unit for detecting an image on the working surface to calculate a movement value, outputting movement value in response to an input signal inputted from the outside and the calculated movement value, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to the detection signal. in the optical pointing device according to another exemplary embodiment of the present invention, the control unit may include an image information output unit for detecting an image on the working surface, and outputting image information on the detected image; a movement value calculation unit for calculating a movement value from the image information, and turning off the illumination unit when the optical pointing device is separated from the working surface in response to the detection signal; and a communication unit for outputting the movement information in response to the calculated movement value and the input signal. in the optical pointing device according to another exemplary embodiment of the present invention, the detection unit may include a push button protruded at a bottom side of the optical pointing device. in the optical pointing device according to another exemplary embodiment of the present invention, the optical pointing device may include a plurality of push buttons. in the optical pointing device according to another exemplary embodiment of the present invention, the detection unit may include a bottom cover arranged at the bottom side of the optical pointing device and having a contact point with a main body of the optical pointing device; an upper cover arranged at the upper side of the optical pointing device and having a contact point with the main body of the optical pointing device; and a gate for causing the detection signal to be inactive when the contact point of the upper cover or the contact point of the bottom cover comes off. in the optical pointing device according to another exemplary embodiment of the present invention, the detection unit may include a light emitting diode for illuminating light on the working surface; and a sensor for detecting the light reflected from the working surface to thus output the detection signal. in yet another exemplary embodiment according to the present invention, a method of controlling an optical pointing device includes: a code generation step that turns on or off an illumination unit in response to a code signal; a determination step that detects light output from the illumination unit to analyzes a code included in the light, to thus determine whether or not the optical pointing device is separated from the working surface, and outputs a determination signal depending on a determination result; and a glaring prevention step that turns off the illumination unit when the optical pointing device is separated from the working surface in response to the determination signal. in the optical pointing device control method according to yet another exemplary embodiment according to the present invention, the code generation step may turn on the illumination unit for a short time enough for a visually very weak signal to be detected. in the optical pointing device control method according to yet another exemplary embodiment according to the present invention, the determination step may include: a detection step that receives light generated from the illumination unit to output a detection signal; and an interpretation step that interprets the detection signal to determine whether or not the optical pointing device is on the working surface, and outputs the determination signal depending on a determination result. in the optical pointing device control method according to yet another exemplary embodiment according to the present invention, the glaring prevention step may convert into an active state in which the movement value is calculated while the illumination unit remains on for most of the time, and the code generation signal is intermittently output, or into an inactive state in which a determination is made whether or not the pointing device moves by intermittently turning on the illumination unit while the illumination unit remains off for most of the time, and the code generation signal is intermittently output, into a glaring prevention state in which the code generation signal is intermittently output while the illumination unit remains off for most of the time, when the optical pointing device is separated from the working surface. in the optical pointing device control method according to yet another exemplary embodiment according to the present invention, the glaring prevention step may further include converting into an idle state in which the illumination unit remains off when the glaring prevention state continues for a predetermined time. brief description of the drawings the above and other features of the present invention will become more apparent to those of ordinary skill in the art by describing in detail preferred embodiments thereof with reference to the attached drawings in which: fig. 1 is a block diagram of a conventional optical mouse; fig. 2 is a state diagram for explaining operation of the conventional optical mouse shown in fig. 1 ; fig. 3 is a diagram for explaining a method of controlling an illumination unit in the conventional optical mouse; fig. 4 is a block diagram of the conventional optical mouse capable of preventing a glaring phenomenon; fig. 5 is a block diagram of an illumination unit of the conventional optical mouse shown in fig. 4 ; fig. 6 is a block diagram of an optical mouse according to a first embodiment of the present invention; fig. 7 is a diagram for explaining a method of determining whether or not the optical mouse is on the working surface, for the optical mouse of the present invention shown in fig. 6 ; fig. 8 is a state diagram for explaining operation of the optical mouse of the present invention shown in fig. 6 ; fig. 9 is a diagram for explaining a method of controlling an illumination unit in the optical mouse of the present invention shown in fig. 6 ; fig. 10 is a block diagram of an optical mouse according to a second embodiment of the present invention; fig. 11 is a block diagram of an optical mouse according to a third embodiment of the present invention; fig. 12 is a block diagram of an optical mouse according to a fourth embodiment of the present invention; and fig. 13 is a block diagram for explaining operation of an illumination unit of the optical mouse of the present invention shown in figs. 10 to 12 . detailed description of the invention the present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. this invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. like numbers refer to like elements throughout the specification. an optical pointing device and a control method thereof according to the present invention will now be described with reference to the accompanying drawings. fig. 6 is a block diagram of an optical mouse according to a first embodiment of the present invention, including a control unit 10 - 1 , an input unit 20 , an illumination unit 32 , a detection sensor 42 , a code interpreter 50 , and a code generator 60 , and the control unit 10 - 1 includes an image information output unit 11 including an image sensor 11 - 1 and a converter 11 - 2 , a movement value calculation unit 14 , and a communication unit 13 . in fig. 6 a lens indicates an optical structure that passes through light reflected from a working surface, and a dotted line indicates a direction in which light radiated from the illumination unit 32 is inputted to the image sensor 11 - 1 and detection sensor 42 . a function of each block shown in fig. 6 will be described below. functions of the image information output unit 11 , the communication unit 13 , and the input unit 20 are the same as those described in fig. 1 . the movement value calculation unit 14 calculates a movement value using digital data inputted from the converter 11 - 2 , and outputs an illumination signal to control the illumination unit 32 in response to a state of the optical mouse 1 , a signal inputted from the communication unit 13 , and a determination signal inputted from the code interpreter 50 . in addition, the movement value calculation unit 14 outputs a code generation signal to control the code generator 60 . the illumination unit 32 turns on or off in response to the illumination signal inputted from the movement value calculation unit 14 and the code signal inputted from the code generator 60 . the code generator 60 outputs a code signal to turn the illumination unit 32 on or off, in response to the code generation signal inputted from the movement value calculation unit 14 . the code signal is a pulse signal, and the illumination unit 32 is turned on when the pulse signal is a “high” level, on the other hand, the illumination unit 32 is turned off when the pulse signal is a “low” level. further, if the duty cycle of the code signal which is the pulse is larger than 50%, the turn-on time of the illumination unit 32 is longer than the turn-off time of the illumination unit 32 , on the other is hand, if the duty cycle of the code signal which is the pulse signal is smaller than 50%, the turn-off time of the illumination unit 32 is longer than the turn-on time of the illumination unit 32 . that is, the turn-on time and the turn-off time of the illumination unit 32 can be varied according to the variation of the duty cycle of the code signal. the detection sensor 42 detects light radiated from the illumination unit 32 to output the detection signal. the code interpreter 50 interprets a detection signal inputted from the detection sensor 42 to determine whether or not the optical mouse is on the working surface, and outputs a determination signal depending on the determination result. in other words, the optical mouse 1 of the present invention shown in fig. 6 repetitively turns the illumination unit 32 on or off depending on a specific code using the code generator 60 , detects this through the detection sensor 42 , determines using the code interpreter 50 whether the code detected by the detection sensor 42 matches a code output using the code generator 60 , and thus determines whether or not the optical mouse is on the working surface. while fig. 6 illustrates that the determination signal output from the code interpreter 50 is inputted to the movement value calculation unit 14 , the determination signal may be inputted to the communication unit 13 . in this case, the communication unit 13 outputs the signal in response to the determination signal, and the movement value calculation unit 14 outputs a control signal to turn the illumination unit 32 on or off in response to the signal inputted from the communication unit 13 . in addition, while fig. 6 illustrates that the movement value calculation unit 14 outputs the illumination signal to control the illumination unit 32 , the communication unit 13 may output the illumination signal. in the same manner, the code generation signal may also be output from the communication unit 13 . in other words, the control unit 10 - 1 of the optical mouse 1 of the present invention shown in fig. 6 calculates and outputs the movement value of the optical mouse using the image sensor 11 - 1 , the converter 11 - 2 , the movement value calculation unit 14 , and the communication unit 13 , and at the same time, and outputs the code generation signal intermittently, turns off the illumination unit 32 when the optical mouse 1 is separated from the working surface in response to the determination signal output from the code interpreter 50 , so that it is possible to prevent a glaring phenomenon. fig. 7 is a diagram for explaining a method of determining whether or not the optical mouse is on the working surface, for the optical mouse of the present invention shown in fig. 6 , in which fig. 7a shows a case where the optical mouse is on the working surface and fig. 7b shows a case where the optical mouse is separated from the working surface. a method of determining whether or not the optical mouse is on the working surface, for the optical mouse of the present invention, will be described below with reference to fig. 7 . as shown in fig. 7a , when the optical mouse is on the working surface, light radiated from the illumination unit 32 is reflected on the working surface, and detected through the detecting sensor 42 . however, as shown in fig. 7b , when the optical mouse 1 is separated from the working surface, light radiated from the illumination unit 32 is not detected through the detection sensor 42 . therefore, by turning the illumination unit 32 on or off such that light radiated from the illumination unit 32 has a certain code, and interpreting light detected through the detection sensor 42 , a determination can be made as to whether the optical mouse 1 is on the working surface. in other words, compared with the conventional optical mouse shown in fig. 4 , for the conventional optical mouse, when light is inputted from the outside, and the sensor of the detection unit 40 detects this, a determination can be erroneously made that the optical mouse is on the working surface. however, the optical mouse of the present invention shown in fig. 6 radiates light having a certain code using the illumination unit 32 , and interprets light detected by the detection sensor 42 to thus determine whether the optical mouse is on the working surface, so that even when light is inputted from the outside, a determination can be exactly made as to whether the optical mouse is separated from the working surface. fig. 8 is a state diagram for explaining operation of the optical mouse of the present invention shown in fig. 6 , and thus the operation of the optical mouse of the present invention will be described below with reference to fig. 8 . the optical mouse of the present invention has an active state in which the movement value is calculated depending on the operation state of the optical mouse while the illumination unit 32 turns on for most of the time, an inactive state in which the determination is made as to whether the optical mouse moves while the illumination unit 32 turns off for most of the time and periodically turns on, and a glaring prevention state and an idle state in which the illumination unit 32 remains undetectably off and completely off state, respectively. the optical mouse turns the illumination unit 32 on or off to output a certain code in the active, inactive, and glaring prevention states, and detects this to determine whether the optical mouse is on the working surface. when the optical mouse moves in the active state, the optical mouse remains the active state (s 1 ). however, when there is no movement of the optical mouse for a predetermined time in the active state, the optical mouse converts into the inactive state (s 2 ). in addition, when the optical mouse is separated from the working surface in the active state, the optical mouse converts into the glaring prevention state (s 7 ). when there is no movement of the optical mouse in the inactive state, the optical mouse remains the inactive state (s 3 ). however, when the movement of the optical mouse is detected, the optical mouse converts into the active state (s 4 ). when there is no movement of the optical mouse for a predetermined time in the inactive state as well, the optical mouse converts into the idle state (s 5 ). in addition, when the optical mouse is separated from the working surface in the inactive state, the optical mouse converts into the glaring prevention state (s 8 ). when a determination is made that the optical mouse is on the working surface in the glaring prevention state, the optical mouse converts into the active state (s 10 ). however, when a determination is made that the optical mouse is separated from the working surface, the optical mouse remains the glaring prevention state (s 9 ). when the optical mouse is separated from the working surface for a predetermined time in the glaring prevention state as well, i.e., when the glaring prevention state continues for a predetermined time, the optical mouse converts into the idle state (s 11 ). in the idle state, the movement of the optical mouse is not detected, and the optical mouse converts into the active state by control of the input unit 20 such as buttons (s 6 ). fig. 9 is a diagram for explaining a method of controlling the illumination unit 32 in the optical mouse of the present invention, in which fig. 9a illustrates a method of controlling the illumination unit 32 in the active state, fig. 9b the inactive state, and fig. 9c in the glaring prevention state, respectively. a method of controlling the illumination unit 32 in the optical mouse of the present invention will be described with reference to fig. 9 . in the active state ( fig. 9a ), the illumination unit 32 turns on periodically with a predetermined first period t 1 , and in addition, the illumination unit 32 turns on or off periodically depending on a predetermined third period t 3 to generate a code, in order to determine whether the optical mouse is on the working surface. in the inactive state ( fig. 9b ), the illumination unit 32 turns on periodically with a predetermined second period t 2 , and in addition, the illumination unit 32 turns on or off periodically depending on a predetermined third period t 3 to generate a code, in order to determine whether the optical mouse is on the working surface. the second period t 2 is set to be longer than the first period t 1 . in the glaring prevention state ( fig. 9c ), while the illumination unit 32 remains the off state basically, the optical mouse turns the illumination unit 32 on or off periodically depending on the predetermined third period t 3 to generate a code, in order to determine whether the optical mouse is on the working surface. turning the illumination unit 32 on or off to generate a code indicates that the illumination unit 32 turns on or off depending on a certain code. at this time, when the illumination unit 32 turns on, a time for the illumination unit 32 to turn on is set to be short enough, i.e., the illumination unit 32 turns on for a short time enough for visually very weak light to be detected, so that the glaring phenomenon can be minimized or prevented. while it is illustrated that the periods t 3 in which the code is generated are the same in the active, inactive, and glaring prevention states, the periods may be set to be different from each other. in other words, the optical mouse of the present invention generates a code periodically using the illumination unit 32 in the active state ( fig. 9a ) and the inactive state ( fig. 9b ), and thus determines whether the optical mouse is on the working surface, and converts into the glaring prevention state ( fig. 9c ) when a determination is made that the optical mouse is separated from the working surface. in the glaring prevention state ( fig. 9c ), while turning the illumination unit 32 off basically, the optical mouse generates a code using the illumination unit 32 , so that a determination is made as to whether the optical mouse is on the working surface. when the code is generated, the illumination unit 32 turns on for a short time enough for a user to detect visually very weak light, so that the glaring phenomenon can be prevented when the optical mouse is turned upside down. in addition, power consumption can also be minimized. fig. 10 is a block diagram showing a block diagram of an optical mouse according to a second embodiment of the present invention, including a control unit 10 - 2 , an input unit 20 , an illumination unit 30 and a push button (pb), and the control unit 10 - 2 includes an image information output unit 11 including an image sensor 11 - 1 and a converter 11 - 2 , a movement value calculation unit 15 , and a communication unit 13 . in fig. 10 , a lens refers to an optical structure that passes light reflected from the working surface to the image sensor 11 - 1 . a function of each block shown in fig. 10 will be described below. functions of the image information output unit 11 , the communication unit 13 , the input unit 20 and the illumination unit 30 are the same as those described in fig. 1 . the movement value calculation unit 15 calculates and outputs the movement value using image information inputted from the converter 11 - 2 , and outputs an illumination signal to control the illumination unit 30 in response to a state of the optical mouse 1 , a detection signal inputted from the push button (pb), and a signal inputted from the communication unit 13 . the push button pb outputs the detection signal depending on whether the optical mouse 1 is on the working surface. in other words, when the optical mouse 1 is on the working surface, the push button pb also remains a contact state, and when the optical mouse 1 is separated from the working surface, the push button pb also become an off state. using this, a determination can be made as to whether the optical mouse 1 is on the working surface, and the detection signal is output depending on a determination result. in other words, the optical mouse according to the second embodiment of the present invention shown in fig. 10 determines whether the optical mouse is separated from the working surface depending on whether the push button pb contacts or not, and when the optical mouse is separated from the working surface, the illumination 30 turns off, so that the glaring phenomenon generated when the optical mouse is turned upside down can be prevented. fig. 11 is a block diagram showing a block diagram of an optical mouse according to a third embodiment of the present invention, including a control unit 10 - 2 , an input unit 20 , an illumination unit 30 and an upper cover uc, a bottom cover bc, and a gate 44 , and the control unit 10 - 2 includes an image information output unit 11 including an image sensor 11 - 1 and a converter 11 - 2 , a movement value calculation unit 15 , and a communication unit 13 . in fig. 11 , a lens refers to an optical structure that passes light reflected from the working surface to the image sensor 11 - 1 . a function of each block shown in fig. 11 will be described below. functions of the image information output unit 11 , the communication unit 13 , the input unit 20 and the illumination unit 30 are the same as those described in fig. 1 , and a function of the movement value calculation unit 15 is the same as that described in fig. 10 . when the optical mouse 1 is turned upside down, the upper cover uc is off from a main body of the optical mouse 1 , and when the optical mouse 1 is separated from the working surface, the bottom cover bc is off from the main body of the optical mouse 1 . the gate 44 outputs the detection signal depending on whether the upper cover uc or the bottom cover bc is off from the main body of the optical mouse 1 . in other words, the optical mouse according to the third embodiment of the present invention shown in fig. 11 is separated from the working surface when one of the upper cover uc or the bottom cover bc is off from the main body of the optical mouse. therefore, using the gate 44 , a determination is made as to whether one of the upper cover uc or the bottom cover bc is off from the main body of the optical mouse 1 , and outputs the detection signal depending on the determination result, so that a determination can be made that the optical mouse is separated from the working surface. thus, when the optical mouse is separated from the working surface, the illumination unit 30 turns off, so that the glaring phenomenon generated when the optical mouse is turned upside down can be prevented. while figs. 10 and 11 illustrate that the detection signal output from the push button pb or the gate 44 is inputted to the movement value calculation unit 15 , it may be inputted to the communication unit 13 . in this case, the communication unit 13 is arranged to inform the movement value calculation unit 15 , in response to the detection signal, whether or not the optical mouse is separated from the working surface. in addition, the communication unit 13 may output an illumination signal to turn the illumination unit 30 on or off directly. in this case, information on whether or not the optical mouse 1 is separated from the working surface can be inputted from the movement value calculation unit 15 , and the detection signal may directly inputted from the push button pb or the gate 44 . in addition, in figs. 10 and 11 , the detection signal output from the push button pb or the gate 44 may be directly used to turn the illumination unit 30 on or off. in this case, the illumination unit 30 of figs. 10 and 11 has the same construction as the illumination unit 31 shown in fig. 5 , and the only difference between them is that the detection signal is inputted from the push button pb or the gate 44 rather than the detection unit 40 . fig. 12 is a block diagram showing a block diagram of an optical mouse according to a fourth embodiment of the present invention, including a control unit 10 - 2 , an input unit 20 , an illumination unit 30 and a detection unit 40 . here, the control unit 10 - 2 of fig. 12 includes an image sensor 11 - 1 , a converter 11 - 2 , a movement value calculation unit 15 , and a communication unit 13 , and the detection unit 40 includes a sensor and a light emitting diode (led). a function of each block shown in fig. 12 will be described below. functions of the image information output unit 11 , the communication unit 13 , the input unit 20 and the illumination unit 30 are the same as those described in fig. 1 , and a function of the movement value calculation unit 15 is the same as that described in fig. 10 and a function of the detection unit 40 is the same as the described in fig. 4 . in other words, the optical mouse according to the fourth embodiment of the present invention shown in fig. 12 determines whether the optical mouse is on the working surface using the detection unit 40 , and thus the movement value calculation unit 15 outputs the illumination signal to turn the illumination unit 30 on or off depending on the determination result. as described in figs. 10 and 11 , the detection signal may be inputted to is the communication unit 13 , and the communication unit 13 may control the illumination unit 30 . fig. 13 is a block diagram for explaining operations of the illumination unit 30 in the optical mouse according to the second to fourth embodiments of the present invention shown in figs. 10 to 12 , in which the illumination unit 30 includes a resistor r 1 , a light emitting diode led, and a driving circuit dr, and the driving circuit dr includes a resistor r 2 and a transistor tr. a function and operation of each block shown in fig. 13 will be described below. the driving circuit dr turns the light emitting diode led on or off in response to the illumination signal inputted from the movement value calculation unit 15 . when the movement value calculation unit 15 outputs the illumination signal, it outputs the illumination signal with reference to a detection signal inputted from the sensor of the detection unit. the push button pb or the gate 44 may be connected rather than the detection unit 40 . in other words, compared with the illumination unit 31 of the conventional optical mouse shown in fig. 5 , only one driving circuit dr is required in the illumination unit 30 of the optical mouse of the present invention, so that the cost is reduced and the circuit is simplified. in other words, when the optical mouse according to the first to third embodiments of the present invention is turned upside down, the illumination unit 30 or 32 turns off, so that the glaring phenomenon can be minimized and power consumption can be minimized, and a determination will not erroneously made that the optical mouse is on the working surface, due to light inputted from the outside of the optical mouse. in addition, the optical mouse according to the fourth embodiment of the present invention is turned upside down, the illumination unit 30 or 32 turns off so that the glaring phenomenon can be prevented, and the cost is reduced and the circuit is simplified relative to the conventional optical mouse having a glaring prevention function. in addition, when the optical mouse is separated from the working surface, the illumination circuit 30 turns off so that unnecessary power consumption can be prevented. therefore, an optical mouse and a control method thereof according to the present invention can prevent a glaring phenomenon generated when the optical mouse is turned upside down, and unnecessary power consumption can be prevented. while preferred embodiments of the present invention have been described above, those skilled in the art will appreciate that a variety of modifications and changes can be made without departing from the spirit and scope of the present invention claimed in the following claims.
|
138-749-140-479-594
|
US
|
[
"US",
"AU",
"WO"
] |
G06T1/00,H04H20/31,H04N1/32,H04N7/16,H04N7/26,H04N21/2389,H04N21/44,H04N21/4627,H04N21/8358,G06K9/00
| 2000-04-19T00:00:00 |
2000
|
[
"G06",
"H04"
] |
applying digital watermarks using printing process correction
|
image color values are modified in accordance with printing process characteristics. digital watermark signal representations are determined and modified in accordance with the characteristics. the modified signal representations are combined with the original image color values. the image is then printed by the printing process. the resulting printed image includes a watermark that is not materially affected by the printing process characteristics.
|
1 . a method of digital watermarking an image comprising: adjusting the image in accordance with values in a first representation associated with a printing process; determining values to convey a digital watermark in the adjusted image; adjusting the values in accordance with a second representation associated with the printing process; and combining the adjusted change values and the image to produce a digital watermarked image. 2 . the method of claim 1 , wherein the first representation comprises a forward dot gain curve. 3 . the method of claim 2 , wherein the second representation comprises a backward dot gain curve. 4 . the method of claim 3 wherein the backward dot gain curve comprises an inverse of the forward dot gain curve. 5 . the method of claim 1 wherein the printing process comprises an offset printing press. 6 . the method of claim 1 wherein the image is watermarked using a scale to black technique. 7 . the method of claim 1 wherein said image is watermarked using a scale to white technique. 8 . a method of steganographically hiding a signal in an image comprising: determining change values to represent the signal in the image; and altering color values of the image by an amount to achieve the change values, wherein the amount includes a compensation for a variation in a relationship of an input color value and at least one of ink and dye provided by a printing process to represent the input color value, and wherein the image includes the signal steganographically embedded therein when printed with the printing process. 9 . the method of claim 8 , wherein the printing process comprises an offset printing process. 10 . the method of claim 8 , wherein the steganographically hiding comprises digital watermarking. 11 . the method of claim 8 , further comprising printing the image, wherein the printed image includes the signal steganographically embedded therein. 12 . a method of processing an image to compensate for variation in a printing process, wherein the image includes a plurality of color values, said method comprising: receiving a representation of a variation in a relationship of an input color value and at least one of ink and dye provided by the printing process to represent the input color value; determining change values needed to alter the image to accommodate a digital watermark embedded therein; adjusting the change values with the representation; and modifying the image with the adjusted change values to accommodate the digital watermark and to compensate for the variation. 13 . the method of claim 12 wherein the printing process comprises an offset printing press.
|
related applications this application is a continuation of u.s. patent application ser. no. 10/209,053, filed jul. 30, 2002 (now u.s. pat. no. 6,700,995). the ser. no. 10/209,053 application is a continuation in part of co-pending u.s. patent application ser. no. 09/553,084, filed apr. 19, 2000 (now u.s. pat. no. 6,590,996). each of these patent documents is herein incorporated by reference. field of the invention the present invention relates steganography and more particularly to the digital watermarks. background and summary of the invention the technology for applying digital watermarks to images and to other types of data is well developed. for example see issued u.s. pat. no. 5,748,783, issued u.s. pat. no. 5,768,426 issued u.s. pat. no. 5,822,435 and the references cited in these patents. also various commercially available products (such as the widely used image editing program photoshop marketed by adobe corporation) have image watermarking capability. there are many other patents and much technical literature available relating to the application of digital watermarks to images and to other types of data. co-pending application ser. no. 09/553,084 (now u.s. pat. no. 6,590,996) describes a technique of color adaptive watermarking. with the technique described in application ser. no. 09/553,084 a change in an image attribute such as luminance (or chrominance) is mapped to a change in color components such that the change is less visible application ser. no. 09/553,084 describes the scale to black and the scale to white techniques for applying watermarks. by using the scale to white method for colors with a high yellow content such as yellow, red and green, and by using the scale to black for blue, cyan and magenta a watermark with a lower visibility and the same detect ability can be embedded in an image. it is known that when an image is printed on a standard offset press, the relationship between the digital value of a color and the amount of ink actually applied by the press is not linear. figs. 1 illustrates the dot gain curve for a typical standard offset printing press. the horizontal axis gives a digital value of a color and the vertical axis indicates the amount of ink actually transferred by the press. the shape of the dot gain curve of offset printing presses is well known. as a result of the dot gain curve illustrated in fig. 1 , when an image containing a watermark is printed on an offset press, a watermark signal in the shadows (i.e. in an area with more ink) is reduced and a watermark signal in the highlights (i.e. in an area with less ink) is amplified. note that the slope of the dot gain curve is different in the shadow area and in the highlight area. thus, the same amount of change in color value produces a different amount of change in the ink applied in the two different areas. the present invention provides a technique which insures that a watermark signal is preserved in an printed image as accurately as possible not withstanding the fact that the dot gain curve of the printing press is not linear. with the present invention, the image data is first modified in accordance with the forward dot gain curve of a printing press, next the watermark tweak values (i.e. the watermark change values) are calculated for this modified image data. the calculated tweak values are then modified in accordance with the backward dot gain curve of the printing press. the modified tweak values are then added to the original image data values to produce a watermarked image. the watermark image is then printed on the printing press. the result is that the effective tweak on printed paper is not materially affected by the dot gain curve of the printing press. brief description of figures fig. 1a shows a forward dot gain curve. fig. 1b shows a backward dot gain curve. fig. 2 illustrates scaling to black. fig. 3 illustrates scaling to white. fig. 4 is a program block flow diagram of the operation of the preferred embodiment. detailed description of embodiments co-pending application ser. no. 09/553,084, filed apr. 19, 2000 (now u.s. pat. no. 6,590,996) describes a system for watermarking images. the system described in application ser. no. 09/553,084 inserts watermarks in images by selecting and modifying colors to obtain approximately equal visibility for all colors. the preferred embodiment of present invention, as described herein, is described as a modification of the system described in application ser. no. 09/553,084. the object of the modifications is to compensate for the dot gain curve of a printer. the entire specification of application ser. no. 09/553,084 is hereby incorporated herein by reference. it is desirable that a watermark embedding algorithm produce luminance changes with approximately equal visibility through color space. adaptive color embedding as described in application ser. no. 09/553,084, selects the colors that are modified to produce a required luminance change, in a way that obtain approximately equal visibility for all colors. the dot gain correction provided by the preferred embodiment described herein approximately compensates for the non-linear effect of the printing process, so that a desired percentage change is achieved on press (that is, in the amount of ink applied to create the image). it is noted that the slope of the dot gain curve is different in the shadow area and in the highlight area. thus, the same amount of change in color value produces a different amount of change in the ink applied in the two different areas. the preferred embodiment insures that a watermark signal (i.e. a change value) is preserved in a printed image as accurately as possible not withstanding the fact that the dot gain curve of the printing press is not linear. as explained in application ser. no. 09/553,084 a watermark can be applied to images using either a scale to black or a using a scale to white technique. with the scale to black technique, the image pixel is like a vector between black and the pixel color value. the vector is increased or decreased as shown in fig. 2 . that is, fig. 2 illustrates the color changes for a luminance change utilizing the scale to black technique. the following table lists for each color, the colors that are modified as a result of a luminance change. the table also indicates the degree to which the modification is visible. for scale to black: color colors modified visibility of the change yellow cyan/magenta high red cyan high green magenta medium blue yellow low cyan magenta/yellow low magenta cyan/yellow low fig. 3 illustrates the color changes that occur with a scale to white technique. the scale to white technique obtains the same luminance change as the scale to black technique; however, when scaling to white the image pixel is a vector between white and the pixel color value as shown in fig. 2 . the following table lists for each color, the colors modified as the result of a luminance change. the table also indicates the degree to which the modification is visible. for scale to white color colors modified visibility of change yellow yellow low red magenta/yellow low green cyan/yellow medium blue cyan/magenta high cyan cyan high magenta magenta medium by using the scale to white method for colors with high yellow content such as yellow and red, and scale to black for blue, cyan, magenta and green a lower visibility mark can be made with the same detectability. scaling to white results in the watermark being applied mainly to the dominant colors, and scaling to black implies that the watermark is mainly in the secondary colors. when images are printed on an offset press, it is known that there is not a straight line relationship between the digital value of the color at any point in the image and the corresponding amount of ink applied to the paper at that point. this is known as dot gain. fig. 1a shows the forward dot gain curve. that is the relationship between the digital value of a color and the amount of ink actually applied. fig. 2b shows a backward dot gain curve. that is, fig. 2 indicates the value needed in order to get a particular amount of ink on the paper. the following is a list of 256 values that generate a curve as shown in figs. 1a . that is, the following is a list of 256 positions on the vertical axis for 256 positions (i.e. for 0 to 255) on the horizontal axis. 0 7 12 18 22 26 29 32 34 37 39 42 44 46 48 50 52 54 55 57 59 60 62 64 65 67 68 70 71 73 74 76 77 78 80 81 83 84 85 86 88 89 90 91 93 94 95 96 97 99 100 101 102 103 104 105 106 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 135 136 137 138 139 140 141 142 143 144 144 145 146 147 148 149 150 150 151 152 153 154 155 155 156 157 158 159 160 160 161 162 163 164 164 165 166 167 168 168 169 170 171 171 172 173 174 175 175 176 177 178 178 179 180 181 181 182 183 184 184 185 186 186 187 188 189 189 190 191 191 192 193 194 194 195 196 196 197 198 198 199 200 201 201 202 203 203 204 205 205 206 207 207 208 209 209 210 211 211 212 213 213 214 215 215 216 216 217 218 218 219 220 220 221 222 222 223 224 224 225 225 226 227 227 228 229 229 230 230 231 232 232 233 234 234 235 235 236 237 237 238 238 239 240 240 241 241 242 243 243 244 244 245 246 246 247 247 248 249 249 250 250 251 251 252 253 253 254 254 255 the following is a list of 256 values that generate the curve shown in fig. 1b . that is, the following are the vertical values for 256 positions (i.e. 0 to 255) on the horizontal axis. 0 1 1 1 1 1 1 1 2 2 2 2 2 3 3 3 3 3 3 4 4 4 4 5 5 5 5 6 6 6 7 7 7 8 8 9 9 9 10 10 11 11 11 12 12 13 13 14 14 15 15 16 16 17 17 18 19 19 20 20 21 22 22 23 23 24 25 25 26 27 27 28 29 29 30 31 31 32 33 34 34 35 36 36 37 38 39 40 40 41 42 43 44 44 45 46 47 48 49 49 50 51 52 53 54 55 56 57 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 86 87 88 89 90 91 92 93 94 96 97 98 99 100 101 103 104 105 106 107 109 110 111 112 113 115 116 117 118 120 121 122 123 125 126 127 129 130 131 132 134 135 136 138 139 140 142 143 144 146 147 149 150 151 153 154 156 157 158 160 161 163 164 166 167 168 170 171 173 174 176 177 179 180 182 183 185 186 188 189 191 193 194 196 197 199 200 202 203 205 207 208 210 211 213 215 216 218 219 221 223 224 226 228 229 231 233 234 236 238 239 241 243 244 246 248 250 251 253 255 it is noted that different offset processes produce different amounts of dot gain; however, with most offset processes, the dot gain curve has the shape shown. for some particular offset processes, the actual values may to 50 or 75 percent of the values given above. the values used in any particular application should be the values appropriate for the particular printing process that will be used to print a particular image. fig. 4 is a block program flow diagram of a program for the preferred embodiment of the invention. the process begins with an image 401 which is in the cymk color space. as indicated by block 402 , the values for each color in the image are first modified in accordance with the values of the forward dot gain curve. this generates a modified image. next as indicated by block 403 calculations are made using the modified image to determine the tweak (i.e. the change) values needed to embed a particular watermark in the modified image. this calculation can be done using known watermarking techniques. in the preferred embodiment, the tweak values are calculated using the technique available in the commercially available photoshop image editing program. however, in other embodiments, other watermarking techniques can be used. the tweak values are next modified in accordance with the backward dot gain curve values as indicated by block 404 . next as indicated by block 405 , the modified tweak values are added to the values in the original image 401 , thereby producing a watermarked image. finally as indicated by block 406 the watermarked image is printed using an offset press which has the forward and backward dot gain values used in blocks 402 and 404 . the watermark can then be read from the printed image using known watermarks reading techniques. in an alternate embodiment of the invention, the tweak values are added to the modified image values and then the resultant image is modified in accordance with the backward dot gain curve values; however, it has been found that in most instances, the process described in fig. 4 eliminates some rounding errors. in some applications, it has been found desirable to add back a constant that controls the amount of the scale to black signal when a color with high yellow-blue saturation is being embedded. this is sometime necessary, since some cameras are insensitive in the blue channel, so changes in yellow are not detected very well. in general to dot gain correction is only applied to the cmy channels, and not to k channel. however, if desired the dot gain correction can be applied to all the channels. the preferred embodiments described above relate to the dot gain curve for offset printing processes. it is noted that other processes such as ink jet printing have a different type of dot gain curve. the invention can be applied to most types of printing processes by merely using a dot gain curve appropriate to the particular process. images watermarked using the embodiments described above can be read with conventional watermark reading techniques. naturally as is conventional the watermark reading technique used should coincide with the particular technique used to generate the change values, that is, with the technique used to watermark the image. while the invention has been described with respect to watermarking images it should be understood that the principle is applicable to other types of data. the preferred embodiment relates to an image in the cymk color space. other embodiments using the same principles can operate on images in various other color spaces. while the invention has been shown and described with respect to preferred embodiments, it should be understood that various changes in form and detail may be make without departing from the spirit and scope to the invention. the scope of the invention is limited only by the appended claims.
|
140-733-833-734-83X
|
US
|
[
"MX",
"EP",
"TW",
"US",
"CA",
"BR",
"WO"
] |
G01D3/08,G01D4/00,G01K7/42,G01R11/25,G08B21/18,G01R35/00,G01R1/36,G08B17/00
| 2013-02-13T00:00:00 |
2013
|
[
"G01",
"G08"
] |
method and apparatus for operating an electricity meter.
|
a method and apparatus that monitors and controls the operation of an electricity meter, and modifies at least one temperature threshold for determining when an alarm message should be transmitted or an electrical connection in the meter should be disconnected. the method and apparatus includes a plurality of sensors that detect temperatures in various locations within the electricity meter.
|
an electricity meter connected between a power source (107) and a load (105), comprising: a first circuit (123) and a second circuit (125); a remote disconnect switch (131); a plurality of temperature sensors (135, 137), wherein a first sensor is proximate to the first circuit (123) and detects a first temperature near the first circuit (123) and a second sensor is proximate to the second circuit (123) and detects a second temperature near the second circuit (123); at least one processor configured to, receive the first temperature from the first sensor (135) and the second temperature from the second sensor (137), compare the first temperature and the second temperature to a first threshold, operate a remote disconnect switch (131) when the at least one of the first temperature and the second temperature exceeds the first threshold, determine an average rate of change based on a short-term temperature average of at least one of the first temperature and the second temperature over a first number of samples and a long-term temperature average of the at least one of the first temperature and the second temperature over a second number of samples, and modify the first threshold when a difference between the first temperature and second temperature is greater than a second threshold and the average rate of change exceeds a third threshold. the electricity meter according to claim 1, wherein the first circuit (123) is proximate to an electrical connection (101) and the processor is configured to determine the first temperature difference when the first temperature is greater than the second temperature. the electricity meter according to claim 1, wherein the second number of samples is greater than the first number of samples. the electricity meter according to claim 3, wherein the first number of samples includes a most recent first temperature at the first location and a predetermined number of samples of the first temperature detected immediately before detecting the most recent first temperature. the electricity meter according to claim3, wherein the second number of samples occur before a first sample of the first number of samples. the electricity meter according to claim 5, wherein the second number of samples of the long-term temperature average includes each sample of the first temperature over a predetermined period of time before the first sample of the first number of samples. the electricity meter according to any of claims 1 to 6, wherein the remote disconnect switch (131) connects the electrical connection (101) between the power source (107) to the load (105) when set to a closed state and disconnects the electrical connection (101) when set to an open state, wherein the first threshold corresponds to a high temperature condition in a meter (100), the first circuit (123) is in the vicinity of the electrical connection (101), and the processor is configured to set the remote disconnect switch (131) to the open state when the first temperature is equal to or greater than the second threshold. the electricity meter according to any of claims 1 to 7, wherein the processor is configured to, compare the other of the at least one of the first temperature and the second temperature to a fourth threshold, operate the remote disconnect switch (131) when the other of the at least one of the first temperature and the second temperature exceeds the third threshold, determine a second short-term temperature average of the other of the at least one of the first temperature and the second temperature over a third number of samples, determine a second long-term temperature average of the other of the at least one of the first temperature and the second temperature over a fourth number of samples, determine a second average rate of change based on the second short-term temperature average and the second long-term temperature average, and modify the fourth threshold when a difference between the first temperature and second temperature is greater than the second threshold and the second average rate of change exceeds the third threshold. a method of monitoring and controlling an operation of an electricity meter (100), comprising: periodically detecting a first temperature of a first location with a first sensor; transmitting the first temperature from the first sensor to a microprocessor; comparing the first temperature to a first threshold for at least one of transmitting an alarm and operating a remote disconnect switch (131) to disconnect an electrical connection (101) of the power source; determining a first temperature average of the first temperature over a short-term number of samples; determining a second temperature average of the first temperature over a long-term number of samples; determining an average rate of change based on the first temperature average and the second temperature average; and modifying the first threshold when an average rate of temperature change is equal to or greater than a predetermined amount for an average rate of temperature change. a non-transitory computer-readable storage medium storing executable instructions, which when executed by one or more processors associated with the electricity meter according to claim 1, causes the one or more processors to perform: periodically detecting a first temperature of a first location and detecting a second temperature of a second location; comparing at least one of the first temperature and the second temperature to a first threshold for transmitting an alarm and a second threshold greater than the first threshold for operating a remote disconnect switch (131); comparing the first temperature and the second temperature to determine a first temperature difference; determining a short-term temperature average of at least one of the first temperature and the second temperature over a first number of samples; determining a long-term temperature average of the at least one of the first temperature and the second temperature over a second number of samples; determining an average rate of change based on the short-term temperature average and the long-term temperature average; and modifying at least one of the first threshold and the second threshold when the first temperature difference is equal to or greater than a third threshold and the average rate of change is equal to or greater than a fourth threshold.
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field the present invention relates to a method and apparatus that monitors a rate of change in temperature and a temperature difference between different locations within an electricity meter, and adjusts alarm and disconnection thresholds accordingly to improve the responsiveness of the electricity meter to potential high temperature conditions. background conventional electricity meters include an electrical connection between a power source and a load. conventional electricity meters detect the temperature inside a meter, and may send alerts and disconnect the power source from the load when a detected temperature reaches set predetermined thresholds. related electricity meters are known from wo 2013/006901 a1 , us 2010/0036625 a1 and us 2002/0105435 a1 . summary one object of the method and apparatus described herein is to monitor the operation of an electricity meter and implement measures in advance of the occurrences of various operating conditions. a further object of the method and the apparatus is to modify operational thresholds for sending an alarm or disconnecting an electrical connection, in response to current operating conditions that indicate the operational thresholds may be exceeded. another object of the method and apparatus is to send an alarm or disconnect an electrical connection at lower thresholds in order to respond earlier to operating conditions that if prolonged, may risk the continued operation of the meter. brief description of the drawings a more complete appreciation of aspects of this disclosure and many of the attendant advantages thereof will be readily obtained by reference to the following detailed description when considered in connection with the accompanying drawings, wherein: figs. 1a and 1b each provide a block diagram for a system including an apparatus for monitoring and controlling the operation of a meter that includes an electrical connection between a power source and a load; fig. 2 is a flow chart illustrating an exemplary process for operating an electricity meter; fig. 3 is a flow chart illustrating an exemplary process for sending an alarm for a high temperature condition; fig. 4 is a flow chart illustrating an exemplary process for disconnecting an electricity meter; fig. 5 is a flow chart illustrating an exemplary process for updating operational thresholds; fig. 6 is a flow chart illustrating an exemplary process for determining a temperature difference; fig. 7 is a flow chart illustrating an exemplary process for evaluating and updating temperature thresholds; and fig. 8 is a flow chart illustrating an exemplary process for calibrating threshold values for an electricity meter. detailed description the invention is defined by the independent claims. according to one aspect of the present disclosure, there is provided a system including a meter (electricity meter or other power measurement device), and a method for monitoring and controlling the operation of the meter, and modifying thresholds for sending an alarm or disconnecting an electrical connection in the meter. the method includes periodically detecting a first temperature of a first location with a first sensor and a second temperature of a second location with a second sensor. at least one of the first temperature and the second temperature are compared to a first threshold for transmitting an alarm and a second threshold for operating a remote disconnect switch. the first temperature is compared second temperature to determine a first temperature difference. a short-term temperature average of at least one of the first temperature and the second temperature is determined for a first number of samples, and a long-term temperature average is determine for a second number of samples of the temperature that was used for the short-term average. the method includes determining an average rate of change based on the short-term temperature average and the long-term temperature average. the method includes modifying at least one of the first threshold and the second threshold when the first temperature difference is equal to or greater than a third threshold and the average rate of change is equal to or greater than a fourth threshold. according to another aspect of the present disclosure, there is provided a system including a meter (electricity meter or other power measurement device, and an apparatus for monitoring and controlling the operation of meter. the apparatus modifies thresholds for sending an alarm or disconnecting an electrical connection in the meter. the apparatus includes a first circuit, a second circuit, a remote disconnect switch, and a plurality of temperature sensors. the plurality of sensors include a first sensor proximate to the first circuit and detects a first temperature near the first circuit, and a second sensor proximate to the second circuit and detects a second temperature near the second circuit. the apparatus includes at least one processor configured to receive the first temperature from the first sensor and the second temperature from the second sensor, and compare at least one of the first temperature and the second temperature to a first threshold. the processor operates a remote disconnect switch or sends a an alarm when the at least one of the first temperature and the second temperature exceeds the first threshold. the processor determines an average rate of change based on a short-term temperature average of at least one of the first temperature and the second temperature over a first number of samples, and a long-term temperature average of the at least one of the first temperature and the second temperature over a second number of samples. the processor modifies the threshold when a difference between the first temperature and second temperature is greater than a second threshold, and the average rate of change exceeds a third threshold. it must be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views. fig. 1a is a block diagram of an electricity meter 100 including an electrical connection 101 in a line 103 that connects a power supply 105 to an electrical load 107. the electrical connection 101 is provided in the line 103 by the contact between contacts 109 of the electricity meter 100 and contacts 111 of a power panel 113. the contacts 111 of the power panel 113 provide a meter socket that receives the contacts 109 of the electricity meter 100. an enclosure 117 of the electricity meter 100 houses a controller 115 (ecu), a first ic 123, and a second ic 125. the first ic 123 receives information from various sensors (not shown) and transmits the information from the various sensors to the controller 115. the controller 115 may operate the disconnect switch 131 to open based on the information transmitted from the first ic 123. the second ic 125 transmits and receives operational information from a user display 127 and the controller 115. the controller 115 transmits operational data to a communications board 129 that transmits information from the controller 115 to a back end 133. the back end 133 being part of a network (not shown) that communicates with multiple electricity meters 100. the disconnect switch 131 is provided in an internal line 103 within the electricity meter 100. the disconnect switch 131 can be operated to disconnect the power supply 105 from the electrical load 107. in addition, the electricity meter 100 is provided with an auxiliary power connection 135, such that when the disconnect switch 131 is opened and the power supply 105 is disconnected from the electrical load 107, the electricity meter 100, and thus the controller 115, is still provided with power. the disconnect switch 131 can be operated remotely. the electricity meter 100 is also provided with a first temperature sensor 137 located on the first ic 123 adjacent to the electrical connection 101. the first sensor 137 detects the temperature of at least one phase of the electrical connection 101. in a poly-phase meter, the first temperature sensor 137 transmits the highest temperature between the phases, or an average temperature for all of the phases, to the controller 115. the electricity meter 100 is also provided with a second temperature sensor 139 located on the second ic 125. the second temperature sensor 139 senses the temperature of the second ic 125 and transmits the temperature to the controller 115. in the embodiment of an electricity meter 100' of fig. 1b , the controller 115 is combined with the first ic 123, and the second temperature sensor 139 transmits temperature readings to the second ic 125. the second ic 125 is configured to receive the temperature reading from the second temperature sensor 139, transmit the reading to the controller 115, and send a high temperature alarm to the communications board 129 and the user display 127. the controller 115 receives temperature readings from the first temperature sensor 137 and the second ic 125, operates the disconnect switch 131, transmits the temperature detected by the first temperature sensor 137 to the second ic 125, and communicates with the communications board 129. the second ic 125 is configured to send the high temperature alarm message to the communications board 129 and the user display 127, when the temperature detected by the first temperature sensor 137, and transmitted by the controller 115, exceeds a threshold temperature. the controller 115 in the embodiments of figs. 1a and 1b can send and receive information from the back end 133, including updated values for threshold values and look up tables used in the exemplary processes. the threshold values may be updated dynamically in response to the detection of certain operational parameters, or external conditions which may be determined by a user or a utility. in particular, the temperatures detected by the first and second temperature sensors (135, 137) may be used individually or together, to determine the degree to which threshold values for sending an alarm or disconnecting the electrical connection 101 are to be changed. one or more additional temperature sensors in different location within the meter may also be used for comparison with one or both of the temperatures detected by the first and second temperature sensors (135, 137). embodiments disclosed herein include temperature sensors provided on first and second ics. in addition, separate stand alone temperature sensing units, including thermistors, thermocouples, or infra-red sensing devices may be mounted on interior portions of an enclosure, or to other components in an electricity meter. for example, one or more temperature sensors may be placed on or near a bus bar of an electrical connection. look up tables used to determine reference rates of change in temperature, can be updated dynamically in response to the detection of operating parameters of an electricity meter, or external conditions that may dictate different permissible rates at which temperature can change. the updates can be provided through a network communication or through onsite maintenance of the electricity meter 100. a controller 115 may include one or more processors or equivalents thereof, such as a central processing unit (cpu) and/or at least one application specific processor (asp). a processor may include one or more circuits or be a circuit that utilizes a computer readable medium, such as a memory circuit (e.g., rom, eprom, eeprom, flash memory, static memory, dram, sdram, and their equivalents), configured to control the processor to perform and/or control the processes and systems of this disclosure. the processor can be a separate device or a single processing mechanism. further, this disclosure can benefit from parallel processing capabilities of a multi-cored cpu. fig. 2 is a flow chart illustrating an exemplary process for operating electricity meter according the embodiments of figs. 1a and 1b and for determining a first temperature in a first location, storing the first temperature separately for each iteration of the process, comparing the first temperature to high temperature alarm and meter disconnection thresholds, and updating those thresholds. in the alternative, a second temperature in a second location may be stored separately for each iteration and be compared to high temperature alarm and meter disconnection thresholds that are different from the thresholds which are compared to the first temperature of the first location. as illustrated in fig. 2 , during a temperature detection step 201 for a poly-phase meter according to figs. 1a and 1b , the temperature of at least two phases of the electrical connection 101 are measured by the sensor 137 on the first ic 123. once detected, a temperature (t φ1 ) of a first phase, and a temperature (t φ2 ) of a second phase are compared at step 203. a first temperature t 1 is set to the first phase temperature (t φ1 )at step 205 if the first phase temperature (t φ1 ) is higher than the second phase temperature (t φ2 ). the first temperature (t 1 ) is set to second phase temperature (t φ2 ) at step 207 if the second phase temperature (t φ2 ) is determined to be higher than the first phase temperature (t φ1 ). in the alternative the first temperature can be an average of the first phase temperature (t φ1 ) and the second phase temperature (t φ2 ). the first temperature (t 1 ) is stored as (t 1(s) ) in a memory unit of the controller 115 at step 209 for each incremented iteration (s) of the process of figure 2 . the process 200 illustrated in fig. 2 , is applied to a meter including multiple phases. the exemplary process 200 for operating an electricity meter may be applied to a single or poly-phase meter. in a meter with a single phase, the first temperature (t 1 ) is the temperature around the single phase of the electrical connection 101. in a poly-phase meter, the temperature at each phase may be detected. further, the first temperature (t 1 ) can be set to the highest temperature detected of the individual phases, or an average of the individual temperatures for all the phases. in a two phase meter, the first phase or the second phase may be connected to phase a, b, or c of a three-phase connection. in the exemplary process illustrated in fig. 2 for operating an electricity meter, the first temperature (t 1 ) is referred to a process for sending an alarm for a high temperature condition. fig. 3 is a flow chart illustrating a high temperature operation 300 for sending an alarm for a high temperature condition according to the present disclosure. the controller 115 of fig. 1a or the second ic 125 in fig. 1b , will determine if a high temperature alarm should be transmitted to the communications board 129 by comparing the first temperature (t 1 ) to a first threshold (t t- max ) for sending an alarm of a high temperature condition at step 301. when the first temperature (t 1 ) is greater than or equal to the first threshold (t t- max ), at least one temperature alarm message is transmitted to the communications board 129 at step 303. the at least one alarm message (or a number of messages, e.g. 6 messages) is sent to the communications board 129, which transmits the message to the back end 133 at step 303. when the first temperature (t 1 ) is not greater than or equal to the first threshold (t t-max ), no alarm message is sent. in the exemplary process illustrated in fig. 2 for operating an electricity meter, the first temperature (t 1 ) is referred to a process for disconnecting a meter (100, 100') after the high temperature operation 300. fig. 4 is a flow chart illustrating an exemplary process for the disconnection operation for disconnecting an electricity meter based on the first temperature (t 1 ). in the disconnection operation, disconnection switch 131 of the electricity meter 100 illustrated in fig. 1 , is operated to disconnect the electrical connection 101 based on the first temperature (t 1 ). as noted above the first temperature (t 1 ) corresponds to the highest temperature between at least two phases of the electrical connection 101 (as noted above, in the alternative (t 1 ) could be the average of the temperatures of all of the phases). in the disconnection operation, it is determined whether a temperature based operation of the disconnect switch has been disabled at step 401. when a second threshold (t s- max ) is equal to zero, it is determined the temperature based operation of the disconnect switch has been disabled and the disconnection operation 400 is ended. the second threshold (t s- max ) corresponds to a second high temperature condition of the electrical connection 101, which can damage the meter (100, 100') if the load 105 is not disconnected from the power source 107. when the second threshold (t s- max ) is not equal to zero, it is determined if the remote disconnect switch 131 must be opened to disconnect the electrical connection 101 by comparing the first temperature (t 1 ) to a second threshold (t s- max ) at step 403. the second threshold (t s- max ) corresponds to the second high temperature condition of the electrical connection 101, which can affect the normal operation of the meter (100, 100') if the load 105 is not disconnected from the power source 107. when the first temperature (t 1 ) is greater than or equal to the second threshold (t s- max ) for a period time ( t 1 ) greater than or equal to a predetermined number (x) of seconds (e.g. 5 seconds), the disconnect switch 131 is operated to be opened at step 403. a disconnect switch open acknowledgement message is transmitted at step 407. at least one disconnect switch open acknowledgement message (or more, e.g. 6 messages) is sent to the communications board 129, which transmits the message to the back end 133 at step 407. when the disconnect switch 131 is opened, a first counter (y) is reset to zero at step 409. as discussed below the first counter (y) is incremented to indicate a number of times the disconnect switch 131 has not opened correctly. a position of the disconnect switch 131 and a current sensor 141 are monitored, to determine if the electrical connection 101 has been properly disconnected at step 411. a measured current (i) is compared to a maximum allowable current (i max ) (e.g..5 a) that can be present when the electrical connection 101 is disconnected. when the position of the disconnect switch is closed or the measured current (i) is greater than the maximum allowable current (i max ), the first counter (y) is increased by 1 at step 413. it is determined whether the disconnect switch 131 failed to open a maximum number of times by comparing the first counter (y) to a maximum count (y max ) at step 415 (i.e. a maximum number of failed attempts to open the disconnect switch 131, such as one or six attempts). when the value of the counter (y) is less than the maximum count (ymax), a period of (u) seconds (e.g. 10 seconds) is allowed to elapse, and the disconnect switch 131 is operated at step 417, and step 411 is repeated. if the counter (y) has increased to (ymax), disconnect switch operation failure message is transmitted at step 419. when it is determined a position of the disconnect switch 131 is open or the measured current (i) is less than the maximum allowable current (i max ) at step 411, the first counter (y) is not increased and the disconnect switch operation failure message is not sent. in the exemplary process illustrated in fig. 2 for operating an electricity meter (100, 100'), the first temperature (t 1 ) is referred to a process for updating operational thresholds after the disconnection operation 400. fig. 5 is a flow chart illustrating an exemplary process for a threshold update 500 for updating operational thresholds. in the threshold update 500, the second temperature corresponding to the temperature of the second ic 125 is evaluated at process 600, evaluate location temperatures (t 2 ). fig. 6 is a flow chart illustrating an exemplary process to determine a first temperature difference according to the evaluate location temperatures (t 2 ). the second sensor 139 is used to determine the second temperature (t 2 ) at step 601. as a result, second temperature (t 2 ) corresponds to a temperature in a second location of the meters (100, 100') illustrated in fig 1a and 1b . a flag (z) is read at step 603. when it is determined that the flag (z) is equal 1, a third threshold (δt loc ) for the first temperature difference between the first location where the first ic 123 is located, and the second location where the second ic 125 is located, is determined in step 611 from t 1 - t 2 . the value of flag (z) not being equal to 1, indicates the first threshold (t t- max ) and the second threshold (t s- max ) are not modified from respective original values. when it is determined the flag (z) is equal to 1, the first temperature t 1 is compared to the second t 2 at step 607. the value of flag (z) being equal to 1, indicates the first threshold t t- max and the second threshold t s- max have are modified from respective original values (as with a previous iteration of the threshold update 500). when it is determined that t 1 has decreased from a previous level that required a change in thresholds, to less than the second temperature t 2 , the first threshold (t t- max ) and the second threshold (t s- max ) are reset to respective original values in step 609. the first temperature difference (δt loc ) between the first location where the first ic 123 is located, and the second location where the second ic 125 is located, is determined as t 1 - t 2 in step 611 after step 609. in the exemplary process illustrated in fig. 5 for updating operational thresholds with the threshold update 500 process, the first temperature difference (δt loc ) determined in the evaluate location temperatures 600 process is compared to a maximum temperature difference (δt max ) at step 503. if the first temperature difference (δt loc ) is not greater than or equal to the maximum temperature difference (δt max ), the flag (z) is set to equal zero in step 505b and the threshold update 500 process ends. however, if the first temperature difference (δt loc ) is greater than or equal to the maximum temperature difference (δt max ), the flag (z) is set equal to 1 in step 505a. this indicates there is a large difference in temperature between different locations within the meter, and the temperature of the electrical connection 101 may be increasing too rapidly. when the flag is set equal to 1, the first temperature (t 1 ) is referred to an evaluate thresholds 700 process. fig. 7 is a flow chart illustrating an exemplary process for evaluating and updating temperature thresholds. in the evaluate thresholds 700 process, an average of the most recent (n) samples of (t 1 ) is determined as a short-term temperature average (t r ) in step 701. a long-term temperature average (t ave(s) ) is calculated in step 703. the long-term temperature average (t ave(s) ) corresponds to an average of all of the samples of t 1 over a time period ( t 2 ) (e.g. 7 minutes). preferably the number of samples in the long term temperature average is large. when a sufficient number of samples are used to determine the long-term temperature average (t ave(s) ), the most recent samples of (t 1 ) will have a small influence on the long-term temperature average (t ave(s) ). thus it is not necessary to perform the step of filtering the most recent samples of (t 1 ) from a calculation of the long-term temperature average (t ave(s) ). on the other hand when the number of samples used to determine the long-term temperature average (t ave(s) ) is not large, it is preferable to exclude the most recent samples of (t 1 ), which may influence/change the long-term temperature (t ave(s) ) a large amount. in this situation it is preferable to determine the long-term temperature average (t ave(s) ) using samples of (t 1 ) occurring over the period of time ( t 2 ), which is immediately before a first sample of the short-term temperature average (t r ). an average rate of change (t l ) is calculated in step 705 as the difference of the short-term temperature average (t r ) and the long term temperature average (t ave(s) ), divided by an average time change (δ t ave ). the average rate of change (t l ) is compared to a fourth threshold for a first maximum rate of change (t l-max1 ) in step 707. the comparison may also be determined by comparing the first maximum rate of change (t l-max1 ) multiplied by average time change (δ t ave ) to the difference of the short-term temperature average (t r ) and the long-term temperature average (t ave(s) ). when the average rate of change (t l ) is greater than or equal to the first maximum rate of change (t l-max1 ), the average rate of change (t l ) is compared to a second maximum rate of change (t l-max2 ) in step 709. when the average rate of change (t l ) is not greater than or equal to the second maximum rate of change (t l-max2 ), the first threshold (t t-max ) for sending the high temperature alarm message and the second threshold (t s-max ) for operating the disconnect switch 131 are reduced by respective first (q 1 ) and second (w 1 ) values in step 711. a threshold change message is sent to the communications board 129 by the controller 115 at step 715. when the average rate of change (t l ) is greater than or equal to the second maximum rate of change (t l-max2 ), the first threshold (t t-max ) and the second threshold (t s-max ) are reduced by respective third (q 1 ) and fourth (w 1 ) values in step 713. a threshold change message is sent to the communications board 129 at step 715. the third (q 2 ) and fourth (w 2 ) values are greater than the first (q 1 ) and second (w 1 ) values respectively. reducing the first threshold (t t-max ) for the sending the high temperature alarm message, and the second threshold (t s-max ) for operating the disconnect switch 131 is advantageous because a continual rise in temperature in the meter (100, 100') can be recognized before higher temperature thresholds that put continued proper operation at risk are reached. the threshold update process 500 ends after it is determined the average rate of change (t l ) is not greater than or equal to the first maximum rate of change (t l-max1 ), or the threshold hold change message is sent in step 715. as illustrated in fig. 2 , the counter (s) is incremented by 1 at step 211 once threshold update process 500 is complete. fig. 8 is a flow chart illustrating an exemplary process for calibrating threshold values for an electricity meter. an electrical meter is turned on at step 801 and a one time calibration of the second threshold (t s- max ), where the second threshold is set to a second temperature sensor 139 threshold for the second ic 125 at step 801. it is determined if the meter (100, 100') is in time alignment at step 803. if the meter (100, 100') is not in time alignment, a flag (f) is set to zero in step 805, and a period of time (o) is allowed to pass at step 807 (e.g. 24 hours - or comparable time period required for the meter to be in time alignment) before a temporary calibration occurs at step 811. if the meter (100, 100') is in time alignment, a flag (f) is set to 1 in step 809, and the temporary calibration occurs at step 811. the flag (f) is read at step 813, and if the flag (f) is equal to zero the time alignment of the meter (100, 100') is determined again at step 803. if the value of the flag (f) is not equal to 0, it is determined if the current time is equal to a time 1 (e.g. 2:00 am) at step 815. if the time is equal to time 1, at step 821 the first threshold (t s- max ) and the second threshold (t t- max ) are permanently calibrated. if the current time is not equal to a time 1 (e.g. 2:00 am), it is determined if the current time is later than a time 2 (e.g. 1:00 am) at step 817. when it is determined the current time is not later that time 2, it is determined if the meter (100, 100') is in time alignment at step 803 in a subsequent iteration of the calibration process 800 of fig. 8 . when the current time is later than time 2, the current (i) is compared to calibration current (i cal ) (e.g. 100 a) in step 819. when the current (i) is less than the calibration current (i cal ), the meter (100, 100') is permanently calibrated at step 821. otherwise it is determined if the meter (100, 100') is in time alignment at step 803 in a subsequent iteration of the calibration process 800 of fig. 8 . the calibration process 800 provides calibration during times where calibration will not be affected by sun loading and temperature gradients by normal bus bar heating of the electrical connection 101. the calibration process can also result in issuing a high temperature alarm message when the calibration results in offsets greater than plus or minus 30° c.
|
140-817-055-624-05X
|
DE
|
[
"AT",
"DE",
"JP",
"EP",
"US"
] |
C08K5/00,C08K5/5419,C08K9/04,C08L83/04,C09K3/10
| 1991-11-28T00:00:00 |
1991
|
[
"C08",
"C09"
] |
one-component rtv compositions.
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the invention relates to compositions which have a long shelf life in the absence of water, but crosslink at room temperature to give elastomers in the presence of water are prepared by mixing (1) an organopolysiloxane containing condensable end groups with (2) an organosilicon compound containing, per molecule, at least three hydrolysable groups bonded directly to silicon, (3) a condensation catalyst, and optionally at least one further substance, and contain, as (3) a condensation catalyst, a product of the reaction of a finely divided, inorganic oxide with a reactive titanium compound.
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composition which has a long shelf life in the absence of water, but crosslinks in the presence of water at room temperature to give elastomers and is prepared by mixing (1) an organopolysiloxane containing condensable terminal groups with (2) an organosilicon compound containing per molecule at least three hydrolysable groups bonded directly to silicon, (3) a condensation catalyst and, if desired, at least one further substance, characterized in that the condensation catalyst (3) is a product of the reaction of a finely divided, inorganic oxide having a particle size of less than 10 »m with a titanium compound capable of reacting with the oxide. composition according to claim 1, characterized in that the reaction product is prepared by mixing a finely divided, inorganic oxide with a reactive titanium compound in amounts of from 0.01 to 50 parts of titanium compound per 100 parts of finely divided inorganic oxide, if desired in the presence of an inert organic solvent, at from 0 to 300°c for a period of from 1 minute to 24 hours. composition according to claim 1 or 2, characterized in that the finely divided inorganic oxide used is silicon dioxide having a specific surface area of at least 50 m²/g (bet). composition according to any of claims 1 to 3, characterized in that the reaction product used has been rendered hydrophobic by reaction with an organosilicon compound. composition according to any of claims 1 to 4, characterized in that the titanium compound capable of reacting with the oxide used has the general formula tix₄ where x is a radical of the formula in which r is an alkyl radical having 1 to 12 carbon atoms per radical, or one radical x is a chelate ligand selected from the group consisting of acetylacetonates, β-diketo groups and β-ketoester groups, or two radicals x together are a dihydric alcohol as chelate ligand. composition according to any of claims 1 to 5, characterized in that the organopolysiloxane (1) containing condensable terminal groups has the general formula where the radicals r⁶ are identical or different, halogenated or unhalogenated monovalent hydrocarbon radicals and cyanoalkyl radicals, each having 1 to 18 carbon atoms per radical, and m is an integer having a value of at least 10. composition according to any of claims 1 to 6, characterized in that the organosilicon compound (2) is a silane of the general formula r⁶ 4-n siz n or a partial hydrolysate thereof containing 2 to 10 silicon atoms per molecule, where the r⁶ radicals are identical or different, halogenated or unhalogenated monovalent hydrocarbon radicals and cyanoalkyl radicals, each having 1 to 18 carbon atoms per radical, n is 3 or 4, and the z radicals are identical or different hydrolysable groups and are selected from the group consisting of acyloxy groups -ocor⁷ and hydrocarbonoxy groups -or⁸, in which r⁷ is a monovalent hydrocarbon radical having 1 to 12 carbon atoms per radical, and r⁸ is an alkyl radical which has 1 to 4 carbon atoms per radical and may be substituted by an ether oxygen atom.
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background of the invention compositions which have a long shelf life in the absence of water, but crosslink in the presence of water at room temperature to form elastomers and which eliminate acetic acid during crosslinking and contain organotin compounds as condensation catalyst are disclosed, for example, in u.s. pat. no. 3,077,465 (published feb. 12, 1963, l. b. bruner et al., dow corning corp.). since organotin compounds are toxic, elastomers prepared in this manner cannot be employed without restrictions, for example, in the foodstuffs sector. u.s. pat. no. 4,525,565 (published jun. 25, 1985, b. laisney et al., rhone-poulenc specialities chimiques) and the corresponding ep 102,268 disclose compositions which have a long shelf life in the absence of water, but crosslink in the presence of water at room temperature to give elastomers and which are prepared by mixing the following constituents: (a) a diorganopolysiloxane containing terminal hydroxyl groups, (b) a silane containing at least three acyloxy groups or oxime groups bonded directly to silicon per molecule, (c) an organotitanium compound containing at least one organosilicon radical which is bonded to each titanium atom by a ti-o-si bond, as condensation catalyst, and (d) a filler the organotitanium compounds, such as tetra(trimethylsiloxy)titanium or bis(trimethylsiloxy)dibutoxytitanium, are soluble in the one-component rtv compositions, i.e., the crosslinking of the compositions is homogeneously catalyzed. de 20 57 730 (published on jun. 16, 1977, s. laufer, deutsche gold- und silber-scheideanstalt, previously roessler) and the corresponding u.s. pat. no. 4,164,509 describe a process for rendering finely divided oxides, for example pyrogenic silicic acid, hydrophobic, in which the finely divided oxides are treated with ester compounds, and dry ammonia gas is passed through the product. suitable ester compounds mentioned are alkoxysilanes, such as tetra-n-butoxy silane, and the corresponding compounds of titanium. it is an object of the present invention to provide compositions which have a long shelf life in the absence of water, but crosslink in the presence of water at room temperature to form elastomers. another object of the present invention is to provide compositions having a long shelf life in the absence of water, but crosslink in the presence of water at room temperature to form elastomers, which contain a condensation catalyst which is significantly less toxic to non-toxic. another object of the present invention is to provide a condensation catalyst which accelerates the crosslinking of the compositions by heterogeneous catalysis. a further object of the present invention is to provide a condensation catalyst whose catalytic activity is not impaired even by storage in the presence of atmospheric moisture over an extended period. a still further object of the present invention is to provide a condensation catalyst which is easy to prepare. summary of the invention the above objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking by providing compositions which have a long shelf life in the absence of water, but crosslink in the presence of water at room temperature to form elastomers which comprises mixing (1) an organopolysiloxane containing condensable terminal groups with (2) an organosilicon compound containing per molecule at least three hydrolyzable groups bonded directly to silicon, (3) a condensation catalyst and optionally, at least one additional substance, wherein the condensation catalyst (3) is a product obtained from the reaction of a finely divided, inorganic oxide with a reactive titanium compound. detailed description of the invention the condensation catalyst (3) is preferably prepared by reacting a finely divided, inorganic oxide with a reactive titanium compound in amounts of from 0.01 to 50 parts, preferably from 0.1 to 10 parts, of titanium compound per 100 parts of finely divided inorganic oxide, optionally in the presence of an inert organic solvent, at from 0.degree. to 300.degree. c., and more preferably from 20.degree. to 100.degree. c., for a period of from 1 minute to 24 hours, and more preferably for from 15 to 60 minutes. the reaction product is preferably prepared under the pressure of the ambient atmosphere, i.e., at about 1020 hpa (abs.); however, it is also possible to use higher or lower pressures. the reactive titanium compound can be employed as a solution in an inert organic solvent. the inorganic oxide can also be employed as a dispersion in an inert organic solvent. if an inert, organic solvent is used during the preparation of the reaction product, it can be removed from the reaction product, preferably by distillation, at from 0.degree. to 150.degree. c. and from 0.01 to 1,000 hpa (abs.). the resultant reaction product of this invention is a pulverulent, insoluble, finely divided solid. free titanium compounds cannot be extracted from this reaction product using nonpolar or polar solvents, such as, for example, toluene or acetone. compositions which contain, as catalyst, a reaction product containing free and unbound titanium compounds as a consequence of using an excess amount of titanium compound, tend to gel and do not form useable elastomers. while organic titanium compounds, such as tetra-n-butoxytitanium, hydrolyze in a short period with atmospheric moisture to give catalytically inactive titanium dioxide, the reaction product of this invention retains its catalytic activity, even after extended storage, without particular protection against atmospheric moisture. the compositions of this invention also have a long shelf life in the absence of moisture. the finely divided inorganic oxide preferably employed for the preparation of the reaction product of this invention has a particle size of less than 10 .mu.m, preferably less than 0.1 .mu.m. examples of finely divided inorganic oxides are silicon dioxide, aluminum oxide, titanium dioxide, quartz sand, mica, iron oxide, zinc oxide, magnesium oxide, zirconium dioxide, and silicates, such as calcium silcate or aluminum silicate. preferred examples of finely divided inorganic oxides are silicon dioxides having a specific surface area of at least 50 m.sup.2 /g (determined by nitrogen adsorption in accordance with astm special technical publication 51, 1941, page 95 ff, i.e., by the so-called "bet method"), preferably from 50 to 500 m.sup.2 /g, especially from 100 to 300 m.sup.2 /g, and in particular pyrogenically produced silicon dioxides, silicic acid hydrogels which have been dewatered with retention of the structure, i.e., so-called "aerogels", and other types of precipitated silicon dioxide. the reactive titanium compound preferably employed in the preparation of the reaction product has the general formula tix.sub.4 where x is a radical of the formula --or or ##str1## in which r is an alkyl radical having from 1 to 12 carbon atoms per radical, or one radical x is a chelate ligand selected from the group consisting of substituted or unsubstituted acetylacetonates, .beta.-diketo groups and .beta.-ketoester groups, or two radicals x together are a dihydric alcohol as chelate ligand. the substituted or unsubstituted acetylacetonates used are preferably those of the formula ##str2## where r.sup.1 is a hydrogen atom or a monovalent hydrocarbon radical having from 1 to 12 carbon atoms per radical, the dihydric alcohol used is preferably one of the formula ##str3## where the r.sup.2 radicals are the same or different and are hydrogen atoms or monovalent hydrocarbon radicals having from 1 to 12 carbon atoms per radical, and a is 0, 1 or 2. examples of alkyl radicals represented by r are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; undecyl radicals, such as the n-undecyl radical, and dodecyl radicals, such as the n-dodecyl radical. a preferred example of r is the n-butyl radical. examples of hydrocarbon radicals represented by r.sup.1 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-tri-methylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; undecyl radicals, such as the n-undecyl radical; dodecyl radicals, such as the n-dodecyl radical; alkenyl radicals, such as the allyl radical; aryl radicals, such as the phenyl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals; and aralkyl radicals, such as the benzyl radical. the preferred example of r.sup.1 is the hydrogen atom. examples of hydrocarbon radicals represented by r.sup.2 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; undecyl radicals, such as the n-undecyl radical; dodecyl radicals, such as the n-dodecyl radical; alkenyl radicals, such as the allyl radical; aryl radicals, such as the phenyl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals; and aralkyl radicals, such as the benzyl radical. the preferred example of r.sup.2 are the hydrogen atom or the methyl radical. in the reaction product of this invention, the filler and the condensation catalyst are combined as a single component. the novel product obtained from the reaction of a finely divided inorganic oxide with a reactive titanium compound or the finely divided inorganic oxide employed in the preparation of the reaction product may be rendered hydrophobic by means of a hydrophobicizer, preferably an organosilicon compound. the organosilicon compound employed is preferably one of the formula r.sup.3.sub.4-x sia.sub.x or (r.sup.3.sub.3 si).sub.y b, in which the r.sup.3 radicals are the same or different and are monovalent hydrocarbon radicals having from 1 to 18 carbon atoms per radical, a is halogen, --oh, --or.sup.4 or --ocor.sup.4, b is nr.sup.5.sub.3-y, r.sup.4 is a monovalent hydrocarbon radical having from 1 to 12 carbon atoms per radical, r.sup.5 is a hydrogen atom or the same as r.sup.4, x is 1, 2 or 3 and y is 1 or 2, or an organo(poly)siloxane comprising units of the formula r.sup.3.sub.z sio.sub.(4-z)/2 where r.sup.3 is the same as above, and z is 1, 2 or 3. examples of radicals represented by r.sup.3 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and allyl radicals; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals, and methyl cyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals, such as o-, m- and p-tolyl radicals; xylyl radicals and ethyl phenyl radicals; and aralkyl radicals, such as the benzyl radical and the alpha- and .beta.-phenylethyl radicals. examples of radicals represented by r.sup.4 are alkyl radicals, such as the methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; and dodecyl radicals, such as the n-dodecyl radical; aryl radicals, such as the phenyl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals; and aralkyl radicals, such as the benzyl radical. preferred examples of r.sup.4 are the methyl and ethyl radicals. examples of organosilicon compounds are alkylchlorosilanes, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, octylmethyldichlorosilane, octadecylmethyldichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane and tert-butyldimethylchlorosilane; alkylalkoxysilanes, such as dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane; trimethylsilanol; cyclic diorgano(poly)siloxanes, such as cyclic dimethyl(poly)siloxanes, and linear diorganopolysiloxanes, such as dimethylpolysiloxanes which are end-blocked by trimethylsiloxy groups, and dimethylpolysiloxanes containing terminal hydroxyl or alkoxy groups. the inorganic oxides which have been rendered hydrophobic preferably contain from 1 to 10% by weight of organosilicon compounds. processes for rendering materials hydrophobic are described, for example, in de 11 63 784. the inert, organic solvent used is preferably a saturated hydrocarbon, such as pentane, hexane, heptane, decane or a mixture thereof, such as a mineral oil, or an aromatic hydrocarbon, such as toluene, xylene, ethyl benzene or a mixture thereof, or an aliphatic alcohol, such as methanol, ethanol, propanol, butanol, pentanol, hexanol or octanol, or a mixture thereof. the condensation catalyst (3) is preferably employed in an amount of from 0.01 to 100 parts, in particular from 0.1 to 50 parts, based on 100 parts of organopolysiloxane (1). the organopolysiloxane (1) containing condensable terminal groups is preferably one of the general formula ho(sir.sup.6.sub.2 o )m.sub.sir.sup.6.sub.2 oh, where the radicals r.sup.6 are the same or different and are substituted or unsubstituted monovalent hydrocarbon radicals having from 1 to 18 carbon atoms per radical, and m is an integer having a value of at least 10. within or along the siloxane chains of the above mentioned formula, other siloxane units may be present in addition to the diorganosiloxane units (sir.sup.6.sub.2 o), which are usually not shown in formulas of this type. examples of other siloxane units of this type, which are usually present as impurities, are those of the formulas r.sup.6 sio.sub.3/2, r.sup.6.sub.3 sio.sub.1/2 and sio.sub.4/2, where r.sup.6 is the same as above. however, the amount of siloxane units of this type other than diorganosiloxane units is preferably at most 10 mol percent, and more preferably at most 1 mol percent, based on the weight of the organopolysiloxanes (1). the organopolysiloxanes (1) preferably have a viscosity of from 100 to 500,000 mpa.s at 25.degree. c. it is possible to employ one type of organopolysiloxane (1) or a mixture of at least two types of organopolysiloxane (1). examples of radical r.sup.6 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and allyl radicals; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals, and methyl cyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethyl phenyl radicals and aralkyl radicals, such as the benzyl radical and the alpha- and .beta.-phenylethyl radicals. examples of substituted radicals represented by r.sup.6 are cyanalkyl radicals, such as the .beta.-cyanethyl radical, and halogenated hydrocarbon radicals, for example haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl radicals. a preferred example of the radical r.sup.6 is the methyl radical. the organosilicon compound (2) containing at least three hydrolyzable groups per molecule which are bonded directly to silicon is preferably a silane of the general formula r.sup.6.sub.4-n siz.sub.n or a partial hydrolyzate thereof containing 2 to 10 silicon atoms per molecule, where r.sup.6 is the same as above, n is 3 or 4,and the radicals z are the same or different hydrolyzable groups and are selected from the group consisting of acyloxy groups --ocor.sup.7 and substituted or unsubstituted hydrocarbonoxy groups --or.sup.8, in which r.sup.7 is a monovalent hydrocarbon radical having from 1 to 12 carbon atoms per radical, and r.sup.8 is an alkyl radical which has from 1 to 4 carbon atoms per radical and may b substituted by an ether oxygen atom. the hydrolyzable group z is preferably the acyloxy group. the organosilicon compound (2) is preferably employed in an amount of from 2 to 10 parts per 100 parts of organopolysiloxane (1). examples of radicals represented by r.sup.7 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radicals; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals, and methyl cyclohexyl radicals; aryl radicals, such as the phenyl and naphthyl radicals; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethyl phenyl radicals, and aralkyl radicals, such as the benzyl radical and the alpha and .beta.-phenylethyl radicals. a preferred example of the radical r.sup.7 is the methyl radical. examples of alkyl radicals represented by r.sup.8 are methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl and tert-butyl radicals. examples of alkyl radicals represented by r.sup.8 which are substituted by an ether oxygen atom are the ethoxy methyl, 2-methoxyethyl, 2-ethoxyethyl and propoxymethyl radicals. preferred examples of r.sup.8 radicals are the methyl and ethyl radicals. it is possible to employ one type of silane or a mixture of at least two types of silanes, or partial hydrolyzates thereof. in addition to components (1), (2) and (3), the compositions of this invention may, if desired, contain additional substances. examples of additional substances are fillers, such as reinforcing and nonreinforcing fillers, plasticizers, pigments, soluble dyes, fragrances, fungicides, resinous organopolysiloxanes, purely organic resins, corrosion inhibitors, oxidation inhibitors, heat stabilizers, solvents, agents for affecting the electrical properties, such as conductive black, flameproofing agents, light stabilizers and agents for extending the skinning time. examples of fillers are reinforcing fillers, i.e., fillers having a specific bet surface area of at least 50 m.sup.2 /g, preferably 50-500 m.sup.2 /g, such as pyrogenically produced silicon dioxides, silicic acid hydrogels which have been dewatered with retention of the structure, i.e., so-called "aerogels", and other types of precipitated silicon dioxide; and nonreinforcing fillers, i.e., fillers having a specific bet surface area of less than 50 m.sup.2 /g, such as quartz sand, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, iron oxide, zinc oxide, titanium dioxide, aluminum oxide, calcium carbonate, magnesium carbonate, zinc carbonate, carbon black, mica and chalk. the fillers may have been rendered hydrophobic by treatment with hydrophobicizers, for example by treatment with organosilanes, organosilazanes or organosiloxanes. it is possible to employ only one type of filler, or it is possible to employ a mixture of at least two fillers. the filler is preferably employed in amounts of from 0 to 200 parts, and more preferably from 0 to 50 parts, based on 100 parts of organopolysiloxane (1). examples of plasticizers are diorganopolysiloxanes which are endblocked by triorganosiloxy groups and are liquid at room temperature, such as dimethylpolysiloxanes which are end-blocked by trimethylsiloxy groups and having viscosity of from 10 to 10,000 mpas at 25.degree. c. the plasticizer is preferably employed in amounts of from 0 to 50 parts, and more preferably from 0 to 10 parts, based on 100 parts of organopolysiloxane (1). in preparing the compositions of this invention, all constituents of the particular composition can be mixed with one another in any desired sequence. this mixing is preferably carried out at room temperature, and contact with water is preferably avoided during this mixing. if desired, however, this mixing can also be carried out at elevated temperatures, for example at a temperature in the range of from 25.degree. to 80.degree. c. the usual water content of air is sufficient for crosslinking the compositions of this invention. if desired, the crosslinking can also be carried out at temperatures higher than room temperature, for example at from 25.degree. to 120.degree. c., or at temperatures lower than room temperature, for example at from -10.degree. to 25.degree. c. it is also possible to carry out the crosslinking at water concentrations which exceed the normal water content of air. the compositions of this invention are suitable as sealants for joints, including vertical joints and similar gaps with separations of, for example, from 10 to 40 mm, for example of buildings, land, water and air vehicles, or as adhesives and putties, for example in glazing, or for the production of protective coatings, including those for surfaces exposed to the constant action of fresh water or sea water, or for the production of coatings which repel adhesive substances, including those for substrates which come into contact with foodstuffs, for example packaging material intended for the storage and/or transport of sticky foodstuffs, such as cakes, honey, confectionery and meat, or for other applications in which it was possible to employ the heretofore known compositions which crosslink at room temperature to give elastomers, such as for the insulation of electrical or electronic devices. preparation of the condensation catalysts a. one g of monomeric tetra-n-butoxytitanium dissolved in 1 g of n-hexane, and 10 g of hexamethyldisilazane are admixed at 25.degree. c. with stirring with 100 g of a pyrogenic silicic acid having a specific bet surface area of 150 m.sup.2 /g. the mixture is homogenized at 25.degree. c. for 30 minutes, and the solvent is removed by distillation at 30.degree. c. at 1 hpa (abs.), giving a white powder. b. the procedure of a is repeated, except that 1 g of tetraisopropoxytitanium is substituted for 1 g of tetra-n-butoxytitanium. a white powder is obtained. c. the procedure of a is repeated, except that 1 g of diisopropoxytitanium bis(acetylacetonate) dissolved in 2 g of isopropanol is substituted for 1 g of tetra-n-butoxytitanium. the mixture is homogenized at 25.degree. c. for one hour, and then additionally conditioned for 2 hours at 80.degree. c. in a drying cabinet. a white powder is obtained. d. five g of monomeric tetra-n-butoxytitanium dissolved in 5 g of mineral oil (commercially available under the trade name "kristallol k 30" from shell) are admixed at 25.degree. c. with stirring with 100 g of a pyrogenic silicic acid having a specific bet surface area of 150 m.sup.2 /g. the mixture is homogenized at 25.degree. c. for 30 minutes, giving a white powder. e. the procedure of d is repeated, except that 25 g of tetra-n-butoxytitanium dissolved in 25 g of mineral oil are substituted for 5 g of tetra-n-butoxytitanium dissolved in 5 g of mineral oil. a white powder is obtained. f. the procedure of d is repeated, except that pyrogenic silicic acid having a specific bet surface area of 150 m.sup.2 /g which has been rendered hydrophobic (commercially available under the trade name "hdk h20" from wacker-chemie gmbh), by treating with dimethyldichlorosilane, and contains dimethylsiloxy groups which are chemically bonded to the surface, is used and the mineral oil is omitted. a white powder is obtained g. the procedure of d is repeated, except that 5 g of a dimethylpolysiloxane which is end-blocked by trimethylsiloxy groups and which has a viscosity of 10 mpas at 25.degree. c. are admixed at 25.degree. c. with the pyrogenic silicic acid, and the mineral oil is omitted. a white powder is obtained. h. ten g of monomeric tetra-n-butoxytitanium are added dropwise at 25.degree. c. to a suspension containing 100 g of a precipitated silicic acid having a specific bet surface area of 170 m.sup.2 /g (commercially available under the trade name "ultrasil vn3" from degussa) in 1000 g of n-hexane. the mixture is homogenized for one hour at 25.degree. c., and the n-hexane is removed by distillation at 30.degree. c. at 100 hpa (abs.), giving a white powder. i. the procedure of h is repeated, except that 100 g of finely divided quartz sand (commercially available under the trade name "silbond 600 tst" from quarzwerke frechen) are substituted for 100 g of precipitated silicic acid, and 1 g of tetra-n-butoxytitanium is used instead of 10 g. a white powder is obtained. j. the procedure of h is repeated, except that 100 g of the colored pigment iron oxide red (commercially available under the trade name "eisenoxid rot" from bayer) are substituted for 100 g of precipitated silicic acid, and 1 g of tetra-n-butoxytitanium is used instead of 10 g. a red powder is obtained. the analytical data for powders a to j (after the powders have been dried at 30.degree. c. and 1 hpa for a period of 2 hours) are summarized in table 1. table 1 ______________________________________ carbon content titanium content water catalyst (% by weight) (% by weight) wettability ______________________________________ a 2.3 0.2 no b 2.2 0.3 no c 2.5 0.2 no d 1.3 0.8 yes e 5.1 3.9 yes f 1.6 0.9 no g 2.5 0.7 no h 3.4 1.4 yes i 0.2 0.2 yes j 0.2 0.2 yes ______________________________________ powders a to j are each extracted with toluene and with acetone and the soluble titanium content is determined. the results are summarized in table 2. table 2 ______________________________________ extraction with acetone extraction with toluene titanium in mg/g of catalyst titanium in mg/g of sio.sub.2 sio.sub.2 ______________________________________ a <0.01 <0.01 b <0.01 <0.01 c <0.01 <0.01 d <0.01 <0.01 e 0.15 0.16 f <0.01 <0.01 g <0.01 <0.01 h <0.01 <0.01 i <0.01 <0.01 j <0.01 <0.01 ______________________________________ examples 1 to 3 five g of ethyltriacetoxysilane and in each case 20 g of catalyst a, b or c are added at 25.degree. c. with the exclusion of moisture to a mixture containing 40 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 80,000 mpa.s at 25.degree. c., 20 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 20,000 mpa.s at 25.degree. c. and 50 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 1000 mpa.s at 25.degree. c. in a laboratory mixer. the resultant compositions are applied as layers 2 mm in thickness on a smooth substrate and left to crosslink at 25.degree. c. and 50% relative atmospheric humidity for a total of 14 days. the skinning time is determined, i.e., the time which passes until a skin has formed on the samples. the shore a hardness in accordance with din 53505, the tear strength and the elongation at break in accordance with din 53504 using an s 3a standard bar are then determined for these elastomers. the results are summarized in table 3. examples 4 to 10 five g of ethyltriacetoxysilane and in each case 2 g of catalyst d to j are added at 25.degree. c. with the exclusion of moisture to a mixture containing 40 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 80,000 mpa.s at 25.degree. c. , 20 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 20,000 mpa.s at 25.degree. c., 50 g of an .alpha.,w-dihydroxydimethylpolysiloxane having a viscosity of 1000 mpa.s at 25.degree. c. and 20 g of pyrogenic silicic acid having a specific bet surface area of 150 m.sup.2 /g which has been rendered hydrophobic by treatment with hexamethyldisilazane, in a laboratory mixer. the resultant compositions are applied as layers 2 mm in thickness on a smooth substrate and left to crosslink at 25.degree. c. and 50% relative atmospheric humidity for a total of 14 days. the skinning time is determined, i.e., the time which passes until a skin has formed on the samples. the shore a hardness in accordance with din 53505, the tear strength and the elongation at break in accordance with din using an s 3a standard bar are then determined for these elastomers. the results are summarized in table 3. table 3 ______________________________________ skinning elongation time shore a tear strength at break example (min) hardness (n/mm.sup.2) (%) ______________________________________ 1 10 35 2.6 330 2 11 30 2.2 350 3 12 31 2.3 320 4 14 31 2.1 380 5* -- -- -- -- 6 11 34 2.6 330 7 10 31 2.2 320 8 9 36 2.3 290 9 14 24 2.2 390 10 15 22 2.1 400 ______________________________________ *the mixture gels even before contact with moisture example 11 a mixture containing catalyst a is prepared in accordance with the procedure described in example 1. the composition is stored in the absence of moisture for 1 month at 50.degree. c. and for 1 year at 25.degree. c. the crosslinking of the composition, the determination of the skinning time and the determination of the mechanical values of the elastomer are then carried out as described under example 1. the results are summarized in table 4. table 4 ______________________________________ storage of the skinning elongation compo- time shore a tear strength at break sition (min) hardness (n/mm.sup.2) (%) ______________________________________ 1 month 10 29 2.3 320 at 50.degree. c. 1 year 9 28 2.3 340 at 25.degree. c. ______________________________________ example 12 catalyst a is stored for 1 year at 25.degree. c. in a sealed drum, but without particular protection against moisture. a mixture is subsequently prepared in accordance with the procedure in example 1. the crosslinking of the composition, the determination of the skinning time and the determination of the mechanical values of the elastomer are then carried out as described under example 1. the results are summarized in table 5. table 5 ______________________________________ storage of skinning elongation catalyst time shore a tear strength at break a (min) hardness (n/mm.sup.2) (%) ______________________________________ 1 year 9 30 2.3 350 at 25.degree. c. ______________________________________
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